NCS000613_Application_20230428

United States Office of Water EPA Form 3510-1
Environmental Protection Agency Washington, D.C. Revised March 2019
Water Permits Division
:.EPA Application Form 1
General Information
NPDES Permitting Program
RECEIVED
APR 2 8 2023
DEMtR-Stormwater Program
Note: All applicants to the National Pollutant Discharge Elimination System (NPDES) permits
program, with the exception of publicly owned treatment works and other treatment works treating
domestic sewage, must complete Form 1. Additionally, all applicants must complete one or more of the
following forms: 213, 2C, 2D, 2E, or 2F. To determine the specific forms you must complete, consult the
"General Instructions" for this form.

Paperwork Reduction Act Notice
The U.S. Environmental Protection Agency estimates the average burden to collect information
and complete Form I to be 2.9 hours for new applicants and 0.9 hours for applicants renewing
existing permits. This estimate includes time to review instructions, search existing data sources,
gather and maintain the needed data, and complete and review the collection of information.
New respondents must also prepare a topographic map. Send comments about the burden
estimate or any other aspect of this collection of information to the Chief, Information Policy
Branch (PM-223), U.S. Environmental Protection Agency, 1200 Pennsylvania Avenue,NW,
Washington, DC 20460,and to the Office of Information and Regulatory Affairs, Office of
Management and Budget, 725 171h Street,NW, Washington, DC 20503, marked"Attention:
Desk Officer for EPA."

DESCRIPTION OF NPDES PERMIT APPLICATION FORMS CONTENTS OF FORM 1 PACKAGE
The application forms for individual National Pollutant Discharge Form 1—General Instructions
Elimination System(NPDES)permits include the following: Form 1—Line-by-Line Instructions
Form 1—General Information(included in this package). Form 1—Activities That Do Not Require Permits
Form 2—Forms Based on Facility or Activity Type (not included Form 1—Glossary
in this package): Form 1—Application
2A. New and Existing Publicly Owned Treatment Works
2B. Concentrated Animal Feeding Operations and
Concentrated Aquatic Animal Production Facilities
2C. Existing Manufacturing, Commercial,Mining, and
Silvicultural Operations
2D, New Manufacturing,Commercial, Mining, and Silvicultural
Operations That Have Not Yet Commenced Discharge of
Process Wastewater
2E, Manufacturing,Commercial,Mining,and Silvicultural
Facilities Which Discharge Only Nonprocess Wastewater
2F. Stormwater Discharges Associated with Industrial Activity
2S. New and Existing Treatment Works Treating Domestic
Sewage
FORM 1—GENERAL INSTRUCTIONS
Who Must Apply for an NPDES Permit? Upon your request,and based on information supplied by you,
With the exceptions described in"Form 1—Activities That Do Not EPA or the authorized NPDES state will determine whether you
Require Permits,"the federal Clean Water Act(33 U.S.C. 1251 et are required to obtain a permit for a particular facility or activity.
seq.)prohibits any person from discharging pollutants into waters Be sure to contact EPA or your state if you have a question.
of the United States without first having been issued a permit Form 1 collects general information only.You must also complete
under the NPDES program. a more detailed application based on your proposed discharge
Who Must Complete Form 1? activity,as follows:
All applicants,other than publicly owned treatment works • If your facility is a concentrated animal feeding operation
(POTWs)and treatment works treating domestic sewage or a concentrated aquatic animal production facility,you
(TWTDS),must submit Form 1. If you operate one of the must also complete Form 2B.
following facilities,you must submit Form 1:concentrated animal 0 If your facility is an existing manufacturing,commercial,
feeding operations and aquatic animal production facilities; mining,or silvicultural facility that currently discharges
manufacturing,commercial,mining,and silvicultural operations; process wastewater,you must also complete Form 2C.
or other industrial facilities. if your facility is a new manufacturing,commercial, mining,
At the state level,either the U.S. Environmental Protection or silvicultural facility that has yet to commence discharge of
Agency(EPA)or an approved state agency administers the process wastewater,you must also complete Form 2D.
NPDES permit program. If you are located in a jurisdiction in 0 If your facility is a new or existing facility(including
which an EPA regional office administers the NPDES permit manufacturing,commercial,mining,and silvicultural
program,you should use Form 1 and all other applicable forms facilities)that discharges only nonprocess wastewater,
described in these instructions.If you are located in a jurisdiction you must also complete Form 2E.
where a state administers the NPDES permit program,contact . If your facility is a new or existing facility whose discharge
the state to determine the forms you should complete.States is composed entirely of stormwater associated with industrial
often develop their own application forms rather than use the activity—excluding discharges from construction activity
federal forms.See http:llwww.epa.gov/npdes/npdes-state- under 122.26(b)(14)(x)or(b)(15)—you must also complete
program-information for a list of states that have approved Form 2F. If the discharge is composed of stormwater and
NPDES permit programs and those that do not. non-stormwater,you must complete Form 2F and you most
Exhibit 1-1 (see end of this section)provides contact information also complete Forms 2C,2D,and/or 2E,as appropriate. See
for each of EPA's 10 regional offices.Since the exhibit's content is Form 2F's instructions for further details.
subject to change,consult EPA's website for the latest information:
http:llwww.epa.govlaboutepa#regional.
1-1

FORM 1—GENERAL INSTRUCTIONS CONTINUED
Where to File Your Completed Form Completion of Forms
• If you are in a jurisdiction with an approved state NPDES Print or type in the specified areas only.If you do not have enough
permit program,file according to the instructions on the state space on the form to answer a question,you may continue on
forms. additional sheets,as necessary,using a format consistent with the
• If you are in a jurisdiction where EPA is the NPDES form.
permitting authority(i.e.,the state is not an NPDES- The NPDES permitting authority could consider your application
authorized state),mail the completed application forms to the incomplete if you do not provide an answer(or indicate"NA"for
EPA regional office that covers the state in which your facility "not applicable")for all questions on Form 1 and the applicable
is located(see Exhibit 1-1). Form 2.
When to File Your Completed Form Provide your EPA Identification Number from the Facility Registry
Because of statutory and regulatory requirements,the deadlines Service,NPDES permit number,and facility name at the top of
for filing applications vary according to your facility or activity type each page of Form 1 and any attachments.If your facility is new
and the type of permit you need.The various permit application (i.e.,not yet constructed),write or type"New Facility"in the space
deadlines are listed in Exhibit 1-2 at the end of this section. provided for the EPA Identification Number and NPDES number.
If you do not know your EPA Identification Number,contact your
Fees NPDES permitting authority.See Exhibit 1-1 for contact
EPA does not require applicants to pay a fee for applying for information.
NPDES permits.However,states that administer the NPDES Do not leave any response areas blank unless the form directs
permit program may charge fees.Consult with state officials for you to skip them. If the form directs you to respond to an item that
further information. does not apply to your facility or activity,enter"NA"for"not
Public Availability of Submitted Information applicable"to show that you considered the item and determined
a response was not necessary for your facility.
EPA will make information from NPDES permit application forms
available to the public for inspection and copying upon request. The NPDES permitting authority will consider your application
claim any information on Form 1 (or related complete when it and any supplementary material are received
You may not c
attachments) la confidential. and completed according to the authority's satisfaction.The
NPDES permitting authority will judge the completeness of any
You may make a claim of confidentiality for any information that application independently of the status of any other permit
you submit to EPA that goes beyond the information required by application or permit for the same facility or activity,
Form 1.If you do not assert a claim of confidentiality at the time
you submit your information to the NPDES permitting authority,
EPA may make the information available to the public without
further notice to you.EPA will handle claims of confidentiality in
accordance with the Agency's business confidentiality regulations
at Part 2 of Title 4 of the Code of Federal Regulations(CFR).
1-2

FORM 1--GENERAL INSTRUCTIONS CONTINUED
Exhibit 1-1.Addresses of EPA Regional Contacts and Covered States
REGION 1 REGION 6
U.S.Environmental Protection Agency,Region 1 U.S.Environmental Protection Agency,Region 6
5 Post Office Square,Suite 100,Boston,MA 02109.3912 1445 Ross Avenue,Suite 1200,Dallas,TX 75202-2733
Phone:[phone];toll free:[phone] Phone:[phone];toll free:[phone]
Fax:[phone] Fax:[phone]
Website:h :l/wwwe a. ovlaboule a! a-r ion-1-new-en land Website:http:llwww.eoa.gov/aboulepalei)a-region-0-south-central
Covered states:Connecticut,Maine,Massachusetts,New Hampshire,Rhode Covered states:Arkansas,Louisiana,New Mexico,Oklahoma,and Texas
Island,and Vermont
REGION 2 REGION 7
U.S.Environmental Protection Agency,Region 2 U.S.Environmental Protection Agency,Region 7
290 Broadway,New York,NY 10007-1866 11201 Renner Boulevard,Lenexa,KS 66219
Phone:[phone]:toll free [phone] Phone:[phone];toll free:[phone]
Fax:[phone] Website:http:llwww.epa.govlaboutepalepa-region-7-midwest
Website:MD./www epa.gov/aboutepalepa-region-2 Covered states:Iowa,Kansas,Missouri,and Nebraska
Covered states:New Jersey,New York,Virgin Islands,and Puerto Rico
REGION 3 REGION 8
U.S.Environmental Protection Agency,Region 3 U.S.Environmental Protection Agency,Region 8
1650 Arch Street,Philadelphia,PA 19103-2029 1595 Wynkoop Street,Denver,CO 80202-1129
Phone:[phone];toll free:[phone] Phone:[phone];tall free:[phone]
Fax:[phone] Fax:[phone]
Website:http:Nwwwepa.govlaboutepalepa-region-3-mid-atlantic Website:htt Ywww a a. ovlaboute ale a-re ion-8-mountains-and• lains
Covered states:Delaware,District of Columbia,Maryland,Pennsylvania,Virginia, Covered states:Colorado,Montana,North Dakota,South Dakota,Utah,and
and West Virginia Wyoming
REGION 4 REGION 9
U.S.Environmental Protection Agency,Region 4 U.S.Environmental Protection Agency,Region 9
Sam Nunn Atlanta Federal Center 75 Hawthorne Street,San Francisco,CA 94105
61 Forsyth Street,SW,Atlanta,GA 30303-8960 Phone:[phone];toll free:(666)EPA-WEST
Phone:[phone];tall free:[phone] Fax:[phone]
Fax:[phone] Website:htt2:llwww.eoa.govlaboutepalepa-region-9-pacific-southwest
Website:http:llwww.epa.govlaboutepalabout•epa-region-4-southeast Covered states Arizona,California,Hawaii,Nevada,Guam,American Samoa,
Covered states:Alabama,Florida,Georgia,Kentucky,Mississippi,North Carolina, and Trust Terrllories
South Carolina,and Tennessee
REGION 5 REGION 10
U.S.Environmental Protection Agency,Region 5 U.S.Environmental Protection Agency,Region 10
77 West Jackson Boulevard,Chicago,IL 60604-3507 1200 Sixth Avenue,Suite 900,Seattle,WA 98101
Phone:[phone]:toll free:[phone] Phone:[phone];toll free:[phone]
Fax:[phone] Fax:[phone]
Website:http:/Awm.ej)a.gov/aboutepa/epa-rec[ion-5 Website;http llwww.epa.govlabouteoaleoa•rggion•10-pacific-northwest
Covered states:Illinois,Indiana,Michigan,Minnesota,Ohio,and Wisconsin Covered states:Alaska,Idaho,Oregon,and Washington
Exhibit 1-2 Filing Dates for NPDES Permit Applications
Permit Application When to File
180 days before your present NPDES permit expires or,if you are a
2A new discharger,180 days before the date on which the discharge is
10 commence unless the NPDES permitting authority has granted
permission for a later date.
2B 180 days before your present NPDES permit expires or 180 days
prior to startup if you are a new facility.
2C 180 days before your present NPDES permit expires.
2D 180 days prior to startup.
2E 180 days before your present NPDES permit expires,or 180 days
prior to startup if you are a new facility.
Construction:90 days prior to dale construction is to commence.
2F Nonconstruction:180 days before your present NPDES permit
expires or 180 days prior to startup if you are a new facility.
2S 180 days before your present NPDES permit expires or 180 days
prior to startup if you are a new facility.
1-3

FORM 1—LINE-BY-LINE INSTRUCTIONS
Section 1.Activities Requiring an NPDES Permit You can find SIC code numbers and descriptions in the
Item 1.1.Review the questions in Item 1.1 to determine if you are 1987 Standard Industrial Classification Manual, prepared by the
required to submit Form 1. Be sure to check the Form 1— Executive Office of the President, Office of Management and
Glossary for the legal definitions of any key terms. Budget.This document is available from the Government Printing
Office,Washington,D.C.An online version of the manual is also
If you answer`Yes"to a question in Item 1.1,then you do not available courtesy of the Occupational Safety and Health
need to complete Form 1,but you must comply with the Administration at http:llwww.osha.gov/pis/imislsic manual.html.
application requirements specified.
You can find NAICS code numbers and descriptions in the North
Item 1.2.Respond to the questions in Items 1.2.1 to 1.2.5, If you American Industrial Classification System Manual prepared by the
answer"Yes"to any question,you must complete Form 1 and the Executive Office of the President,Office of Management and
Form 2 application specified. See Exhibit 1-2 for filing deadlines. Budget.This document is available from the National Technical
If you answer"No"to every question in Items 1.1 and 1.2,then Information Service(NTIS)in Alexandria,Virginia.It is also
you do not need an NPDES permit, and you do not need to available online at http:!lwww.census.govleos/www/naics/.
complete and return any of the NPDES application forms. Use the latest edition of the manuals. If you have any questions
Section 2,Name,Mailing Address,and Location about the appropriate SIC or NAICS codes for your facility,
Item 2.1.Enter the facility's official or legal name. Do not use a contact your NPDES permitting authority.
colloquial name, Section 4.Operator Information
Item 2.2.Provide your EPA Identification Number from the Item 4.1.Give the legal name of the person,firm, public
Facility Registry Service if you have an existing facility. It you do organization,or other entity that operates the facility described in
not know your EPA Identification Number,contact your NPDES this application.This may or may not be the same as the facility's
permitting authority. If your facility is new(i.e.,not yet name.The operator of the facility is the legal entity that controls
constructed),write or type"New Facility." the facility's operation rather than the plant or site manager.Do
not use a colloquial name.
Item 2.3.Give the name(first and last),title,work telephone
number, and email address of the person who is thoroughly Item 4.2.Indicate whether the entity listed in response to Item 4.1
familiar with the operation of the facility and with the facts also owns the facility by marking the appropriate box.
reported in this application.The NPDES permitting authority will Item 4.3.Indicate the ownership status of the operator of the
contact the person listed if they have questions on the material facility by marking the appropriate box.If the facility is a federal
submitted. facility(i.e.,owned by the U.S.government),check the box for
Item 2.4.Give the complete mailing address of the office to which "Public—federal."If the facility is owned by a state government,
the NPDES permitting authority should send correspondence. check the box for"Public—state."If the facility is owned by a
This often is not the address used to designate the location of the county government,municipal(e.g.,city or town)government.
facility or activity. tribal government,school district,water district,or other local
government entity,check the box for"Other public"and specify
Item 2.5.Give the address or location of the facility identified the type of government entity.If the facility is owned by a
under Item 2.1. If the facility lacks a street name or route number, corporation or other private entity,check the box for"Private."If
give the most accurate, alternative geographic information (e.g., the facility has mixed ownership(e.g.,public/private)or is not
section number or quarter section number from county records or owned by an entity of the types previously listed,check the box
"at intersection of Routes 425 and 22").Also provide the county for"Other"and specify the type of entity.
name,county code(if known),city or town,state,and zip code.
Items 4.4 to 4.6.Enter the telephone number, address,and email
For concentrated aquatic animal production facilities,provide the address of the operator identified in Item 4.1.
address or location of the production area(i.e.,the location where
the animals are contained,grown,or held). Section 5.Indian Land
Section 3.SIC and NAICS Codes Item 5.1. Indicate whether the facility is located on Indian Land.
Items 3.1 and 3.2.List,in descending order of significance, up to Section 6.Existing Environmental Permits
four 4-digit standard industrial classification(SIC)codes and Item 6.1.Check the appropriate boxes and provide the permit
North American Industrial Classification System(NAICS)codes numbers for all relevant federal, state, and local environmental
that best describe your facility in terms of the principal products or permits or construction approvals received or applied for under
services it produces or provides.If the SIC or NAICS codes do any of the programs listed below. If you have more than one
not adequately describe your facility's products or services,you currently effective permit under a particular permit program for
have the option to provide additional descriptive information. your facility,list the additional permit numbers on the application
form or on a separate sheet of paper.
1-4

FORM 1—LINE-BY-LINE INSTRUCTIONS CONTINUED
• Hazardous waste management program under the Resource (e.g.,residential,commercial).An example of an acceptable
Conservation and Recovery Act(RCRA). location map is shown as Exhibit 1-3 at the end of these
• Underground Injection Control(UIC)program under the Safe instructions.Note: Exhibit 1-3 is provided for illustration only; it
Drinking Water Act(SDWA), does not show an actual facility.
• NPDES program under the Clean Water Act(CWA). If the facility is a concentrated animal feeding operation,you are
• Prevention of Significant Deterioration(PSD)program under not required to provide the topographic map required by this
the Clean Air Act(CAA). section of Form 1. Instead,you are required to provide a
topographic map as specified in Section 4 of Form 2B.
• Non attai n m ent program under the CAA.
Item 7.1.Note that you have completed your topographic map
• National Emission Standards for Hazardous Pollutants and attached it to the application.
(NESHAPs)preconstruction approval under the CAA.
Section 8.Nature of Business
• Ocean dumping permits under the Marine Protection Briefly describe the nature of your business(e.g.,products
Research and Sanctuaries Act(MPRSA).
produced or services provided).See Examples 1 and 2.
• Dredge or fill permits under Section 404 of the CWA.
Other federal,state,or local environmental permits. Example 1
' Facilities Subject to 40 CFR 426,Subparts F and G
Section 7.Map Industry A is an auto tempered and auto laminated glass
Unless the facility is a concentrated animal feeding operation, manufacturing facility subject to effluent limitation guidelines
provide a topographic map(s)of the area extending at least one (ELGs)for the"Automotive Glass Tempering"and"Automotive
mile beyond the property boundaries of the facility that clearly Glass Laminating"subcategories of the"Glass Manufacturing"
shows the following: point source category at 40 CFR 426,subparts F and G.At the
• The legal boundaries of the facility. facility,glass is cut and then passed through a series of
processes that grind and polish the edges,bend the glass,and
• The location and serial number of each of your existing and then temper the glass to produce side and back windows for
proposed intake and discharge structures. automobiles.Tempering involves heating the glass near the
• All hazardous waste management,storage,and disposal melting point,then rapidly cooling it to increase its mechanical
facilities. and thermal endurance.The facility also produces automobile
• Each well where you inject fluids underground. windshields and undertakes processes that laminate a plastic
sheet between two layers of glass and that prepare the glass for
• All wells,springs,surface water bodies, and drinking water lamination(e.g.,cutting, bending, and washing).
wells that are in the public record or otherwise known to you
and that are located in the map area. Example 2
If the facility has associated water intakes,discharge structures, Facility Not Subject to ELGs
hazardous waste disposal sites,or injection wells and these items Industry B undertakes batch-type resin manufacturing operations.
are located more than one mile from the facility,include them on It has aboveground storage tanks for raw materials and finished
the map if possible. If you cannot, attach additional sheets goods, resin loading operations, and warehouses for 55-g0on
describing the location of the structures,disposal site(s),or well(s) drums of finished product. Industry B manufactures alkyd,
and identify the U.S.Geological Survey(USGS)or other map saturated and unsaturated polyester resins in batches using
corresponding to the location(s). reactor vessels and mix tanks.Most of the feedstock liquids are
pumped from storage tanks to the kettles and mixers via a closed
On each map, include the map scale,a meridian arrow showing piping system.Additional feedstocks are added manually as
north,and latitude and longitude to the nearest second.Latitude solids from bags and sacks via manways,which are located on
and longitude coordinates may be obtained in a variety of ways, top of the kettles.The resin is then chemically reacted in the
including use of hand held devices(e.g..a GPS enabled kettles.After the reaction step finishes,the resin is transferred
smartphone),internet mapping tools(e.g., from the kettles to the mix tanks,where solvents are added to
hUps:llmynasadata.larc.nasa.gov/latitudelongitude-finder/), thin it.The primary byproduct of the reaction is water vapor
geographic information systems(e.g.,ArcView),or paper maps containing condensed soluble organics.The byproduct flows to
from trusted sources(e.g.,USGS). an isolation tank where the vapors are directed to an onsite
On all maps of rivers,show the direction of the current. In tidal thermal oxidizer.The finished resin is then pumped through one
waters,show the directions of ebb and flow tides. of three types of filtration systems into finished goods storage
tanks,55-gallon drums,350-gallon intermediate bulk container
You may develop your map by going to USGS's National Map totes,or directly into tanker trucks.A typical batch takes about 30
website at http:l/nationalmao.govl.(For a map from this site, use hours to complete.
the traditional 7.5-minute quadrangle format. If none is available,
use a USGS 15-minute series map.)You may also use a plat or
other appropriate map.Briefly describe land uses in the map area
1-5

FORM 1—LINE-BY-LINE INSTRUCTIONS CONTINUED
Section 9.Cooling Water Intake Structures FEDERAL REGULATIONS AT 40 CFR 122.22 REQUIRE THIS
Item 9.1.Indicate whether the facility uses cooling water.If yes, APPLICATION TO BE SIGNED AS FOLLOWS:
continue to Item 9.2.If no,skip to Item 10.1. A. For a corporation,by a responsible corporate officer.For the
Item 9.2.Identify the source of the cooling water.For example, purpose of this section,a responsible corporate officer
indicate whether the cooling water is from a surface water, means:(1)a president,secretary,treasurer,or vice-president
groundwater well,public water system,or treated effluent that of the corporation in charge of a principal business function,
would otherwise be discharged to a water of the U.S, or any other person who performs similar policy-or decision-
making functions for the corporation,or(2)the manager of
If the facility uses a cooling water intake structure as described in one or more manufacturing,production,or operating facilities,
40 CFR 125,Subparts I and J,the facility may have additional provided the manager is authorized to make management
application requirements under 40 CFR 122.21(r).Note that the decisions which govern the operation of the regulated facility
information required by 40 CFR 122.21(r)is not requested as part including having the explicit or implicit duty of making major
of Form 1.Contact your NPDES permitting authority to determine capital investment recommendations,and initiating and
the specifics of what you should provide and when. directing other comprehensive measures to assure long term
Section 10.Variance Requests environmental compliance with environmental laws and
An applicant(other than a POTW)may request a variance from regulations;the manager can ensure that the necessary
otherwise applicable effluent limitations under certain conditions systems are established or actions taken to gather complete
described at 40 CFR 122.21(m). and accurate information for permit application requirements;
and where authority to sign documents has been assigned or
Item 10.1.If known at the time of application,check all of the delegated to the manager in accordance with corporate
authorized variances that you plan to request or renew. Note that procedures.
you are not being asked to submit any other information at this B. For a partnership or sole proprietorship,by a general partner
time.Contact your NPDES permitting authority to determine the or the proprietor,respectively.
specifics of what you should provide and when.The ability to
request a variance is not limited to the time of application,and an C. For a municipality,state,federal,or other public facility,by
applicant may request a variance consistent with statutory and either a principal executive officer or ranking elected official.
regulatory requirements. For purposes of this section,a principal executive officer of a
federal agency includes:(1)The chief executive officer of the
Section 11.Checklist and Certification agency,or(2)a senior executive officer having responsibility
Item 11.1.Review the checklist provided.In Column 1,mark the for the overall operations of a principal geographic unit of the
sections of Form 1 that you have completed and are submitting agency(e.g.,Regional Administrators of EPA).
with your application.In Column 2,indicate for each section
whether you are submitting attachments.
Item 11.2.The Clean Water Act provides for severe penalties for
submitting false information on this application form.CWA Section
309(c)(2)provides that,"Any person who knowingly makes any
false statement,representation,or certification in any application,
...shall upon conviction,be punished by a fine of no more than
$10,000 or by imprisonment for not more than six months,or
both."
1-6

Exhibit 1--3.Example Topographic Map
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1-7

FORM 1—ACTIVITIES THAT DO NOT REQUIRE PERMITS
You are not required to obtain an NPDES permit if your discharge Any discharge in compliance with the instructions of an On-
is in one of the following categories,as provided by the CWA and Scene Coordinator pursuant to 40 CFR 300(The National Oil
NPDES regulations at 40 CFR 122 to 125.(However,under CWA and Hazardous Substances Pollution Contingency Plan)or
Sections 510 and 312,some discharges exempted from the 33 CFR 153.10(e)(Pollution by Oil and Hazardous
federal NPDES requirements may still be regulated by a state Substances).
permitting authority.) Any introduction of pollutants from non point-source
• Any discharge of sewage from vessels and any effluent from agricultural and silvicultural activities,including stormwater
properly functioning marine engines,laundry,shower,and runoff from orchards,cultivated crops,pastures,range lands,
galley sink wastes,or any other discharge incidental to the and forest lands,but not discharges from concentrated
normal operation of a vessel,including vessels of the Armed animal feeding operations as defined in 40 CFR 122.23,
Forces within the meaning of section 312 of the CWA and discharges from concentrated aquatic animal production
recreational vessels within the meaning of section 502(25)of facilities as defined in 40 CFR 122.23,discharges from
the CWA. None of these exclusions apply to rubbish,trash, concentrated aquatic animal production facilities as defined
garbage,or other such materials discharged overboard;nor in 40 CFR 122.24,discharges to aquaculture projects as
to other discharges when the vessel is operating in a defined in 40 CFR 122.25,and discharges from silvicultural
capacity other than as a means of transportation such as point sources as defined in 40 CFR 122.27.Note; Per 40
when used as an energy or mining facility,a storage facility CFR 122.26(b)(14)(ii),facilities classified within SIC 24,
or a seafood processing facility,or when secured to a Industry Group 241,that are rock crushing,gravel washing,
storage facility or a seafood processing facility,or when log sorting,or log storage facilities operated in connection
secured to the bed of the ocean,contiguous zone or waters with silvicultural activities defined in 40 CFR 122.27(b)(2)—(3)
of the United States for the purpose of mineral or oil and Industry Groups 242 through 249;26(except 265 and
exploration or development. 267),28(except 283),29,311,32(except 323),33,3441,
• Discharges of dredged or fill material into waters of the and 373(not included are all other types of silviculture
United States that are regulated under CWA Section 404. facilities)are considered stormwater discharges associated
with industrial activity,and are required to obtain an NPDES
• The introduction of sewage,industrial wastes,or other permit.
pollutants into publicly owned treatment works by indirect • Return flows from irrigated agriculture.
dischargers.Plans or agreements to switch to this method of
disposal in the future do not relieve dischargers of the • Discharges into a privately owned treatment works,except as
obligation to have and comply with permits until all the NPDES permitting authority may otherwise require under
discharges of pollutants to waters of the United States are 40 CFR 122.44(m).
eliminated.(See also 40 CFR 122.47(b).)This exclusion • Discharges from a water transfer."Water transfer"means an
does not apply to the introduction of pollutants to privately activity that conveys or connects waters of the United States
owned treatment works or to other discharges through pipes, without subjecting the transferred water to intervening
sewers,or other conveyances owned by a state,municipality, industrial,municipal,or commercial use.This exclusion does
or other party not leading to treatment works. not apply to pollutants introduced by the water transfer
activity itself to the water being transferred.
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FORM 1—GLOSSARY
Note:This glossary includes terms used in the various NPDES application forms,including Form 1.The definitions are from the NPDES
regulations at 40 CFR 122.2 unless otherwise specified.If you have any questions concerning the meaning of any of these terms,contact
your NPDES permitting authority.
ANIMAL FEEDING OPERATION(defined at§122.23)means a lot or facility(other than an aquatic animal production facility)where the
following conditions are met;
• Animals(other than aquatic animals)have been,are,or will be stabled or confined and fed or maintained for a total of 45 days or
more in any 12-month period;and
• Crops,vegetation,forage growth,or post-harvest residues are not sustained in the normal growing season over any portion of the lot
or facility.
APPLICATION means the EPA standard national forms for applying for a permit,including any additions,revisions,or modifications to the
forms;or forms approved by EPA for use in approved states,including any approved modifications or revisions.
APPROVED PROGRAM or APPROVED STATE means a State or interstate program which has been approved or authorized by EPA
under part 123.
AQUACULTURE PROJECT(defined at§122.25)means a defined managed water area which uses discharges of pollutants into that
designated area for the maintenance or production of harvestable freshwater,estuarine,or marine plants or animals.DESIGNATED
PROJECT AREA means the portions of the waters of the United States within which the permittee or permit applicant plans to confine the
cultivated species,using a method or plan or operation(including,but not limited to,physical confinement)which,on the basis of reliable
scientific evidence,is expected to ensure that specific individual organisms comprising an aquaculture crop will enjoy increased growth
attributable to the discharge of pollutants,and be harvested within a defined geographic area.
AVERAGE MONTHLY DISCHARGE LIMITATION means the highest allowable average of daily discharges over a calendar month,
calculated as the sum of all daily discharges measured during that month divided by the number of daily discharges measured during that
month.
AVERAGE WEEKLY DISCHARGE LIMITATION means the highest allowable average of daily discharges over a calendar week,
calculated as the sum of all daily discharges measured during a calendar week divided by the number of daily discharges measured during
that week.
BEST MANAGEMENT PRACTICES(BMPs)means schedules of activities,prohibitions of practices,maintenance procedures,and other
management practices to prevent or reduce the pollution of waters of the United States.BMPs include treatment requirements,operation
procedures,and practices to control plant site runoff,spillage or leaks,sludge or waste disposal,or drainage from raw material storage.
BIOSOLIDS(see sewage sludge).
BYPASS(defined at§122.41(m))means the intentional diversion of waste streams from any portion of a treatment facility.
COMBINED SEWER OVERFLOW(CSO)means a discharge from a combined sewer system(CSS)at a point prior to the Publicly Owned
Treatment Works(POT"Treatment Plant(defined at§403.3(r)).
COMBINED SEWER SYSTEM(CSS)means a wastewater collection system owned by a State or municipality(as defined by section
502(4)of the CWA)which conveys sanitary wastewaters(domestic,commercial and industrial wastewaters)and storm water through a
single-pipe system to a Publicly Owned Treatment Works(POTW)Treatment Plant(as defined at§403.3(r)).
CONCENTRATED ANIMAL FEEDING OPERATION(defined at§ 122.23)means an animal feeding operation that is defined as a Large
CAFO or as a Medium CAFO by the terms of(A)or(B)below,or that is designated as a CAFO in accordance with 40 CFR 122.23(c).Two
or more AFOs under common ownership are considered to be a single AFO for the purposes of determining the number of animals at an
operation,if they adjoin each other or if they use a common area or system for the disposal of wastes,
A. LARGE CONCENTRATED ANIMAL FEEDING OPERATION(LARGE CAFO)means an AFO that stables or confines as many as or
more than the numbers of animals specified in any of the following categories:
1. 700 mature dairy cows,whether milked or dry;
2. 1,000 veal calves;
3. 1,000 cattle other than mature dairy cows or veal calves.Cattle includes but is not limited to heifers,steers,bulls and cow/calf
pairs;
4. 2,500 swine each weighing 55 pounds or more;
5. 10,000 swine each weighing less than 55 pounds;
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FORM 1—GLOSSARY CONTINUED
6. 500 horses;
7. 10,000 sheep or lambs;
8. 55,000 turkeys;
9. 30,000 laying hens or broilers,if the AFO uses a liquid manure handling system;
10. 125,000 chickens(other than laying hens),if the AFO uses other than a liquid manure handling system;
11. 82,000 laying hens,if the AFO uses other than a liquid manure handling system;
12. 30,000 ducks(if the AFO uses other than a liquid manure handling system);or
13. 5,000 ducks(if the AFO uses a liquid manure handling system).
B. MEDIUM CONCENTRATED ANIMAL FEEDING OPERATION(MEDIUM CAFO)means any AFO with the type and number of
animals that fall within any of the ranges listed below and which has been defined or designated as a CAFO.An AFO is defined as a
Medium CAFO if:
1. The type and number of animals that it stables and confines falls within any of the following ranges:
a. 200 to 699 mature dairy cows,whether milked or dry;
b. 300 to 999 veal calves;
c. 300 to 999 cattle other than mature dairy cows or veal calves.Cattle includes but is not limited to heifers,steers,bulls and
cow/calf pairs;
d. 750 to 2,499 swine each weighing 55 pounds or more;
e. 3,000 to 9,999 swine each weighing less than 55 pounds;
f. 150 to 499 horses;
g. 3,000 to 9,999 sheep or lambs;
h. 16,500 to 54,999 turkeys;
i. 9,000 to 29,999 laying hens or broilers,if the AFO uses a liquid manure handling system;
j. 37,500 to 124,999 chickens(other than laying hens),if the AFO uses other than a liquid manure handling system;
k. 25,000 to 81,999 laying hens,if the AFO uses other than a liquid manure handling system;
I. 10,000 to 29,999 ducks(if the AFO uses other than a liquid manure handling system);ore
m. 1,500 to 4,999 ducks(if the AFO uses a liquid manure handling system);and
2. Either one of the following conditions are met:
a. Pollutants are discharged into waters of the United States through a man-made ditch,flushing system,or other similar man-
made device;or
b. Pollutants are discharged directly into waters of the United States which originate outside of and pass over,across,or
through the facility or otherwise come into direct contact with animals confined in the operation.
CONCENTRATED AQUATIC ANIMAL PRODUCTION FACILITY(defined at§122.24)means a hatchery,fish farm,or other facility which
contains,grows,or holds aquatic animals in either of the following categories,or which the Director designates as such on a case-by-case
basis:
A. Cold water fish species or other cold water aquatic animals including,but not limited to,the Saimonidae family of fish(e.g.,trout and
salmon)in ponds,raceways,or other similar structures which discharge at least 30 days per year but does not include:
1. Facilities which produce less than 9,090 harvest weight kilograms(approximately 20,000 pounds)of aquatic animals per year;
and
2. Facilities which feed less than 2,272 kilograms(approximately 5,000 pounds)of food during the calendar month of maximum
feeding.
B. Warm water fish species or other warm water aquatic animals including,but not limited to,the Ameiuridae, Cetrarchiciae,and
Cyprinidae families of fish(e.g.,respectively,catfish,sunfish,and minnows)in ponds,raceways,or other similar structures which
discharge at least 30 days per year,but does not include;
1. Closed ponds which discharge only during periods of excess runoff;or
2. Facilities which produce less than 45,454 harvest weight kilograms(approximately 100,000 pounds)of aquatic animals per year.
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FORM 1—GLOSSARY CONTINUED
CWA means the Clean Water Act(formerly referred to as the Federal Water Pollution Control Act or Federal Water Pollution Control Act
Amendments of 1972)Public Law 92-500,as amended by Public Law 95-217,Public Law 95-576,Public Law 96483 and Public Law
97-117,33 U.S.C. 1251 et seq.
CWA AND REGULATIONS means the Clean Water Act(CWA)and applicable regulations promulgated thereunder.In the case of an
approved State program,it includes State program requirements.
DAILY DISCHARGE means the"discharge of a pollutant"measured during a calendar day or any 24-hour period that reasonably
represents the calendar day for purposes of sampling.For pollutants with limitations expressed in units of mass,the"daily discharge"is
calculated as the total mass of the pollutant discharged over the day.For pollutants with limitations expressed in other units of
measurement,the"daily discharge"is calculated as the average measurement of the pollutant over the day.
DIRECT DISCHARGE means the"discharge of a pollutant."
DIRECTOR means the Regional Administrator or the State Director,as the context requires,or an authorized representative.When there
is no"approved State program,"and there is an EPA administered program,"Director"means the Regional Administrator.When there is
an approved State program,"Director"normally means the State Director.In some circumstances,however,EPA retains the authority to
take certain actions even when there is an approved State program.(For example,when EPA has issued an NPDES permit prior to the
approval of a State program,EPA may retain jurisdiction over that permit after program approval,see§123.1.)In such cases,the term
"Director"means the Regional Administrator and not the State Director.
DISCHARGE(OF A POLLUTANT)means:
• Any addition of any pollutant or combination of pollutants to waters of the United States from any point source;or
• Any addition of any pollutant or combination of pollutants to the waters of the contiguous zone or the ocean from any point source
other than a vessel or other floating craft which is being used as a means of transportation.
This definition includes discharges into waters of the United States from:surface runoff which is collected or channelled by man;
discharges through pipes,sewers,or other conveyances owned by a State,municipality,or other person which do not lead to a treatment
works;and discharges through pipes,sewers,or other conveyances,leading into privately owned treatment works.This term does not
include an addition of pollutants by any"indirect discharger".
DISCHARGE MONITORING REPORT means the EPA uniform national form,including any subsequent additions,revisions,or
modifications for the reporting of self-monitoring results by permittees.DMRs must be used by"approved States"as well as by EPA.EPA
will supply DMRs to any approved State upon request.The EPA national forms may be modified to substitute the state agency name,
address,logo,and other similar information,as appropriate,in place of EPA's.
DRAFT PERMIT means a document prepared under§124.6 indicating the Directors tentative decision to issue or deny,modify,revoke
and reissue,terminate,or reissue a"permit."A nofice of intent to terminate a permit,and a notice of intent to deny a permit,as discussed
in§124.5,are types of"draft permits."A denial of a request for modification,revocation and reissuance,or termination,as discussed in
§124.5,is not a"draft permit."A"proposed permit"is not a"draft permit."
EFFLUENT LIMITATION means any restriction imposed by the Director on quantities,discharge rates,and concentrations of"pollutants"
which are"discharged"from"point sources"into"waters of the United States,"the waters of the"contiguous zone,"or the ocean.
EFFLUENT LIMITATIONS GUIDELINES means a regulation published by the Administrator under section 304(b)of the CWA to adopt or
revise"effluent limitations."
ENVIRONMENTAL PROTECTION AGENCY(EPA)means the United States Environmental Protection Agency.
FACILITY or ACTIVITY means any NPDES"point source"or any other facility or activity(including land or appurtenances thereto)that is
subject to regulation under the NPDES program.
GENERAL PERMIT means an NPDES"permit"issued under§122.28 authorizing a category of discharges under the CWA within a
geographical area.
HAZARDOUS SUBSTANCE means any substance designated under 40 CFR part 116 pursuant to section 311 of the CWA.
INDIAN COUNTRY(or INDAN LANDS)means:
• All land within the limits of any Indian reservation under the jurisdiction of the United States Government,notwithstanding the
issuance of any patent,and,including rights-of-way running through the reservation;
• All dependent Indian communities with the borders of the United States whether within the originally or subsequently acquired territory
thereof,and whether within or without the limits of a state;and
• All Indian allotments,the Indian titles to which have not been extinguished,including rights-of-way running through the same.
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FORM 1—GLOSSARY CONTINUED
INDIAN TRIBE means any Indian Tribe,band,group,or community recognized by the Secretary of the Interior and exercising
governmental authority over a Federal Indian reservation.
INDIRECT DISCHARGE means a nondomestic discharger introducing"pollutants"to a"publicly owned treatment works."
LARGE MUNICIPAL SEPARATE STORM SEWER SYSTEM(defined at§122.26(b)(4))means all municipal separate storm sewers that
are either:
(i)Located in an incorporated place with a population of 250,000 or more as determined by the 1990 Decennial Census by the Bureau of
the Census(Appendix F of 40 CFR 122);or
(ii)Located in the counties listed in appendix H of 40 CFR 122,except municipal separate storm sewers that are located in the
incorporated places,townships or towns within such counties;or
(iii)Owned or operated by a municipality other than those described in paragraphs(i)or(ii)and that are designated by the Director as part
of the large or medium municipal separate storm sewer system due to the interrelationship between the discharges of the designated
storm sewer and the discharges from municipal separate storm sewers described under paragraphs(i)or(ii). In making this determination
the Director may consider the following factors:
(A)Physical interconnections between the municipal separate storm sewers;
(B)The location of discharges from the designated municipal separate storm sewer relative to discharges from municipal separate storm
sewers described in paragraph(i);
(C)The quantity and nature of pollutants discharged to waters of the United States;
(D)The nature of the receiving waters;and
(E)Other relevant factors;or
(iv)The Director may,upon petition,designate as a large municipal separate storm sewer system,municipal separate storm sewers
located within the boundaries of a region defined by a storm water management regional authority based on a jurisdictional,watershed,or
other appropriate basis that includes one or more of the systems described in paragraphs(i),(ii),(iii).
LOG SORTING AND LOG STORAGE FACILITIES(defined at§122.27)means facilities whose discharges result from the holding of
unprocessed wood,for example,logs or roundwood with bark or after removal of bark held in self-contained bodies of water(mill ponds or
log ponds)or stored on land where water is applied intentionally on the logs(wet decking).(See 40 CFR 429,subpart I,including the
effluent limitations guidelines.)
MAJOR FACILITY means any NPDES"facility or activity"classified as such by the Regional Administrator,or,in the case of"approved
State programs,"the Regional Administrator in conjunction with the State Director.
MAXIMUM DAILY DISCHARGE LIMITATION means the highest allowable"daily discharge."
MEDIUM MUNICIPAL SEPARATE STORM SEWER SYSTEM(defined at§122.26(b)(7))means all municipal separate storm sewers that
are either:
(i)Located in an incorporated place with a population of 100,000 or more but less than 250,000,as determined by the 1990 Decennial
Census by the Bureau of the Census(appendix G of 40 CFR 122);or
(ii)Located in the counties listed in appendix I of 40 CFR 122,except municipal separate storm sewers that are located in the incorporated
places,townships or towns within such counties;or
(iii)Owned or operated by a municipality other than those described in paragraph(i)or(ii)and that are designated by the Director as part
of the large or medium municipal separate storm sewer system due to the interrelationship between the discharges of the designated
storm sewer and the discharges from municipal separate storm sewers described under paragraph(i)or(ii).In making this determination
the Director may consider the following factors:
(A)Physical interconnections between the municipal separate storm sewers;
(B)The location of discharges from the designated municipal separate storm sewer relative to discharges from municipal separate storm
sewers described in paragraph(i);
(C)The quantity and nature of pollutants discharged to waters of the United States;
(D)The nature of the receiving waters;or
(E)Other relevant factors;or
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FORM 1—GLOSSARY CONTINUED
(iv)The Director may,upon petition,designate as a medium municipal separate storm sewer system,municipal separate storm sewers
located within the boundaries of a region defined by a storm water management regional authority based on a jurisdictional,watershed,or
other appropriate basis that includes one or more of the systems described in paragraphs(i),(ii),(iii)of this section.
MUNICIPALITY means a city,town,borough,county,parish,district,association,or other public body created by or under State law and
having jurisdiction over disposal of sewage,industrial wastes,or other wastes,or an Indian tribe or an authorized Indian tribal organization,
or a designated and approved management agency under section 208 of the CWA.
MUNICIPAL SEPARATE STORM SEWER(defined at§122.26(b)(8))means a conveyance or system of conveyances(including roads
with drainage systems,municipal streets,catch basins,curbs,gutters,ditches,man-made channels,or storm drains):
• Owned or operated by a State,city,town,borough,county,parish,district,association,or other public body(created by or pursuant to
State law)having jurisdiction over disposal of sewage,industrial wastes,stormwater,or other wastes,including special districts under
State law such as a sewer district,flood control district or drainage district,or similar entity,or an Indian tribe or an authorized Indian
tribal organization,or a designated and approved management agency under section 208 of the CWA that discharges to waters of the
United States.
• Designed or used for collecting or conveying stormwater.
• Which is not a combined sewer;and
• Which is not part of a POTW as defined at 40 CFR 122.2.
MUNICIPAL SLUDGE(see sewage sludge)
NATIONAL POLLUTANT DISCHARGE ELIMINATION SYSTEM(NPDES)means the national program for issuing,modifying,revoking
and reissuing,terminating,monitoring and enforcing permits,and imposing and enforcing pretreatment requirements,under sections 307,
402,318,and 405 of the CWA.The term includes an"approved program."
NEW DISCHARGER means any building,structure,facility,or installation:
• From which there is or may be a"discharge of pollutants;"
• That did not commence the"discharge of pollutants"at a particular"site"prior to August 13, 1979;
• Which is not a"new source;"and
• Which has never received a finally effective NPDES permit for discharges at that"site."
This definition includes an"indirect discharger"which commences discharging into'waters of the United States"after August 13, 1979. It
also means any existing mobile point source(other than an offshore or coastal oil and gas exploratory drilling rig or a coastal oil and gas
developmental drilling rig)such as a seafood processing rig,seafood processing vessel,or aggregate plant,that begins discharging at a
"site"for which it does not have a permit;and any offshore or coastal mobile oil and gas exploratory drilling rig or coastal mobile oil and gas
developmental drilling rig that commences the discharge of pollutants after August 13, 1979,at a"site"under EPA's permitting jurisdiction
for which it is not covered by an individual or general permit and which is located in an area determined by the Regional Administrator in
the issuance of a final permit to be an area of biological concern. In determining whether an area is an area of biological concern,the
Regional Administrator shall consider the factors specified in 40 CFR 125.122(a)(1)through(10).
An offshore or coastal mobile exploratory drilling rig or coastal mobile developmental drilling rig will be considered a"new discharger'only
for the duration of its discharge in an area of biological concern.
NEW SOURCE means any building,structure,facility,or installation from which there is or may be a"discharge of pollutants,"the
construction of which commenced:
• After promulgation of standards of performance under section 306 of the CWA which are applicable to such source,or
• After proposal of standards of performance in accordance with section 306 of the CWA which are applicable to such source,but only
if the standards are promulgated in accordance with section 306 within 120 days of their proposal.
OWNER OR OPERATOR means the owner or operator of any"facility or activity"subject to regulation under the NPDES program.
PERMIT means an authorization,license,or equivalent control document issued by EPA or an"approved State"to implementthe
requirements of this part and parts 123 and 124."Permit"includes an NPDES"general permit"(§122.28). Permit does not include any
permit which has not yet been the subject of final agency action,such as a"draft permit"or a"proposed permit."
PESTICIDE DISCHARGES TO WATERS OF THE UNITED STATES FROM PESTICIDE APPLICATION means the application of
biological pesticides,and the application of chemical pesticides that leave a residue,from point sources to waters of the United States. In
the context of this definition of pesticide discharges to waters of the United States from pesticide application,this does not include
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FORM 1—GLOSSARY CONTINUED
agricultural storm water discharges and return flows from irrigated agriculture,which are excluded by law(33 U.S.C. 1342(I);33 U.S.C.
1362(14)).
PESTICIDE RESIDUE for the purpose of determining whether a NPDES permit is needed for discharges to waters of the United States
from pesticide application,means that portion of a pesticide application that is discharged from a point source to waters of the United
States and no longer provides pesticidal benefits.It also includes any degradates of the pesticide.
POINT SOURCE means any discernible,confined,and discrete conveyance,including but not limited to,any pipe,ditch,channel,tunnel,
conduit,well,discrete fissure,container,rolling stock,concentrated animal feeding operation,landfill leachate collection system,vessel or
other floating craft from which pollutants are or may be discharged.This term does not include return flows from irrigated agriculture or.
agricultural stormwater runoff.(See§122.3).
POLLUTANT means dredged spoil,solid waste,incinerator residue,filter backwash,sewage,garbage,sewage sludge,munitions,
chemical wastes,biological materials,radioactive materials(except those regulated under the Atomic Energy Act of 1954,as amended(42
U.S.C.2011 et seq.)),heat,wrecked or discarded equipment,rock,sand,cellar dirt and industrial,municipal,and agricultural waste
discharged into water.It does not mean:
• Sewage from vessels;or
• Water,gas,or other material which is injected into a well to facilitate production of oil or gas,or water derived in association with oil
and gas production and disposed of in a well,if the well used either to facilitate production or for disposal purposes is approved by
authority of the State in which the well is located,and if the State determines that the injection or disposal will not result in the
degradation of ground or surface water resources.Note:Radioactive materials covered by the Atomic Energy Act are those
encompassed in its definition of source,byproduct,or special nuclear materials.Examples of materials not covered include radium
and accelerator-produced isotopes.See Train v.Colorado Public Interest Research Group,Inc.,426 U.S. 1 (1976).
PRIMARY INDUSTRY CATEGORY means any industry category listed in the NRDC settlement agreement(Natural Resources Defense
Council et aI.v. Train,8 E.R.C.2120(D.D.C. 1976),modified 12 E.R.C.1833(D.D.C. 1979));also listed in appendix A of part 122.
PRIVATELY OWNED TREATMENT WORKS means any device or system which is(1)used to treat wastes from any facility whose
operator is not the operator of the treatment works and(2)not a"POTW."
PROCESS WASTEWATER means any water which,during manufacturing or processing,comes into direct contact with or results from the
production or use of any raw material,intermediate product,finished product,byproduct,or waste product.
PROPOSED PERMIT means a state NPDES"permit"prepared after the close of the public comment period(and,when applicable,any
public hearing and administrative appeals)which is sent to EPA for review before final issuance by the State.A"proposed permit"is not a
"draft permit."
PUBLICLY OWNED TREATMENT WORKS or POTW(defined at§403.3)means a treatment works as defined by CWA Section 212,
which is owned by a state or municipality(as defined by CWA Section 502(4)).This definition includes any devices or systems used in the
storage,treatment,recycling,and reclamation)of municipal sewage or industrial wastes of a liquid nature.This definition also includes
sewers,pipes,and other conveyances only if they convey wastewater to a POTW.The term also means the municipality as defined in
CWA Section 502(4),which has jurisdiction over the indirect discharges to and the discharges from such a treatment works.
REGIONAL ADMINISTRATOR means the Regional Administrator of the appropriate Regional Office of the Environmental Protection
Agency or the authorized representative of the Regional Administrator.
ROCK CRUSHING AND GRAVEL WASHING FACILITIES(defined at§122.27)means facilities which process crushed and broken
stone,gravel,and riprap(See 40 CFR 436,subpart B,including the effluent limitations guidelines).
SCHEDULE OF COMPLIANCE means a schedule of remedial measures included in a"permit",including an enforceable sequence of
interim requirements(for example,actions,operations,or milestone events)leading to compliance with the CWA and regulations.
SECONDARY INDUSTRY CATEGORY means any industry category which is not a primary industry category.
SEWAGE FROM VESSELS means human body wastes and the wastes from toilets and other receptacles intended to receive or retain
body wastes that are discharged from vessels and regulated under section 312 of the CWA,except that with respect to commercial
vessels on the Great Lakes this term includes graywater.For the purposes of this definition,"graywater"means galley,bath,and shower
water.
SEWAGE SLUDGE means any solid,semi-solid,or liquid residue removed during the treatment of municipal waste water or domestic
sewage.Sewage sludge includes,but is not limited to,solids removed during primary,secondary,or advanced waste water treatment,
scum,septage,portable toilet pumpings,type III marine sanitation device pumpings(33 CFR 159),and sewage sludge products.Sewage
sludge does not include grit or screenings,or ash generated during the incineration of sewage sludge.
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FORM 1—GLOSSARY CONTINUED
SILVICULTURAL POINT SOURCE(defined at§122.27)means any discernible,confined,and discrete conveyance related to rock
crushing,gravel washing,log sorting,or log storage facilities which are operated in connection with silvicultural activities and from which
pollutants are discharged into waters of the United States.This term does not include non-point source silvicultural activities such as
nursery operations,site preparation,reforestation and subsequent cultural treatment,thinning,prescribed burning,pest and fire control,
harvesting operations,surface drainage,or road construction and maintenance from which there is natural runoff.However,some of these
activities(such as stream crossing for roads)may involve point source discharges of dredged or fill material which may require a CWA
Section 404 permit(see 33 CFR 209.120 and part 233).
SITE means the land or water area where any"facility or activity"is physically located or conducted,including adjacent land used in
connection with the facility or activity.
SLUDGE-ONLY FACILITY means any"treatment works treating domestic sewage"whose methods of sewage sludge use or disposal are
subject to regulations promulgated pursuant to section 405(d)of the CWA and is required to obtain a permit under§122.1(b)(2),
STANDARDS FOR SEWAGE SLUDGE USE OR DISPOSAL means the regulations promulgated pursuant to section 405(d)of the CWA
which govern minimum requirements for sludge quality,management practices,and monitoring and reporting applicable to sewage sludge
or the use or disposal of sewage sludge by any person.
STATE means any of the 50 States,the District of Columbia,Guam,the Commonwealth of Puerto Rico,the Virgin Islands,American
Samoa,the Commonwealth of the Northern Mariana Islands,the Trust Territory of the Pacific Islands,or an Indian Tribe as defined in
these regulations which meets the requirements of§123.31 of this chapter.
STATE DIRECTOR means the chief administrative officer of any State or interstate agency operating an"approved program,"or the
delegated representative of the State Director.If responsibility is divided among two or more State or interstate agencies,"State Director"
means the chief administrative officer of the State or interstate agency authorized to perform the particular procedure or function to which
reference is made.
STORMWATER(or STORM WATER)(defined at§122.26(b)(13))means stormwater runoff,snow melt runoff,and surface runoff and
drainage.
STORMWATER DISCHARGE ASSOCIATED WITH INDUSTRIAL ACTIVITY(defined at§122.26(b)(14))means the discharge from any
conveyance that is used for collecting and conveying stormwater and that is directly related to manufacturing,processing or raw materials
storage areas at an industrial plant.The term does not include discharges from facilities or activities excluded from the NPDES program
under this part 122.For the categories of industries identified in this section,the term includes,but is not limited to,stormwater discharges
from industrial plant yards;immediate access roads and rail lines used or traveled by carriers of raw materials,manufactured products,
waste material,or by-products used or created by the facility;material handling sites;refuse sites;sites used for the application or disposal
of process waste waters(as defined at 40 CFR 401);sites used for the storage and maintenance of material handling equipment;sites
used for residual treatment,storage,or disposal;shipping and receiving areas;manufacturing buildings;storage areas(including tank
farms)for raw materials,and intermediate and final products;and areas where industrial activity has taken place in the past and significant
materials remain and are exposed to stormwater.For the purposes of this paragraph,material handling activities include storage,loading
and unloading,transportation,or conveyance of any raw material,intermediate product,final product,by-product or waste product.The
term excludes areas located on plant lands separate from the plant's industrial activities,such as office buildings and accompanying
parking lots as long as the drainage from the excluded areas is not mixed with stormwater drained from the above described areas.
Industrial facilities(including industrial facilities that are federally,State,or municipally owned or operated that meet the description of the
facilities listed in paragraphs 1 through 14 below)include those facilities designated under the provisions of 40 CFR 122.26(a)(1)(v).The
following categories of facilities are considered to be engaging in"industrial activity"for purposes of 40 CFR 122,26(b)(14):
1. Facilities subject to stormwater effluent limitations guidelines,new source performance standards,or toxic pollutant effluent standards
under 40 CFR Subchapter N(except facilities with toxic pollutant effluent standards which are exempted under paragraph 11 below);
2. Facilities classified as Standard Industrial Classification 24,Industry Group 241 that are rock crushing,gravel washing,log sorting,or
log storage facilities operated in connection with silvicultural activities defined in 40 CFR 122.27(b)(2)—(3)and Industry Groups 242
through 249;26(except 265 and 267),28(except 283),29,311,32(except 323),33,3441,373;(not included are all other types of
silvicultural facilities);
3. Facilities classified as Standard Industrial Classifications 10 through 14(mineral industry)including active or inactive mining
operations(except for areas of coal mining operations no longer meeting the definition of a reclamation area under 40 CFR 434.11(1)
because the performance bond issued to the facility by the appropriate SMCRA authority has been released,or except for areas of
non—coal mining operations which have been released from applicable State or Federal reclamation requirements after
December 17, 1990)and oil and gas exploration,production,processing,or treatment operations,or transmission facilities that
discharge stormwater contaminated by contact with or that has come into contact with,any overburden,raw material,intermediate
products,finished products,byproducts or waste products located on the site of such operations;(inactive mining operations are
mining sites that are not being actively mined,but which have an identifiable owner/operator;inactive mining sites do not include sites
1-15

FORM 1-GLOSSARY CONTINUED
where mining claims are being maintained prior to disturbances associated with the extraction,beneficiation,or processing of mined
materials,nor sites where minimal activities are undertaken for the sole purpose of maintaining a mining claim);
4. Hazardous waste treatment,storage,or disposal facilities,including those that are operating under interim status or a permit under
subtitle C of RCRA;
5. Landfills,land application sites,and open dumps that receive or have received any industrial wastes(waste that is received from any
of the facilities described under this subsection)including those that are subject to regulation under subtitle D of RCRA;
6. Facilities involved in the recycling of materials,including metal scrapyards,battery reclaimers,salvage yards,and automobile
junkyards,including but limited to those classified as Standard Industrial Classification 5015 and 5093;
7. Steam electric power generating facilities,including coal handling sites;
8. Transportation facilities classified as Standard Industrial Classifications 40,41,42(except 4221-25),43,44,45,and 5171 which have
vehicle maintenance shops,equipment cleaning operations,or airport deicing operations.Only those portions of the facility that are
either involved in vehicle maintenance(including vehicle rehabilitation,mechanical repairs,painting,fueling,and lubrication),
equipment cleaning operations,airport deicing operations,or which are otherwise identified under paragraphs 1-7 or 9-11 are
associated with industrial activity;
9. Treatment works treating domestic sewage or any other sewage sludge or wastewater treatment device or system,used in the
storage treatment,recycling,and reclamation of municipal or domestic sewage,including land dedicated to the disposal of sewage
sludge that are located within the confines of the facility,with a design flow of 1.0 mgd or more,or required to have an approved
pretreatment program under 40 CFR 403.Not included are farm lands,domestic gardens or lands used for sludge management
where sludge is beneficially reused and which are not physically located in the confines of the facility,or areas that are in compliance
with section 405 of the CWA;
10. Construction activity including clearing,grading and excavation,except operations that result in the disturbance of less than five acres
of total land area.Construction activity also includes the disturbance of less than five acres of total land area that is a part of a larger
common plan of development or sale if the larger common plan will ultimately disturb five acres or more;
11. Facilities under Standard Industrial Classifications 20,21,22,23,2434,25,265,267,27,283,285,30,31 (except 311),323,34
(except 3441),35,36,37(except 373),38,39,and 4221-25.
TOXIC POLLUTANT means any pollutant listed as toxic under section 307(a)(1)or,in the case of"sludge use or disposal practices,"any
pollutant identified in regulations implementing section 405(d)of the CWA.
TREATMENT WORKS TREATING DOMESTIC SEWAGE(TWTDS)means a POTW or any other sewage sludge or waste water
treatment devices or systems,regardless of ownership(including federal facilities),used in the storage,treatment,recycling,and
reclamation of municipal or domestic sewage,including land dedicated for the disposal of sewage sludge.This definition does not include
septic tanks or similar devices.For purposes of this definition,"domestic sewage"includes waste and waste water from humans or
household operations that are discharged to or otherwise enter a treatment works.In States where there is no approved State sludge
management program under section 405(f)of the CWA,the Regional Administrator may designate any person subject to the standards for
sewage sludge use and disposal in 40 CFR 503 as a"treatment works treating domestic sewage,"where he or she finds that there is a
potential for adverse effects on public health and the environment from poor sludge quality or poor sludge handling,use or disposal
practices,or where he or she finds that such designation is necessary to ensure that such person is in compliance with 40 CFR 503.
UPSET(defined at§122.41(n))means an exceptional incident in which there is unintentional and temporary noncompliance with
technology based permit effluent limitations because of factors beyond the reasonable control of the permittee.An upset does not include
noncompliance to the extent caused by operational error,improperly designed treatment facilities,inadequate treatment facilities,lack of
preventive maintenance,or careless or improper operation.
VARIANCE means any mechanism or provision under section 301 or 316 of the CWA or under 40 CFR 125,or in the applicable"effluent
limitations guidelines"which allows modification to or waiver of the generally applicable effluent limitation requirements or time deadlines of
the CWA.This includes provisions which allow the establishment of alternative limitations based on fundamentally different factors or on
sections 301(c),301(g),301(h),301(i),or 316(a)of the CWA.
WATERS OF THE UNITED STATES as defined at§122.2.
WHOLE EFFLUENT TOXICITY(WET)means the aggregate toxic effect of an effluent measured directly by a toxicity test.
1-16

EPA Identification Number NPDES Permit Number Facility Name Form Approved 03105/19
International Tie OMB No.2040-0004
Form U.S.Environmental Protection Agency
t COMA Application for NPDES Permit to Discharge Wastewater
NPDES GENERAL INFORMATION
SECTIONe •D i
1.1 Applicants Not Required to Submit Form 1
Is the facility a new or existing publicly owned Is the facility a new or existing treatment works
1.1.1 treatment works? 1.1'2
treating domestic sewage.
If yes, STOP. Do NOT complete ® No If yes, STOP.Do NOT ® No
Form 1.Complete Form 2A. complete Form 1. Complete
Form 2S.
1.2 Applicants Required to Submit Form 1
1.2.1 Is the facility a concentrated animal feeding 1.2.2 Is the facility an existing manufacturing,
operation or a concentrated aquatic animal commercial,mining,or silvicultural facility that is
IL production facility? currently discharging process wastewater?
oYes 4 Complete Form 1 No Yes 4 Complete Form No
z and Form 26. 1 and Form 2C.
1.2.3 Is the facility a new manufacturing,commercial, 1.2.4 Is the facility a new or existing manufacturing,
mining,or silvicultural facility that has not yet commercial,mining,or silvicultural facility that
commenced to discharge? discharges only nonprocess wastewater?
❑ Yes 4 Complete Form 1 ❑ No ❑ Yes 4 Complete Form No
and Form 2D. 1 and Form 2E.
1.2.5 Is the facility a new or existing facility whose
W discharge is composed entirely of stormwater
a associated with industrial activity or whose
discharge is composed of both stormwater and
non-stormwater?
® Yes 4 Complete Form 1 E] No
and Form 2F
unless exempted by
40 CFR
122.26(b)(14)(x)or
(b)(15).
SECTION 2. NAME,MAILING ADDRESS,AND LOCATIONr
2.1 Facility Name
International Tie Disposal, LLC-Project Tie
0 2.2 EPA Identification Number
Y
l)
U
0 New Facility
R 2.3 Facility Contact
Name(first and last) Title Phone number
Basil A. Polivka Director of Pyrolysis 704-321-0802
Email address
[e-mail]
C6, 2A Facility mailing Address
a
Street or P.O.box
13700 Providence Rd
City or town State ZIP code
Weddington NC 28104
EPA Form 3510-1(revised 3-19) Page 1

EPA Identification Number NPOES Permit Number Facility Name Form Approved 03/05/19
International Tie OMB No.2040-0004
2.5 Facility Location
Street,route number,or other specific identifier
Q o 174 Marks Creek Church Road
cn U
o County name County code(if known)
g U Richmond
E a City or town State ZIP code
z Hamlet NC 28345
SECTION •D 1
3.1 SIC Code(s) Description(optional)
3624 Carbon and Graphite Products
N
d
a
U
Z 3.2 NAICS Code(s) Description(optional)
R 335991 Carbon and Graphite Product Manufacturing
U
V7
4.1 Name of Operator
International Tie Disposal, LLC
0 4.2 Is the name you listed in Item 4.1 also the owner?
co
E m Yes ❑ No
0
4.3 Operator Status
❑ Public—federal ❑ Public—state ❑ Other public(specify)
o ® Private ❑ Other(specify)
4.4 Phone Number of Operator
704-321-O B02
4.5 0 eratorAddress
Street or P.O.Box
E 13700 Providence Rd
City or town State ZIP code
o 0 Weddington NC 2B104
12
a Email address of operator
O [e-mail]
SECTION • I
5.1 Is the facility located on Indian Land?
M ca
J ❑ Yes ❑ No
EPA Form 3510.1(revised 3-19) Page 2

EPA identification Number NPDES Permit Number Facility Name Form Approved 03l05119
International Tie OMB No.2040-0004
SECTION -• 1
6.1 Existing Environmental Permits(check all that apply and print or type the corresponding permit number for each)
CU
❑ NPDES(discharges to surface ❑ RCRA(hazardous wastes) ❑ UIC(underground injection of
22 water) fluids)
n E
w a ® PSD(air emissions) ❑ Nonattainment program(CAA) ❑ NESHAPs(CAA)
NCDEQ 10676R00
w ❑ Ocean dumping(MPRSA) ❑ Dredge or fill(CWA Section 404) ❑ Other(specify)
SECTIONr
7.1 Have you attached a topographic map containing all required information to this application?(See instructions for
specific requirements.)
®Yes ❑ No ❑ CAFO—Nat Applicable(See requirements in Form 213)
SECTIONOF 1
8.1 Describe the nature of your business.
Project Tie is a greenfield biochar manufacturing facility. The facility will receive untreated lumber and
creosote-treated railroad ties by railcar in the tie unloading/sorting area. Received materials will be offloaded
N and stacked in the raw material storage area. Raw material from the storage area is then fed into a crusher
c where it's reduced in size to 3 to.4-inch by 12 to 18-inch and then loaded into individual kilns. The crusher is
uncovered and located on a 200'x200'asphalt pad.A kiln loaded with raw material is then transported to the
°a processing area. Pyrolysis is initiated with natural gas combustion and continues to process for 7 to 8 hours
0 after the kiln burner is turned off. Kilns that have completed pyrolysis are then moved to a cooling area for 10
to 18 hours.After the cool-down period,the kiln containing biochar is transported to the biochar handling and
z packaging line located inside multiple sealed intermodal shipping containers. The biochar is then bagged in
super sacks and moved to the biochar storage area for loading onto railcars.
SECTION •• F
9A Does your facility use cooling water?
a�
❑ Yes ❑ No -* SKIP to Item 10.1.
9.2 Identify the source of cooling water. (Note that facilities that use a cooling water intake structure as described at
40 CFR 125, Subparts 1 and J may have additional application requirements at 40 CFR 122.21(r).Consult with your
o U) NPDES permitting authority to determine what specific information needs to be submitted and when.)
o R
� C
SECTION1 VARIANCE REQUESTS1 1
10.1 Do you intend to request or renew one or more of the variances authorized at 40 CFR 122.21(m)?(Check all that
en apply.Consult with your NPDES permitting authority to determine what information needs to be submitted and
when.)
❑ Fundamentally different factors(CWA ❑ Water quality related effluent limitations(CWA Section
Section 301(n)) 302(b)(2))
co
❑ Non-conventional pollutants(CWA ❑ Thermal discharges(CWA Section 316(a))
Section 301(c)and(g))
® Not applicable
EPA Form 3510-1(revised 3-19) Page 3

EPA Identification Number NPOES Permit Number Facility Name Form Approved 03105/19
International Tie OMB No.2040-0004
CERTIFICATIONSECTION 11.CHECKLIST AND rl
11.1 In Column 1 below, mark the sections of Form 1 that you have completed and are submitting with your application.
For each section,specify in Column 2 any attachments that you are enclosing to alert the permitting authority. Note
that not all applicants are required to provide attachments.
Column 1 Column 2
® Section 1:Activities Requiring an NPDES Permit ❑ wl attachments
® Section 2: Name,Mailing Address,and Location ❑ wl attachments
® Section 3: SIC Codes ❑ wf attachments
® Section 4: Operator Information ❑ wi attachments
❑ Section 5: Indian Land ❑ wl attachments
® Section 6: Existing Environmental Permits ® wi attachments
m
E wl topographic
® Section 7: Map ® map El wl additional attachments
o ® Section 8: Nature of Business ® wi attachments
❑ Section 9:Cooling Water Intake Structures ❑ wl attachments
a
❑ Section 10:Variance Requests ❑ wl attachments
Section 11:Checklist and Certification Statement ❑ wl attachments
Y
w 11.2 Certification Statement
U
l certify under penalty of law that this document and all attachments were prepared under my direction or supervision
in accordance with a system designed to assure that qualified personnel properly gather and evaluate the
information submitted.Based on my inquiry of the person or persons who manage the system,or those persons
directly responsible for gathering the information, the information submitted is, to the best of my knowledge and
belief, true, accurate, and complete.l am aware that there are significant penalties for submitting false information,
including the possibility of fine and imprisonment for knowing violations.
Name(print or type first and last name) Official title
Basil Polivka II Member
Signature Date signed
April 26th, 2023
Click to go back to the beginning of Form
EPA Form 3510-1(revised 3-19) Page 4

United States Office of Water EPA Form 3510-2F
Environmental Protection Agency Washington,D.C. Revised March 2019
Water Permits Division
..EPA Application Form 2F
Stormwater Discharges
Associated with Industrial
Activity
NPDES Permitting Program
Note: Complete this form and Form 1 if you are a new or existing facility whose discharge is composed
entirely of stormwater associated with industrial activity,excluding discharges from construction
activity under 40 CFR 122.26(b)(14)(x)or(b)(15). If your discharge is composed of stormwater and
non-stormwater, you must complete Forms 1 and 2F,and you must complete Form 2C, 21), or 2E, as
appropriate. See the"Instructions" inside for further details.

Paperwork Reduction Act Notice
The U.S. Environmental Protection Agency estimates the average burden to collect and complete
Form 2F to be 28.1 hours.The estimate includes time for reviewing instructions, searching existing data
sources, gathering and maintaining the needed data,and completing and reviewing the collection of
information. Send comments about the burden estimate or any other aspect of this collection of
information, including suggestions for reducing the burden,to the Chief, Information Policy Branch
(PM-223), U.S. Environmental Protection Agency, 1200 Pennsylvania Avenue,NW, Washington, DC
20460, and to the Office of Information and Regulatory Affairs, Office of Management and Budget,
725 171h Street,NW, Washington, DC 20503, marked "Attention: Desk Officer for EPA."

FORM 2F—INSTRUCTIONS
General Instructions Where to File Your Completed Form
Who Must Complete Form 2F? Submit your completed application package(Forms 1 and 2F plus
You must complete Form 2F if you answered"Yes"to Item 1.2.5 on any other applicable forms)to your NPDES permitting authority.
Form 1—that is,you are a new or existing facility and your Consult Exhibit 1-1 of Form 1's"General Instructions"to identify
discharge is composed entirely of stormwater associated with your NPDES permitting authority.
industrial activity(excluding discharges from construction activity Public Availability of Submitted Information
under 40 CFR 122.26(b)(14)(x)or(b)(15))orcomposed of
stormwater and non-stormwater and are seeking coverage under The U.S.Environmental Protection Agency(EPA)will make
an individual National Pollutant Discharge Elimination System information from NPDES permit application forms available to the
(NPDES)permit.Note that applicants in the latter category must public for inspection and copying upon request.You may not claim
also complete Forms 2C,2D,or 2E,as applicable.See inset any information on Form 2F(or related attachments)as confidential.
below, You may make a claim of confidentiality for any information that you
submit to EPA that goes beyond the information required by Form
Notes 2F.Note that NPDES permitting authorities will deny claims for
• Form 2F must be completed by any operator of treating any effluent data(estimated or actual)as confidential.If you
a facility that discharges stormwater associated do not assert a claim of confidentiality at the time you submit your
with industrial activity or the operator of any information to the NPDES permitting authority,EPA may make the
stormwater discharger that EPA is evaluating for information available to the public without further notice to you.EPA
designation as a significant contributor of will handle claims of confidentiality in accordance with the Agency's
pollutants to waters of the United States,or as business confidentiality regulations in Part 2 of Title 40 of the Cade
contributing to a violation of a water quality of Federal Regulations(CFR).
standard. Completion of Forms
• For discharges composed entirely of Print or type in the specified areas only.If you do not have enough
stormwater,the operator must complete space on the form to answer a question,you may continue on
Form 2F in conjunction with Form 1. additional sheets,as necessary,using a format consistent with the
• For discharges of stormwater combined with form.
process wastewater,the operator must
complete and submit Form 2F,Form 1,and Provide your EPA Identification Number from the Facility Registry
Form 2C.Process wastewater is water that Service,NPDES permit number,and facility name at the top of each
comes into direct contact with or results from page of Form 2F and any attachments. If your facility is new(i.e.,
the production or use of any raw material, not yet constructed),write or type"New Facility"in the space
intermediate product,finished product, provided for the EPA Identification Number an NPDES permit
byproduct,waste product,or wastewater. number.If you do not know your EPA Identification Number,contact
• For discharges of stormwater combined with your NPDES permitting authority.See Exhibit 1-1 of Form 1's
"General Instructions"for contact information.Additionally,for
complete Form 2F,Form 1,and Form 2E.oup wastewater,the operator must Tables A through D,provide the applicable outfall number at the top
c F of each page.
Nonprocess wastewater includes noncontact
cooling water and sanitary wastes that are not Do not leave any response areas blank unless the form directs you
regulated by effluent guidelines,except to skip them.If the form directs you to respond to an item that does
discharges by educational,medical,or not apply to your facility or activity,enter"NA"for"not applicable"to
commercial chemical laboratories. show that you considered the item and determined a response was
• For new discharges of stormwater associated not necessary for your facility.
with industrial activity that will be combined with The NPDES permitting authority will consider your application
other new non-stormwater discharges,the complete when it and any supplementary material are received and
operator must submit Form 2F,Form 1,and completed according to the authority's satisfaction.The NPDES
Form 2D. permitting authority will judge the completeness of any application
independently of the status of any other permit application or permit
for the same facility or activity.
Definitions
The legal definitions of all key terms used in these instructions and
Form 2F are in the"Glossary"at the end of the"General
Instructions"in Form 1.
2F-1

FORD 2F—INSTRUCTIONS CONTINUED
Line-by-Line Instructions Section 3.Site Drainage Map
Section 1.Outfall Location Item 3.1 Attach a site drainage map showing the topography of the
Item 1.1.Identify each of the facility's outfalls by number.For each facility. If a topographic map is unavailable,you may provide an
outfall,specify the latitude and longitude to the nearest 15 seconds outline of drainage areas served by the outfall(s)covered in the
and name of the receiving water. Latitude and longitude application.The site map must include the following information:
coordinates may be obtained in a variety of ways,including use of . Each of its drainage and discharge structures.
hand held devices(e.g.,a GPS enabled smartphone),internet . The drainage area of each stormwater outfall.
mapping foals(e.g.,
httosalmynasadata.larc.nasa.gov/latitudelongitude-finde ,rl� • Paved areas and buildings within the drainage area of each
geographic information systems(e.g.,ArcView),or paper maps stormwater outfall;each past or present area used for outdoor
from trusted sources(e.g.,U.S.Geological Survey or USGS).The storage or disposal of significant materials;each existing
location of each outfalI(i.e.,where the coordinates are collected) structural control measure to reduce pollutants in stormwater
shall be the location where collected and concentrated stormwater runoff;materials loading and access areas;and areas where
flows are discharged from the facility such that the first receiving pesticides,herbicides,soil conditioners,and fertilizers are
water body into which the discharge flows,either directly or applied.
through a separate storm sewer system,is a water of the United . Each hazardous waste treatment,storage,or disposal facility
States. If you need further guidance in responding to Item 1.1,refer (including each area not required to have a Resource
to http:llwww.epa.govlgeosoaiialllatitudelonqitude-data-standard. Conservation and Recovery Act permit and is used for
Note: In EPA's stormwater permits,"outfalls"are referred to as accumulating hazardous waste for less than 90 days under
"discharge points." 40 CFR 262.34).
• Each well where fluids from the facility are injected
Note that space has been provided on the form for six outfalls. If underground.
you have more than this number,type your information on a
separate sheet of paper in a format similar to that of the form. • Springs and other surface water bodies that receive stormwater
Make sure you note the EPA Identification Number,NPDES permit discharges from the facility.
number,and facility name at the top of the page and indicate the When you have completed and attached your site map to Form 2F,
specific item of the form to which you are responding—Item 1.1 in answer"Yes"to Item 3.1.
this case.In other sections of the form,you will be asked to provide Section 4.Pollutant Sources
information by outfall number(Sections 2,4, 5,and 7). Item 4.1.List all outfalls discharging stormwater. Provide an
Section 2.Improvements estimate of the impervious surface area drained by the outfall.
Item 2.1.Indicate it you are required by any federal,state,or local Specify units of measure.(Impervious surfaces are surfaces where
authority to meet an implementation schedule for constructing, stormwater runs off at rates significantly higher than background
upgrading,or operating wastewater treatment equipment or rates--e.g., predevelopment levels.They include paved areas,
practices or any other environmental programs that could affect the building roofs,parking lots,and roadways.)
discharges described in this application.The requirements include, Provide an estimate of the total surface area(impervious and
but are not limited to,permit conditions,administrative enforcement pervious areas)drained by each outfall(within a mile radius of the
orders,enforcement compliance schedule letters,stipulations, facility).You may use the site map developed under Item 3.1 to
court orders,and grant or loan conditions.If yes,continue to Item estimate the total area drained by each oulfall. For areas under
2.2.If no,skip to Section 3. 5 acres,consult your NPDES permitting authority to determine
Item 2.2.Briefly identify and describe each applicable project(e.g., whether the area should be reported to the nearest tenth of an acre
consent decree,enforcement order,or permit condition).For each or nearest quarter of an acre.
condition,specify the affected outfall number(s),the source(s)of Item 4.2.Provide a narrative description of the following:
the discharge,the required final compliance date,and the
projected final compliance date. Significant materials that in three years prior to the submittal of
this application have been treated,stored,or disposed of in a
Item 2.3.OPTIONAL ITEM.Indicate if you have attached any manner to allow exposure to stormwater.
sheets describing any additional water pollution control programs • Method of treatment,storage,or disposal of such materials.
(or other environmental projects that could affect your discharges)
that you may now have underway or planned. If you attach • Materals management practices employed,in the three years
additional sheets,indicate in the attachment whether each program prior to the submittal of this application,to minimize contact by
is actually underway or is planned,and indicate your actual or these materials with stormwater runoff.
planned schedule for construction.Be sure to note your EPA • Materials loading and access areas.
Identification Number, NPDES permit number,and facility name at • The location,manner,and frequency in which pesticides,
the top of any attached pages. herbicides,soil conditioners,and fertilizers are applied.
You should identify your significant materials by chemical name,
2F-2

FORM 2F—INSTRUCTIONS CONTINUED
form(e.g.,powder,liquid,etc.),and type of container or treatment Tables A,B,C,and D
unit. Indicate any materials treated,stored,or disposed of Items 7.2 to 7.17.These items require you to collect and report data
together.The term"significant materials"includes,but is not in Tables A through D,at the end of Form 2F,for the parameters and
limited to:raw materials;fuels;materials such as solvents, pollutants listed in Exhibits 2F-2,2F-3,and 2F4(at the end of the
detergents,and plastic pellets;finished materials such as metallic instructions).The instructions for completing Tables A through D are
products;raw materials used in food processing or production; table-specific,as are the criteria for determining who should
hazardous substances designated under Section 101(14)of the complete them.
Comprehensive Environmental Response,Compensation,and
Liability Act;any chemical the facility is required to report pursuant Important note:Read the"General Instructions for Reporting,
to Section 313 of Title III of the Superfund Amendments and Sampling,and Analysis"below before completing Items 7.2 to 7.17.
Reauthorization Act;and fertilizers;pesticides;and waste products Item 7.2 and Table A.All applicants must complete Table A.If the
such as ashes,slag,and sludge that have the potential to be discharge is an existing discharge and your discharge is composed
released with stormwater discharges. exclusively of stormwater(i.e.,no process or nonprocess
Item 4.3.For each outfall,list the location and type of existing wastewater)then you only need to provide monitoring data for oil and
structural and non-structural control measure(s)to reduce grease,total phosphorus,total Kjeldahl nitrogen,and total nitrogen.
pollutants in stormwater runoff.Structural controls include Indicate NA"for not applicable"in the columns for all other
structures that enclose materials handling or storage areas; parameters.Answer"Yes"to Item 7.2 once you have completed this
structures that cover materials;and berms,dikes,or diversion task.
ditches around manufacturing,production,storage,or treatment Item 7.3 and Table B.Indicate whether the facility is subject to an
units and retention ponds. Spill prevention plans,employee effluent limitations guideline(ELG)(see 40 CFR Subchapter N to
training,visual inspections,preventive maintenance,and determine which pollutants are limited in ELGs)or if the facility is
housekeeping measures are examples of non-structural controls. subject to effluent limitations in an NPDES permit for its process
wastewater or stormwater(if the facility is operating under an existing
Describe the treatment,including the schedule and type of maintenance activities performed,and the ultimate disposal of any NPDES permit).If yes,continue to Item 7.4.If no,skip to Item 7.5.
solid or fluid wastes other than by discharge.For each structural Note:Stormwater discharges from certain industrial sources or
control identified,indicate the type of treatment the stormwater activities have specific ELGs for which they must comply.These
receives using the codes in Exhibit 2F-1,at the end of the stormwater-specific ELGs include:
instructions.For each non-structural control identified,indicate Regulated Discharge 40 CFR Section
"Not Applicable"in the"Codes from Exhibit 2F-1"column. Discharges resulting from spraydown or intentional Part 429,Subpart I
Section 5.Non-Stormwater Discharges wetting of logs at wet deck storage areas
Runoff from phosphate fertilizer manufacturing facilities Part 418,Subpart A
Item 5.1.Provide a certification that all outfalls that should contain that comes into contact with any raw materials,finished
stormwater discharges associated with industrial activity have product,byproducts or waste products(SIC 2874)
been tested or evaluated for the presence of non-stormwater Runoff from asphalt emulsion facilities Part 443,Subpart A
discharges.Tests for such non-stormwater discharges can include Runoff from material storage piles at cement Part 411,Subpart C
smoke tests,fluorometric dye tests,analysis of accurate manufacturing facilities
schematics,and others. Mine dewatering discharges at crushed stone, Part 436,Subparts B,
construction sand and gravel,or industrial sand mining C,and D
Item 5.2.Include a description of the method used,the date of any facilities
testing,and the onsite drainage points that were directly observed Runoff from hazardous waste and non-hazardous waste Part 445,Subparts A
during a test used to support the certification in Item 5.1.All non- landfills and B
stormwater discharges must be identified in a Form 2C,2D,or 2E. Runoff from coal storage piles at steam electric Part 423
See"Who Must Complete Form 2F?"above for more information. generating facilities
Section 6.Significant Leaks or Spills Runoff containing urea from airfield pavement deicing at Part 449
existing and new primary airports with 1,000 or more
Item 6.1.Describe any significant leaks or spills of toxic or annual non-propeller aircraft departures
hazardous pollutants at the facility within the three years prior to Item 7.4.In Table B,list all pollutants that are limited in an ELG to
the submittal of this application.Include the approximate date and which the facility is subject and all pollutants listed in the facility's
location of the spill or leak and the type and amount of material NPDES permit for its process wastewater(if the facility is operating
released. under an existing NPDES permit)and provide quantitative data for
Section 7.Discharge Information each pollutant(provide actual data for existing dischargers and
Item 7.1.Answer whether you are a new source or new discharge. estimated data for new sources and new dischargers).If a pollutant
Contact your NPDES permitting authority to determine if you are a in Exhibits 2F-2 or 2F-3 is indirectly limited by an ELG through an
new source or new discharge. indicator(e.g.,use of total suspended solids as an indicator to
control the discharge of iron and aluminum),you must provide data
for the pollutant in Table B.Complete one table for each outfall.
Answer"Yes"to Item 7A once you have completed this task.
2F-3

FORM 2F—INSTRUCTIONS CONTINUED
Item 7.5 and Table C.Table C requires you to address the Item 7.11. Provide quantitative data in Table C for those pollutants
pollutants in Exhibits 2F-2,2F-3,and 2F4 for each outfall. in Exhibit 2F-3 that you expect to be discharged in concentrations
Pollutants in each of these exhibits are addressed differently. of 10 ppb or greater(provide actual data for existing dischargers
Indicate whether you know or have reason to believe any pollutants and estimated data for new sources and new dischargers).Answer
in Exhibit 2F-2 are present in the discharge. If yes,continue to Item "Yes"to Item 7.11 once you have completed this task.
7.6. If no,skip to Item 7.7. Item 7.12.Indicate whether you expect acrolein,acrylonitrile,2,4-
Item 7.6,For each outfall,list all pollutants in Exhibit 2F-2 that you dinitrophenol,or 2-methyl-4,6-dinitrophenol to be discharged in
know or have reason to believe are present in the discharge in concentrations of 100 ppb or greater.If yes,continue to Item 7.13.
Table C(except pollutants previously listed in Table 8 that are If no,skip to Item 7.14.
limited directly or indirectly by an ELG)and either report quantitative Item 7.13.Provide quantitative data in Table C for the pollutants
data or briefly describe the reasons the pollutant is expected to be identified in Item 7.12 that you expect to be discharged in
discharged.Answer"Yes"to Item 7.6 once you have completed this concentrations of 100 ppb or greater(provide actual data for
task. existing dischargers and estimated data for new sources and new
Item 7.7.This item asks if you qualify as a"small business. If so, dischargers).Answer"Yes"to Item 7,13 once you have completed
you are exempt from the reporting requirements for the organic toxic this task.
pollutants listed in Exhibit 2F-3. Item 7.14.For any pollutants you expect to be present in the
You can qualify as a small business in two ways: (1) If your facility is discharge at concentrations less than 10 ppb(or less than 100 ppb
a coal mine and if your probable total annual production is less than for the above four pollutants),either submit quantitative data or
100,000 tons per year,you may submit past production data or briefly describe the reasons the pollutant is expected to be
estimated future production(such as a schedule of estimated total discharged in Table C.Answer"Yes"to Item 7.14 once you have
production under 30 CFR 795.14(c))instead of conducting analyses completed this task,
for the organic toxic pollutants;(2)If your facility is not a coal mine Item 7.15.Indicate whether you know or have reason to believe
and if your gross total annual sales for the most recent three years any pollutants in Exhibit 2F4 are present in the discharge.If yes,
average less than$100,000 per year(in second quarter 1980 continue to Item 7.16.If no,skip to Item 7.17.
dollars),you may submit sales data for those years instead of Item 7.16.For each outfall,list any pollutant in Exhibit 2F-4 that
conducting analyses for the organic toxic pollutants.The production you know or believe to be present in the discharge in Table C and
or sales data must be for the facility that is the source of the explain why you believe it to be present. No analysis is required,
discharge.The data should not be limited to production or sales for but if you have analytical data,you must report it.Answer"Yes'to
the process or processes that contribute to the discharge,unless Item 7.16 once you have completed this task.
those are the only processes at your facility. For sales data,in
situations involving intra-corporate transfer of goods and services, Note:Under40 CFR 117.12(a)(2),certain discharges of hazardous
the transfer price per unit should approximate market prices for substances(listed in Exhibit 2F-5)may be exempted from the requirements of
those goods and services as closely as possible. Sales figures for CWA Section 311,which establishes reporting requirements,civil penalties,
years after 1980 should be indexed to the second quarter of 1980 by and liability tar cleanup costs for spills of oil and hazardous substances.A
using the gross national product price deflator(second quarter of discharge of a particular substance can be exempted if the origin,source,and
amount of the discharged substances are identified in the NPDES permit
19BO= 100).This index is available online from the U.S. Department application or in the permit,it the permit contains a requirement for treatment
of Commerce,Bureau of Economic Analysis at of the discharge,and if the treatment is in place.If you would like to apply for
http:llwww.bea.gov/national/pdf]SNTables.odf, an exemption from the requirements of CWA Section 311,attach additional
sheets of paper to your application,selling forth the following information:
If you qualify as a small business according to the criteria above, 1. The substance and the amount of each substance that might be
answer"Yes'to Item 7.7 and skip to Item 7.18,Otherwise, answer discharged.
"No"and continue to Item 7.8. 2. The origin and source of the discharge of the substance.
Item 7.8.Indicate whether you know or have reason to believe any 3. The treatment to be provided for the discharge by:
pollutants In Exhibit 2F-3 are present in the discharge. If yes, a. An onsite treatment system separate from any treatment system
treating your normal discharge;
continue to Item 7.9. If no,skip to Item 7.10. b. A treatment system designed to treat your normal discharge and that
Item 7.9.For each outfall,list all pollutants in Exhibit 2F-3 that you is additionally capable of treating the amount of the substance
know or have reason to believe are present in the discharge in identified under paragraph 1 above;or
c. Any combination of the above.
Table C(except pollutants previously listed in Table B).Answer
"Yes"to Item 7.9 once you have completed this task. See 40 CFR 117.12(a)(2)and(c)or contact your NPDES permitting authority
for further information on exclusions from CWA Secbon 311.
Item 7.10.Indicate whether you expect any of the pollutants from
Exhibit 2F-3 to be discharged in concentrations of 10 parts per Item 7.17 and Table D.Provide data for the storm event(s)that
billion(ppb)or greater. If yes,continue to Item 7.11. If no,skip to resulted in the maximum daily discharges for the flow weighted
Item 7.12. composite sample in Table D.If sampling is conducted during more
than one storm event,you only need to report the information
2F-4

FORM 2F—INSTRUCTIONS CONTINUED
requested on Table D for the storm event(s)that resulted in any Section 10.Checklist and Certification Statement
maximum pollutant concentration reported on Tables A through C. Item 10.1.Review the checklist provided on the application.In
Provide flow measurements or estimates of the flow rate,as well as Column 1,mark the sections of Form 2F that you have completed
the total amount of discharge for the storm event(s)sampled,the and are submitting with your application.For each section in
method of flow measurement,or estimation.Provide the data and Column 2,indicate whether you are submitting attachments.
duration of the storm event(s)sampled,rainfall measurements,or Item 10.2.The Clean Water Act(CWA)provides for severe
estimates of the storm event that generated the sampled runoff and penalties for submitting false information on this application form.
the duration between the storm event sampled and the end of the Section 309(c)(2)of the CWA provides that,"Any person who
previous measurable(greater than 0.1 inch rainfall)storm event. knowingly makes any false material statement,representation,or
Answer"Yes"to Item 7.17 once you have completed this task. certification in any application,...shall upon conviction be punished
Used or Manufactured Toxics by a fine of not more than$10,000 or by imprisonment for not more
Item 7.18.Review Exhibits 2F-2 through 2F4 and determine if you than six months or both."
currently use or manufacture any of the pollutants listed as FEDERAL REGULATIONS AT 40 CFR 122.22 REQUIRE THIS
intermediate or final products or byproducts.If so,answer"Yes." APPLICATION TO BE SIGNED AS FOLLOWS:
You should also answer"Yes"if you know or have reason to
believe that 2,3,7,8-tetrachloro-dibenzo-p-dioxin(TCDD)is A. For a corporation,by a responsible corporate officer,For the
discharged or if you use or manufacture 2,4,5-tdchlorphenoxy purpose of this section,a responsible corporate officer means:
acetic acid(2,4,5-T);2-(2,4,5-t6chlorophenoxy)propanoic acid (1)a president,secretary,treasurer,or vice-president of the
(Silvex,2,4,5-TP);2-(2,4,5-trichlorophenoxy)ethyl,2,2- corporation in charge of a principal business function,or any
dichloropropionate(Erbon);0,0-dimethyl 0-(2,4,5-trichlorphenyl) other person who performs similar policy-or decision-making
phosphorothioate(Ronnel);2,4,5-tdchlorophenol(TCP);or functions for the corporation,or(2)the manager of one or
hexachlorophene(HCP).If your answer to Item 7.18 is"No,"skip to more manufacturing,production,or operating facilities,
Section 8. provided the manager is authorized to make management
decisions which govem the operation of the regulated facility
Item 7.19.List all of the toxic pollutants identified under Item 7.18, including having the explicit or implicit duty of making major
including TCDD.Note that the NPDES permitting authority may capital investment recommendations,and initiating and
waive or modify the requirement if you demonstrate that it would be directing other comprehensive measures to assure long term
unduly burdensome to identify each toxic pollutant and the NPDES environmental compliance with environmental laws and
permitting authority has adequate information to issue your permit. regulations;the manager can ensure that the necessary
You may not claim any information submitted in response to Item systems are established or actions taken to gather complete
7.18 as confidential;however,you do not have to distinguish and accurate information for permit application requirements;
between use or production of the pollutants or list the amounts. and where authority to sign documents has been assigned or
Section 8.Biological Toxicity Testing Data delegated to the manager in accordance with corporate
Item 8.1.Answer whether you know of or have reason to believe procedures.
that biological toxicity testing has been conducted of your B. For a partnership or sole proprietorship,by a general partner
wastewater treatment,including engineering reports or pilot plant or the proprietor,respectively.
studies. If no,skip to Section 9.Otherwise,continue. C. For a municipality,state,federal,or other public facility,by
Item 8.2.List any tests of which you are aware and their purposes. either a principal executive officer or ranking elected official.
For purposes of this section,a principal executive officer of a
Section 9.Contract Analysis Information federal agency includes:(1)The chief executive officer of the
Item 9.1.Indicate if any of the analyses performed in Section 7 agency,or(2)a senior executive officer having responsibility
were performed by a contract laboratory or consulting firm.If no, for the overall operations of a principal geographic unit of the
skip to Section 10.If yes,continue to Item 9.2. agency(e.g.,Regional Administrators of EPA).
Item 9.2.Provide the name,address,phone number,and pollutants END
analyzed by the laboratory or consulting firm(s)in the spaces Submit your completed Form 1,Form 2F,and
provided. all associated attachments
(and any other required NPDES application forms)
to your NPDES permitting authority.
2F-5

General Instructions for Reporting,Sampling,and Analysis
Important note:Read these instructions before completing Tables byproducts,and any previous analyses known to you of your
A through C and Section 7 of Form 2F. effluent or similar effluent.
General Items Sampling
Complete the applicable tables for each outfall at your facility.Be The collection of the samples for the reported analyses should be
sure to note the EPA Identification Number,NPDES permit supervised by a person experienced in performing sampling of
number,facility name,and applicable outfall number at the top of industrial wastewater or stormwater discharges.You may contact
each table page and any associated attachments. your NPDES permitting authority for detailed guidance on sampling
You may report some or all of the required data by attaching techniques and for answers to specific questions.See Exhibit 1-1 of
separate sheets of paper instead of completing Tables A through C Form 1 for contact information.Any specific requirements in the
for each of your outfalls so long as the sheets contain all of the analytical methods—for example,sample containers,sample
required information and are similar in format to Tables A through preservation,holding times,and the collection of duplicate
C.For example,you may be able to print a report in a compatible samples—must be followed.
format from the data system used in your gas chromatography/ The time when you sample should be representative of your normal
mass spectrometry(GC/MS)analysis completed under Table B. operation,to the extent feasible,with all processes that contribute
If you are an existing discharger,you are required to report actual wastewater in normal operation,and with your treatment system
quantitative data.See"Use of Historic Data"below for use of operating properly with no system upsets.Collect samples from the
historic data.If you are a new source or discharge,you may supply center of the flow channel,where turbulence is at a maximum,at a
estimated data along with the source of each estimate.If you have site specified in your present NPDES permit,or at any site adequate
quantitative data available,however,you must provide it.Base for the collection of a representative sample.
estimates on available,in-house or contractor engineering reports, Grab samples must be taken in the first 30 minutes of discharge(or
or any other studies performed on the proposed facility.Use the as soon thereafter as practicable)for pH,temperature,cyanide,total
following codes to report your source information in the"Source of phenols,residual chlorine,oil and grease,fecal coliform(including
Information"column: E.cob)and enterococci(previously known as fecal streptococcus at
Data Source Code 40 CFR 122.26(d)(2)(iii)(A)(3)),and volatile organic compounds.
Engineering reports t You are not required to analyze a flow-weighted composite for these
Actual data from pilot plants 1 parameters.
Estimates from other engineering 2 For all other pollutants,both a grab sample collected during the first
reports 30 minutes(or as soon thereafter as practicable)of the discharge
Data from other similar plants 3 and a flow-weighted composite sample must be analyzed.However,
Best professional estimates 4 a minimum of one grab sample may be taken for effluents from
Others 5 and het cif on holding ponds or other impoundments with a retention period of
greater than 24 hours.
No later than 24 months after your facility commences to
discharge,you must complete and submit sampling and analysis All samples must be collected from the discharge resulting from a
data for the pollutants and parameters in Tables A through C. storm event that is greater than 0.1 inches and at least 72 hours
However,you need not report results for tests you have already from the previously measurable(greater than 0.1 inch rainfall)storm
performed and reported under the discharge monitoring event.Where feasible,the variance in the duration of the event and
requirements of your NPDES permit. the total rainfall of the event should not exceed 50 percent from the
Table A requires you to report at least one analysis for each average or median rainfall event in that area.
pollutant listed.Tables B and C require you to report analytical data A grab sample must be taken during the first 30 minutes of the
in two ways.For some pollutants addressed in Tables B and C,if discharge(or as soon thereafter as practicable),and a flow-
you know or have reason to know that the pollutant is present in weighted composite must be taken for the entire event or for the first
your discharge,you may be required to list the pollutant and test three hours of the event.
(sample and analyze)and report the levels of the pollutants in your Grab and composite samples are defined as follows:
discharge.For all other pollutants addressed in Tables B and C,
you must list the pollutant if you know or have reason to know that Grab sample:An individual sample of at least 100 milliliters
the pollutant is present in the discharge,and either report collected during the first 30 minutes(or as soon thereafter as
quantitative data for the pollutant or briefly describe the reasons practicable)of the discharge.This sample is to be analyzed
the pollutant is expected to be discharged,(See Items 7.2 through separately from the composite sample.
7.17 of the instructions for completing Tables A through C.).Base Flow-weighted composite sample:A flow-weighted composite
your determination that a pollutant is/will be present in your sample may be taken with a continuous sampler that proportions the
discharge on your knowledge of the facility's raw materials, amount of sample collected with the flow rate or as a combination of
material management practices,maintenance chemicals,history of a minimum of three sample aliquots taken in each hour of discharge
spills and releases,intermediate and final products and
2F-6

General Instructions for Reporting,Sampling,and Analysis Continued
for the entire event or for the first three hours of the event,with All reporting of values for metals must be in terms of"total
each aliquot being at least 100 milliliters and collected with a recoverable metal"unless:
minimum period of 15 minutes between aliquot collections.The
composite must be flow proportional;the time interval between An applicable,promulgated ELt specifies the limitation for the
either each aliquot or the volume of each aliquot must be metal in dissolved,valent,or total form;
proportional to either the stream(effluent)flow at the time of • All approved analytical methods for the metal inherently
sampling or the total stream(effluent)flow since the collection of measure only its dissolved form(e.g.,hexavalent chromium);
the previous aliquot.Aliquots may be collected manually or or
automatically.Where GC/MS volatile organic analysis is required, . The NPDES permitting authority has determined that in
aliquots must be combined in the laboratory immediately before establishing case-by-case limitations it is necessary to express
analysis.Only one analysis for the composite sample is required. the limitations of the metal in dissolved,valent,or total form to
Use of Historical Data carry out the provisions of the CWA.
Existing data may be used,if available,in lieu of sampling If you measure only one grab sample and one flow-weighted
conducted solely for the purposes of this application,provided it is composite sample for a given outfall,complete only the"Maximum
representative of the present discharge and was collected within Daily Discharge"columns in the tables and enter"'I"in the"Number
3 years of the application due date.If you sample for a listed of Storm Events Sampled"column.The NPDES permitting authority
pollutant on a monthly or more frequent basis,summarize the data may require you to conduct additional analyses to further
collected within one year of the application for the pollutant(s)at characterize your discharges.
issue. If you measure more than one value for a grab sample or a flow-
Among the factors that would cause the data to be weighted composite sample for a given outfall and those values are
unrepresentative are significant changes in production level; representative of your discharge,you must report them.You must
changes in raw materials,processes,or final products;and describe your method of testing and analysis.
changes in stormwater treatment.The NPDES permitting authority The"Average Daily Discharge"column on Tables A to C is not
may request additional information,including current quantitative compulsory but should be filled out if data are available.To
data,if they determine it to be necessary to assess your complete the"Average Daily Discharge"column,determine the
discharges.The NPDES permitting authority may allow or establish average of all values within the last year and report the
appropriate site-specific sampling procedures or requirements concentration and mass.Report the total number of storm events
including sampling locations,the season in which the sampling sampled under the"Number of Storm Events Sampled"column.
takes place,the minimum duration between the previous
measurable storm event and the storm event sampled,the Substantially Identical Outfalls
minimum or maximum level of precipitation required for an If you have two or more substantially identical outfalls,you may
appropriate storm event,the form of precipitation sampled(snow request permission from your NPDES permitting authority to sample
melt or rainfall),protocols for collecting samples under 40 CFR 1361 and analyze only one outfall and submit the results of the analysis
and additional time for submitting data on a case-by-case basis. for all substantially identical outfalls.If your request is granted,
Reporting submit the following information on a separate sheet attached to the
Report sampling results for all pollutants in Tables A through C as application form:the identity of the outfall you did test and an
concentration and mass,with the exception of flow,temperature, explanation of how it is substantially identical to the outfall(s)that
pH,color,and fecal coliform organisms. you did not test.
Flow,temperature,pH,color,and fecal coliform organisms must Analysis
be reported as million gallons per day(mgd),degrees Celsius Except as specified below,all required quantitative data shall be
(°C),standard units,color units,and most probable number per collected in accordance with sufficiently sensitive analytical methods
100 milliliters(MPN/100 mQ,respectively.Use the following approved under 40 CFR 136 or required under 40 CFR chapter I,
abbreviations in the columns requiring"units"in Tables A through subchapter N or 0.A method is"sufficiently sensitive"when:
C.
• The method minimum level(ML)is at or below the level of the
Concentration Mass applicable water quality criterion for the measured pollutant or
m=parts per million Ibs=pounds pollutant parameter.
m /L=milligrams per liter ton=tons(English tons . The method ML is above the water quality criterion,but the
b=parts per billion mg=milligrams amount of the pollutant or pollutant parameter in the facility's
IL=micrograms per liter q=grams discharge is high enough that the method detects and
MPN=most probable number per ka=kilograms
quantifies the level of the pollutant or pollutant parameter in the
100 milliliters T=tonnes metric tnnql discharge.
2F-7

General Instructions for Reporting,Sampling,and Analysis Continued
• The method has the lowest ML of the analytical methods select a different method from the remaining EPA-approved
approved under 40 CFR 136 or required under 40 CFR methods that is sufficiently sensitive consistent with 40 CFR
chapter I,subchapter N or 0,for the measured pollutant or 122.21(e)(3)(i).Where no other EPA-approved methods exist,you
pollutant parameter. must select a method consistent with 40 CFR 122.21(e)(3)(ii).
Consistent with 40 CFR 136,you may provide matrix-or sample- When there is no analytical method that has been approved under
specific MLs rather than the published levels.Further,where you 40 CFR 136;required under 40 CFR chapter I,subchapter N or 0,
can demonstrate that,despite a good faith effort to use a method and is not otherwise required by the NPDES permitting authority,
that would otherwise meet the definition of"sufficiently sensitive," you may use any suitable method but shall provide a description of
the analytical results are not consistent with the quality assurance the method.When selecting a suitable method,other factors such
(QA)lquality control(QC)specifications for that method,then the as a method's precision,accuracy,or resolution,may be considered
NPDES permitting authority may determine that the method is not when assessing the performance of the method.
performing adequately and the NPDES permitting authority should
2F-8

Exhibit 2F-1.Codes for Treatment Units and Disposal of Wastes Not Discharged
1. PHYSICAL TREATMENT PROCESSES
1—A.................Ammonia stripping 1—M................Grit removal
1-13.................Dialysis 1—N................Microstraining
1—C................Diatomaceous earth filtration 1-0................Mixing
1—D................Distillation 1—P................Moving bed filters
1—E.................Electrodialysis 1—Q................Multimedia filtration
1—F.................Evaporation 1—R................Rapid sand filtration
1—G................Flocculation 1—S................Reverse osmosis(hyperfiltration)
1—H................Flotation 1—T................Screening
1-1..................Foam fractionation 1—U................Sedimentation(settling)
1—J.................Freezing 1—V................Slow sand filtration
1—K.................Gas-phase separation 1—W...............Solvent extraction
1—L.................Grinding(comminutors) 1—X................Sorption
2. CHEMICAL TREATMENT PROCESSES
2—A.................Carbon adsorption 2—G................Disinfection(ozone)
2-13.................Chemical oxidation 2—H................Disinfection(other)
2—C................Chemical precipitation 2—I..................Electrochemical treatment
2—D................Coagulation 2—J.................Ion exchange
2—E.................Dechlorination 2—K................Neutralization
2—F.................Disinfection(chlorine) 2—L.................Reduction
3, BIOLOGICAL TREATMENT PROCESSES
3—A.................Activated sludge 3—E................Pre-aeration
3-13.................Aerated lagoons 3—F................Spray irrigation/land application
3—C................Anaerobic treatment 3—G................Stabilization ponds
3—D................Nitrification—denitrification 3—H................Trickling filtration
4. WASTEWATER DISPOSAL PROCESSES
4—A.................Discharge to surface Water 4—C................Reuse/recycle of treated effluent
4—B.................Ocean discharge through outfall 4—D................Underground injection
5. SLUDGE TREATMENT AND DISPOSAL PROCESSES
5—A.................Aerobic digestion 5—M................Heat drying
5—B.................Anaerobic digestion 5—N................Heat treatment
5—C................Belt filtration 5-0................Incineration
5—D................Centrifugation 5—P................Land application
5—E.................Chemical conditioning 5—Q................Landfill
5—F.................Chlorine treatment 5—R................Pressure filtration
5—G................Composting 5—S................Pyrolysis
5—H................Drying beds 5—T................Sludge lagoons
5-1..................Elutriation 5—U................Vacuum filtration
5—J.................Flotation thickening 5—V................Vibration
5—K.................Freezing 5—W...............Wet oxidation
5—L.................Gravity thickening
2F-9

Exhibit 2F-2.Conventional and Nonconventional Pollutants(40 CFR 122.21,Appendix D,Table IV)
Bromide
Chlorine,total residual
Color
Fecal coliform
Fluoride
Nitrate-nitrite
Nitrogen,total organic(as N)
Oil and grease
Phosphorus(as P),total
Radioactivity(as alpha,total;beta,total;radium,total;and radium 226,total)
Sulfate(as SO4)
Sulfide(as S)
Sulfite(as S03)
Surfactants
Aluminum,total
Barium,total
Boron,total
Cobalt,total
Iron,total
Magnesium,total
Molybdenum,total
Manganese,total
Tin,total
Titanium,total
2F-10

Exhibit 2F-3.Toxic Pollutants(40 CFR 122.21,Appendix D,Tables II and III)
Toxic Pollutants and Total Phenol
Antimony,total Copper,total Silver,total
Arsenic,total Lead,total Thallium,total
Beryllium,total Mercury,total Zinc,total
Cadmium,total Nickel,total Cyanide,total
Chromium,total Selenium,total Phenols,total
GCIMS Fraction—Volatile Compounds
Acrolein Dichlorobromomethane 1,1,2,2-tetrachloroethane
Acrylonitrile 1,1-d ichlorcethane Tetrach loroethylene
Benzene 1,2-dichloroethane Toluene
Bromoform 1,1-dichloroethylene 1,2-trans-dichloroethylene
Carbon tetrachloride 1,2-dichloropropane 1,1,1-trichloroethane
Chlorobenzene 1,3-dichloropropylene 1,1,2-trichloroethane
Chlorodibromomethane Ethylbenzene Tdchloroethylene
Chloroethane Methyl bromide Vinyl chloride
2-Chloroethylvinyl ether Methyl chloride
Chloroform Methylene chloride
GC/MS Fraction—Acid Compounds
2-chlorophenol 2,4-dinitrophenol Pentachlorophenol
2,4-dichlorophenol 2-nitrophenol Phenol
2,4-dimethylphenol 4-nitrophenol 2,4,6-trichlorophenol
4,6-dinitro-o-cresol P-chloro-m-cresol
GCIMS Fraction—Base/Neutral Compounds
Acenaphthene 4-chlorophenyl phenyl ether Hexachlorobenzene
Acenaphthylene Chrysene Hexachlorobutadiene
Anthracene Dibenzo(a,h)anthracene Hexachlorocyclopentadiene
Benzidine 1,2-dichlorobenzene Hexachloroethane
Benzo(a)anthracene 1,3-dichlorobenzene Indeno(1,2,3-cd)pyrene
Benzo(a)pyrene 1,4-dichlorobenzene Isophorone
3,4-benzofluoranthene 3,3-dichlorobenzidine Naphthalene
Benzo(ghi)perylene Diethyl phthalate Nitrobenzene
Benzo(k)fluoranthene Dimethyl phthalate N-nitrosodimethylamine
Bis(2-chloroethoxy)methane Di-n-butyl phthalate N-nitrosodi-n-propylamine
Bis(2-chloroethyl)ether 2,4-dinitrotoluene N-nitrosodiphenylamine
Bis(2-chloroisopropyl)ether 2,6-dinitrotoluene Phenanthrene
Bis(2-ethylhexyl)phthalate Di-n-octyl phthalate Pyrene
4-bromophenyl phenyl ether 1,2-diphenylhydrazine(as azobenzene) 1,2,44dchlorobenzene
Butyl benzyl phthalate Fluoranthene
2-chloronaphthalene Fluorene
GCIMS Fraction—Pesticides
Aldrin Dieldrin PCB-1254
a-BHC a-endosulfan PCB-1221
(i-BHC (3-endosulfan PCB-1232
y-BHC Endosulfan sulfate PCB-1248
6-BHC Endrin PCB-1260
Chlordane Endrin aldehyde PCB-1016
4,4'-DDT Heptachlor Toxaphene
4,4'-DDE Heptachlor epoxide
4,4'-DDD PCB-1242
2F-11

Exhibit 2F-4.Certain Hazardous Substances and Asbestos(40 CFR 122.21,Appendix D,Table V)
Toxic Pollutant
Asbestos
Hazardous Substances
Acetaldehyde Dintrobenzene Naphthenic acid
Allyl alcohol Diquat Nitrotoluene
Allyl chloride Disulfoton Parathion
Amyl acetate Diuron Phenolsulfonate
Aniline Epichlorohydrin Phosgene
Benzonitrile Ethion Propargite
Benzyl chloride Ethylene diamine Propylene oxide
Butyl acetate Ethylene dibromide Pyrethrins
Butylamine Formaldehyde Quinoline
Captan Furfural Resorcinol
Carbaryl Guthion Strontium
Carbofuran Isoprene Strychnine
Carbon disulfide Isopropanolamine Styrene
Chlorpyrifos Kelthane 2,4,5-T(2,4,54richlorophenoxyacetic
acid)
Coumaphos Kepone TDE(tetrachlorodiphenyl ethane)
Cresol Malathion 2,4,5-TP[2-(2,4,54richlorophenoxy)
propanoic acid]
Crotonaldehyde Mercaptodimethur Trichlorofon
Cyclohexane Methoxychlor Triethanolamine
2,4-D(2,4-dichlorophenoxyacetic acid) Methyl mercaptan Triethylamine
Diazinon Methyl methacrylate Trimethylamine
Dicamba Methyl parathion Uranium
Dichlobenil Mevinphos Vanadium
Dichlone Mexacarbate Vinyl acetate
2,2-dichloropropionic acid Monoethyl amine Xylene
Dichlorvos Monomethyl amine Xylenol
Diethyl amine Naled Zirconium
Dimethyl amine
2F-12

Exhibit 2F-5.Hazardous Substances
1.Acetaldehyde 73.Caplan 144.Ferrous sulfate
2.Acetic acid 74.Carbaryl 145.Formaldehyde
3.Acetic anhydride 75.Carbofuran 146.Formic acid
4.Acetone cyanohydrin 76.Carbon disulfide 147.Fumaric acid
5.Acetyl bromide 77.Carbon tetrachloride 148.Furfural
6.Acetyl chloride 78.Chlordane 149.Guthion
7.Acrolein 79.Chlorine 150.Heptachlor
8.Acrylonitrile 80.Chlorobenzene 151.Hexachlorocyctopentadiene
9.Adipic acid 81.Chloroform 152.Hydrochloric acid
10.Aldrin 82.Chloropyrifos 153.Hydrofluoric acid
11.Ally!alcohol 83.Chlorosulfonic add 154.Hydrogen cyanide
12.Allyl chloride 84.Chromic acetate 155.Hydrogen sulfide
13.Aluminum sulfate 85.Chromic add 156.Isoprene
14.Ammonia 86.Chromic sulfate 157.Isopropanolamine dodecylbenzenesulfonate
15.Ammonium acetate 87.Chromous chloride 158.Kelthane
16.Ammonium benzoate 88.Cobaltous bromide 159.Kepone
17.Ammonium bicarbonate 89.Cobaltous formate 160.Lead acetate
18.Ammonium bichromate 90.Cobaltous sulfamate 161.Lead arsenate
19.Ammonium bifluoride 91.Coumaphos 162.Lead chloride
20.Ammonium bisulfite 92.Cresol 163.Lead fluoborate
21.Ammonium carbamate 93,Crotonaldehyde 164.Lead fluorite
22.Ammonium carbonate 94.Cupric acetate 165.Lead iodide
23.Ammonium chloride 95.Cupric acetoarsenite 166.Lead nitrate
24.Ammonium chromate 96.Cupric chloride 167.Lead stearate
25.Ammonium citrate 97.Cupric nitrate 168.Lead sulfate
26.Ammonium fluoroborate 98.Cupric oxalate 169.Lead sulfide
27.Ammonium fluoride 99.Cupric sulfate 170.Lead thiocyanate
28.Ammonium hydroxide 100.Cupric sulfate ammoniated 171.Lindane
29.Ammonium oxalate 101.Cupric tartrate 172.Lithium chromate
30.Ammonium silicofluoride 102.Cyanogen chloride 173.Malathion
31.Ammonium sulfamate 103.Cydohexane 174.Maleic add
32.Ammonium sulfide 104.2,4•D acid(2,4-dichlorophenoxyace@c add) 175.Maleic anhydride
33.Ammonium sulfite 105.2,4-D esters(2,4-dichlorophenoxyacetic acid esters) 176.Mercaptodimethur
34.Ammonium tartrate 106.DDT 177.Mercuric cyanide
35.Ammonium thiocyanate 107.Diazinon 178.Mercuric nitrate
36.Ammonium thiosulfate 108.Dicamba 179.Mercuric sulfate
37.Amyl acetate 109.Dichlobenil 180.Mercuric thiocyanate
38.Aniline 110.Dichlone 181.Mercurous nitrate
39.Antimony pentachloride 111.Dichlorobenzene 182.Methoxychlor
40.Antimony potassium tartrate 112.Dichloropropane 183.Methyl mercaptan
41.Antimony dibromide 113.Dichlorcpropene 184.Methyl methacrylate
42.Antimony tichloride 114.Dichloropropene-dichloproropane mix 185.Methyl parathion
43.Antimony trifluoride 115.2,2-dichloropropionic add 186.Mevinphos
44.Antimony trioxide 116.Dichlorvos 187.Mexacarbate
45.Arsenic disulfide 117.Dieldrin 188.Monoethylamine
46.Arsenic pentoxide 118.Diethylamine 189.Monomethylamine
47.Arsenic dichloride 119.Dimethylamine 190.Naled
48.Arsenic trioxide 120.Dinitrobenzene 191.Naphthalene
49.Arsenic brisulfide 121.Dinitrophenol 192.Naphthenic add
50.Barium cyanide 122.Dinitrotoluene 193.Nickel ammonium sulfate
51.Benzene 123.Diquat 194.Nickel chloride
52.Benzoic acid 124.Disulfoton 195,Nickel hydroxide
53.Benzonitrile 125.Diuron 196.Nickel nitrate
54.Benzoyl chloride 126.Dode0benzesulfonic acid 197.Nickel sulfate
55.Ben#chloride 127.Endosulfan 198.Nitric add
56.Beryllium chloride 128.Endrin 199.Nitrobenzene
57.Beryllium fluoride 129.Epidrlorchydrin 200.Nitrogen dioxide
58.Beryllium nitrate 130.Ethion 201.Nitrophenol
59.Butylacetate 131.Ethylbenzene 202.Nitrotoluene
60.n-butytphthalate 132.Ethylenediamine 203.Paraformaldehyde
61.Butylamine 133.Ethylene dibromide 204.Parathion
62.Butyric acid 134.Ethylene dichloride 205.Pentachlorophenol
63.Cadmium acetate 135.Ethylene diaminetetracetc acid(EDTA) 205.Phenol
64.Cadmium bromide 136.Ferric ammonium citrate 207.Phosgene
65.Cadmium chloride 137.Ferric ammonium oxalate 208.Phosphoric acid
66.Calcium arsenate 138.Ferric chloride 209.Phosphorus
67.Calcium arsenite 139.Ferric fluoride 210.Phosphorus oxychloride
68.Calcium carbide 140.Ferric nitrate 211.Phosphorus pentasulfide
69.Calcium chromate 141.Ferric sulfate 212.Phosphorus tichloride
70.Calcium cyanide 142.Ferrous ammonium sulfate 213.Polychlorinated biphenyls(PCB)
71.Calcium dodecyibenzenesulfonate 143.Ferrous chloride 214.Potassium arsenate
72.Calcium hypochlorite 215.Potassium arsenite
2F-13

Exhibit 2F-5.Hazardous Substances
216.Potassium bichromate 245.Sodium phosphate(dibasic) 271.Uranyl acetate
217.Potassium chromate 246.Sodium phosphate(tribasic) 272.Uranyl nitrate
218.Potassium cyanide 247.Sodium selenite 273.Vanadium penoxide
219.Potassium hydroxide 248.Strontium chromate 274.Vanadyl sulfate
220.Potassium permanganate 249.Strychnine 275.Vinyl acetate
221.Propargite 250.Styrene 276.Vinylidene chloride
222.Propionic add 251.Sulfuric acid 277.Xylene
223.Propionic anhydride 252.Sulfur monochloride 278.Xylenol
224.Propylene oxide 253.2,4,5-T add(2,4,5-trichlorophenoxyacetc add) 279.Zinc acetate
225.Pyrethrins 254.2,4,5-T amines(2,4,5-trichlorophenoxy acetic add 280.Zinc ammonium chloride
226.Quinoline amines) 281.Zinc borate
227.Resorcinol 255.2,4,5-T esters(2,4,5-trichtorophenoxy acetic add 282.Zinc bromide
228.Selenium oxide esters) 283.Zinc carbonate
229.Silver nitrate 256.2,4,5-T salts(2,4,5-Wchlorophenoxy acetic add 284.Zinc chloride
230.Sodium salts) 285.Zinc cyanide
231.Sodium arsenate 257.2,4,5-TP acid(2,4,5-trichlorophenoxy propanoic 286.Zinc fluoride
232.Sodium arsenite acid) 287.Zinc formate
233.Sodium bichromate 258.2,4,5-TP add esters(2,4,5-trichlorophenoxy 288.Zinc hydrosulfite
234.Sodium bifuoride propanoic acid esters) 289.Zinc nitrate
235.Sodium bisulfite 259.TDE(tetrachlorodiphenyl ethane) 290.Zinc phenolsulfonate
236.Sodium chromate 260.Tetraethyl lead 291.Zinc phosphide
237.Sodium cyanide 261.Tetraethyl pyrophosphate 292.Zinc silioofluodde
238.Sodium dodecylbenzenesulfonate 262.Thallium sulfate 293.Zinc sulfate
239.Sodium fluoride 263.Toluene 294.Zirconium nitrate
240.Sodium hydrosulfide 264.Toxaphene 295.Zirconium potassium fluoride
241.Sodium hydroxide 265.Trichlorofon 296.Zirconium sulfate
242.Sodium hypochlorite 266.Trichloroethylene 297.Zirconium tetrachloride
243.Sodium methylate 267.Trichlorophenol
244.Sodium nitrite 268.Triethanolamine dodecylbenzenesulfonate
269.Triethylamine
270.Trimethylamine
2F-14

EPA Identification Number NPDES Permit Number Facility Name Form Approved 03i05119
International Tie Disposal,LLC- OW No,2040-0004
Form M Environmental Protection Agency
2F \.EPA Application for NPDES Permit to Discharge Wastewater
NPDES STORMWATER DISCHARGES ASSOCIATED WITH INDUSTRIAL ACTIVITY
SECTIONOUTFALL LOCATION1
1.1 Provide information on each of the facilit 's outfalls in the table below
Outfall Receiving Water Name Latitude Longitude
Number
441 UT to Mill Creek 34 SSA 35.76' N 79' 37' 54.6i' W
0
0
a
co
u
0
fO
O n n o v
SECT ION 2.IM PROVEM1
2.1 Are you presently required by any federal, state,or local authority to meet an implementation schedule for constructing,
upgrading,or operating wastewater treatment equipment or practices or any other environmental programs that could
affect the discharges described in this application?
❑ Yes ❑✓ No 4 SKIP to Section 3.
2.2 Briefly identify each applicable project in the table below.
Brief Identification and Affected Outfalls Final Compliance Dates
Description of Project (list outfali numbers) Source(s)of Discharge
Required Projected
c
a�
E
m
n
0
�..
a
E
2.3 Have you attached sheets describing any additional water pollution control programs(or other environmental projects
that may affect your discharges)that you now have underway or planned?(Optional Item)
❑ Yes ❑ No
EPA Form 3510-21'(Revised 3-19) Page 1

EPA Identification Number NPOES Permit Number Facility Name Form Approved 03/05/19
International Tie Disposal,LLC- OMB No.2040-0004
SECTION 3.SITE D• I
m 3.1 Have you attached a site drainage map containing all required information to this application?(See instructions for
W LV CLspecific guidance.)
® Yes ❑ No
SECTION 4.POLLUTANT SOURCESi
4.1 Provide information on the facility's pollutant sources in the table below.
Outfall Impervious Surface Area Total Surface Area Drained
Number (within a mile radius of the facility) (within a mile radius of the facility)
specify units specify units
001 2.62 Acres 135.S S Acres
specify units specify units
specify units specify units
specify units specify units
specify units specify units
specify units specify units
4.2 Provide a narrative description of the facility's significant material in the space below,(See instructions for content
requirements.)
Significant materials consist of legacy railroad ties treated with wood-tar creosote(roughly 15-30 years prior),diesel
fuel and propane.The only materials that will be exposed to stormwater are the legacy railroad ties stored in the
Storage Area and the crusher located on a 200'x 200'asphalt pad.
to Diesel fuel will be stored in a 1,000-gallon double-walled AST.Propane will be stored in a 10,000-gallon tank.
Tanks will utilize transfer valves to fuel on-site equipment/vehicles.
? Forklifts,etc.will be stored in the maintenance area.They will be taken off site for repairs.They will not be stored
0
IL outside.
4.3 Provide the location and a description of existing structural and non-structural control measures to reduce pollutants in
stormwater runoff. See instructions forspecificguidance.)
Stormwater Treatment
Codes
Outfall from
Number Control Measures and Treatment Exhibit
2F-1
list
001 Biochar processing located in intermodal shipping containers N/A
001 Diesel fuel is located in a double-walled AST N/A
001 Legacy RR tie storage yard and sorting area are at farthest location from outfall N/A
001 Employee training,visual inspections,preventive maintenance,&housekeeping measures N/A
EPA Form 3510-2F(Revised 3-19) Page 2

EPA Identification Number NPDES Permit Number Facility Name Form Approved 03/05/19
International Tie Disposal,LLC OMB No.2040-0004
SECTION •N STORMVVATER DISCHARGES(40
5.1 1 certify under penalty of law that the outfall(s) covered by this application have been tested or evaluated for the
presence of non-stormwater discharges. Moreover, t certify that the outfalls identified as having non-stormwater
discharges are described in either an accompanying NPDES Form 2C,2D,or 2E application.
Name(print or type first and last name) Official title
N/A-New Facility
Signature Date signed
N/A-New Facility
L' 5.2 Provide the testing information requested in the table below.
cc
Outfall Onsite Drainage Points
o Number Description of Testing Method Used Date(s)of Testing Directly Observed
During Test
N/A-New Facility
0
e
0
z
SECTION + OR 41
6.1 Describe any significant leaks or spills of toxic or hazardous pollutants in the last three years.
n N/A-New Facility
co
O
Y
N
J
C
C
01
N
SECTIONA' •' • 41
See the instructions to determine the pollutants and parameters you are required to monitor and,in turn,the tables you must
a cam lete.Not all applicants need to complete each table.
7.1 Is this a new source or new discharge?
o ❑ Yes 4 See instructions regarding submission of ❑ No 4 See instrucfions regarding submission of
estimated data. actual data.
Tables A,B,C,and D
7.2 Have you completed Table A for each outfall?
❑ Yes ❑✓ No
EPA Form 3510-217(Revised 3-19) Page 3

EPA Identification Number NPDES Permit Number Facility Name Form Approved 03105/19
International Tie Disposal,LLC- OMB No.2040-0004
7.3 Is the facility subject to an effluent limitation guideline(ELG)or effluent limitations in an NPDES permit for its process
wastewater?
❑ Yes ✓❑ No 4 SKIP to Item 7.5.
7.4 Have you completed Table B by providing quantitative data for those pollutants that are(1)limited either directly or
indirectly in an ELG and/or(2)subject to effluent limitations in an NPDES permit for the facility's process wastewater?
❑ Yes ❑ No
7.5 Do you know or have reason to believe any pollutants in Exhibit 2F-2 are present in the discharge?
❑ Yes ✓❑ No 4 SKIP to Item 7.7.
7.6 Have you listed all pollutants in Exhibit 2F-2 that you know or have reason to believe are present in the discharge and
provided quantitative data or an explanation for those pollutants in Table C?
❑ Yes ✓❑ No
7.7 Do you qualify for a small business exemption under the criteria specified in the Instructions?
❑ Yes 4SKIP to Item 7.18. ❑✓ No
7.8 Do you know or have reason to believe any pollutants in Exhibit 217-3 are present in the discharge?
❑ Yes ❑✓ No 4 SKIP to Item 7.10.
7Z 7.9 Have you listed all pollutants in Exhibit 2F-3 that you know or have reason to believe are present in the discharge in
c Table C?
w
0 ElYes ❑ No
0 7.10 Do you expect any of the pollutants in Exhibit 2F-3 to be discharged in concentrations of 10 ppb or greater?
V
E ❑ Yes ✓❑ No 4 SKIP to Item 7.12.
7.11 Have you provided quantitative data in Table C for those pollutants in Exhibit 2F-3 that you expect to be discharged in
L, concentrations of 10 ppb or greater?
R
❑ Yes ❑ No
7.12 Do you expect acrolein,acrylonitrile,2,4-dinitrophenol,or 2-methyl-4,6-dinitrophenol to be discharged in concentrations
of 100 ppb or greater?
❑ Yes ✓❑ No 4 SKIP to Item 7.14.
7.13 Have you provided quantitative data in Table C for the pollutants identified in Item 7.12 that you expect to be
discharged in concentrations of 100 ppb or greater?
❑ Yes ❑ No
7.14 Have you provided quantitative data or an explanation in Table C for pollutants you expect to be present in the
discharge at concentrations less than 10 ppb(or less than 100 ppb for the pollutants identified in Item 7.12)?
❑ Yes ❑✓ No
7.15 Do you know or have reason to believe any pollutants in Exhibit 2F4 are present in the discharge?
❑ Yes ❑✓ No 4 SKIP to Item 7.17.
7.16 Have you listed pollutants in Exhibit 217-4 that you know or believe to be present in the discharge and provided an
explanation in Table C?
❑ Yes ❑ No
7.17 Have you provided information for the storm event(s)sampled in Table D?
❑ Yes ✓❑ No
EPA Form 3510-2F(Revised 3-19) Page 4

EPA Identification Number NPDES Permit Number FaDi ity Name Form Approved 03105/19
International Tie Disposal,LLC- OMB No,2040-0004
a Used or Manufactured Toxics
7.18 Is any pollutant listed on Exhibits 2F-2 through 2F-4 a substance or a component of a substance used or
omanufactured as an intermediate or final product or byproduct?
C ❑ Yes ❑ No i SKIP to Section 8.
0
7.19 List the pollutants below,including TCDD if applicable.
1. 4. 7.
d
2. 5. 8.
0 3. 6. 9.
SECTION • • • i
8.1 Do you have any knowledge or reason to believe that any biological test for acute or chronic toxicity has been made on
;? any of your discharges or on a receiving water in relation to your discharge within the last three years?
0
❑ Yes a❑ No 4 SKIP to Section 9,
8.2 Identify the tests and their purposes below.
Test(s) Purpose of Test(s) Submitted to NPDES Date Submitted
x Permitting Authority?
0
❑ Yes 11 No
U
o ❑ Yes ❑ No
0
m
❑ Yes ❑ No
SECTION ' CONTRACT ANALYSIS INFORMATIONI
9.1 Were any of the analyses reported in Section 7(on Tables A through C)performed by a contract laboratory or
consulting firm?
❑ Yes ❑� No 4 SKIP to Section 10.
9.2 Provide information for each contract laboratory or consulting firm below.
Laboratory Number 1 Laboratory Number 2 Laboratory Number 3
Name of laboratory/firm
0
.6
0
y Laboratory address
a
= Phone number
0
U
Pollutant(s)analyzed
EPA Form 3510-2F(Revised 3-19) Page 5

EPA Identification Number NPDES Permit Number Facility Name Form Approved 03105/19
International Tie Disposal,LLC OMB No.2040-0004
SECTION1 CHECKLIST AND CERTIFICATION +t
10.1 In Column 1 below,mark the sections of Form 2F that you have completed and are submitting with your application.For
each section,specify in Column 2 any attachments that you are enclosing to alert the permitting authority.Note that not
all applicants are required to complete all sections or provide attachments.
Column 1 Column 2
❑✓ Section 1 ❑ wl attachments(e.g.,responses for additional outfalls)
✓❑ Section 2 ❑ wl attachments
✓❑ Section 3 ✓❑ wl site drainage map
✓❑ Section 4 ❑ wl attachments
✓❑ Section 5 ❑ wl attachments
c
✓❑ Section 6 ❑ wl attachments
E ❑ Section 7 ❑ Table A ❑ wl small business exemption request
o ❑ Table B ❑ wl analytical results as an attachment
❑ Table C ❑ Table D
'E
-o
❑✓ Section 8 ❑ wlattachments
c
❑✓ Section 9 ❑ wlattachments(e.g.,responses for additional contact laboratories or firms)
_ ❑✓ Section 10 ❑
10.2
Certification Statement
/certify under penalty of law that this document and all attachments were prepared under my direction or supervision in
accordance with a system designed to assure that qualified personnel properly gather and evaluate the information
submitted.Based on my inquiry of the person or persons who manage the system or those persons directly responsible
for gathering the information, the information submitted is, to the best of my knowledge and belief, true, accurate,and
complete./am aware that there are significant penalties for submitting false information, including the possibility of fine
and imprisonment for knowing violations.
Name(print or type first and last name) Official title
Basil polivka II Member
Signature Date signed
April 26th,2023
EPA Form 3510-21'(Revised 3-19) Page 6

EPA Identification Number NPDES Permit Number Facility Name Ouffall Number Form Approved 03r05/19
International Tie Disposal,LLC- OMB No.2040-0004
TABLE A.CONVENTIONAL AND NON • s i
You must provide the results of at least one analysis for every pollutant in this table.Complete one table for each outfall.See instructions for additional details and requirements.
Maximum Dally Discharge Average Daily Discharge Source of
(specify units) (specify units) Number of Storm Information
Pollutant or Parameter Grab Sample Taken Grab Sample Taken (new sourcefiew
During First FIo W Composite
ed During First Flo Composite
Events Sampled dischargers only,use
30 Minutes Composite 30 Minutes Composite codes in Instructions)
1. Oil and grease
2. Biochemical oxygen demand(BODs)
3. Chemical oxygen demand(COD)
4. Total suspended solids(TSS)
5. Total phosphorus
6. Total Kjeldahl nitrogen(TKN)
7. Total nitrogen(as N)
pH(minimum)
8.
pH(maximum)
Sampling shall be conducted according to sufficiently sensitive test procedures(i.e.,methods)approved under 40 CFR 136 for the analysis of pollutants or pollutant parameters or
required under 40 CFR chapter I,subchapter N or 0.See instructions and 40 CFR 122.21(e)(3).
EPA Form 3510-21'(Revised 3.19) Page 7

This page intentionally left blank.

EPA Identification Number NPDES Permit Number Facility Name Outfall Number Form Approved 03r05/19
International Tie Disposal,LLC- OMB No.2040-0004
TABLE + • • + AND •N CONVENTIONAL POLLUTANTS +I CFR 122.26(c)(1)(i)(E)(4)and 40
List each pollutant that is limited in an effluent limitation guideline(ELG)that the facility is subject to or any pollutant listed in the facility's NPDES permit for its process wastewater(lithe
facility is operating under an existing NPDES permit).Complete one table for each outfall.See the instructions for additional details and requirements.
Maximum Daily Discharge Average Daily Discharge Source of
s units) (sp units Number of Storm Information
Pollutant and CAS Number(if available) Grab Sample Taken Grab Sample Taken (new sourcelnex
During First Flo Composite
ed During First FlComposite Events Sampled discliargers onty;use
30 Minutes Composite 30 Minutes Composite codes in instructions)
Sampling shall be conducted according to sufficiently sensitive test procedures(i.e.,methods)approved under 40 CFR 136 for the analysis of pollutants or pollutant parameters or
required under 40 CFR chapter I,subchapter N or 0.See instructions and 40 CFR 122.21(e)(3).
EPA Form 3510-2F(Revised 3-19) Page 9

This Page intentionally left blank.

EPA Identification Number NPDES Permit Number Facility Name Outfall Number Form Approved 03/05/19
International Tie Disposal,LLC- OMB No.2040-0004
TABLE C.TOXIC POLLUTANTS,CERTAIN HAZARDOUS SUBSTANCES,AND ASBESTOS(40 CFR 122.26(c)(1)(i)(E)(4)and 40 CFR 122.21(g)(7)(vi)(B)and(vii))'
List each pollutant shown in Exhibits 2F-2,2F-3,and 21F4 that you know or have reason to believe is present.Complete one table for each outfall.See the instructions for additional
details and requirements.
Maximum Daily Discharge Average Daily Discharge Source of
s ed units (sped units Number of Storm Information
Pollutant and CAS Number(if available) Grab Sample Taken Flow-Weighted Grab Sample Taken Flow-Weighted Events Sampled (new scurce/new
During First During First dischargers only,use
30 Minutes Composite 30 Minutes Composite codes in instructions)
Creosol; CAS Number:93-S1-6 N/A 5,USDA Report
Sampling shall be conducted according to sufficiently sensitive test procedures(i.e.,methods)approved under 40 CFR 136 for the analysis of pollutants or pollutant parameters or
required under 40 CFR chapter I,subchapter N or 0.See instructions and 40 CFR 122.21(e)(3).
EPA Form 3510-2F(Revised 3-19) Page 11

This page intentionally left blank.

EPA Identification Number NPDES Permit Number Facility name Outfall Number Form Approved 03105I19
International Tie Disposal,LLC- OMB No.2040-0004
TABLE D.STORM EVENT INFORMATION41
Provide data for the storm event(s)that resulted in the maximum daily discharges for the flow-weighted composite sample.
Number of Hours Between
Total Rainfall During Maximum Flow Rate During Rain Event
Duration of Storm Event Beginning of Storm Measured and Total Flow from Rain Event
Date of Storm Event (in hours) Storm Event End of Previous Measurable Rain (in gallons or specify units)
(in inches) Event (in gpm or specify units)
Provide a description of the method of flow measurement or estimate.
EPA Form 3510-2F(Revised 3-19) Page 13

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� + Management Plan
for the Hamlet Tie Disposal and Pyrolysis Facility
Prepared for CSX Corporation
April 21st,2022
13700 Providence Road,Suite 200
Weddington,NC 28104
polivkaintl.com
P. 704.321.0802,F. 704.321.0805

Draft Waste Management Plan-Short Version
The Purpose of a Waste Management Plan and Hove
Things Are Classified As Such:
A Waste Management Plan gives a good picture of what kinds of wastes one can expect
to generate in the course of a project, or operation of one's business. The purpose of such a plan
is to ensure that a company responsibly manages its own resources efficiently. Lacking a plan
prevents foresight, which can result in financial or environmental burdens. It is therefore of
great utility.
The Hamlet, NC Facility that is permitted to process railroads ties via an exciting new
technology is anticipated to be low on waste according to its strict definitional limits.
Nonetheless, for our purposes, "waste"will be interpreted more broadly to include anything of
non-trivial quantities generated both on site, or received on site. This will naturally include
more traditional wastes like garbage from human consumption, and less traditional "wastes"
like railroad ties, or Biochar; both of which will be sold.
A more thorough Waste Management Plan would include some discussion of how
exactly the waste will be safely managed, but due to the rather small nature of our waste
stream, and the draft nature of this plan, it will suffice to say that where applicable, N95 face
masks will be used (as when disposing of air filters, which are rather dusty), or where
applicable gloves will be worn (as when handling treated wood waste).
Additionally, it is taken for granted that records will be kept for most of the waste
streams generated since they are either products for sale, regularly scheduled disposal, or
items requiring replacement.
Everything has been arranged as simply and straightforwardly as possible. Estimates on
weight are provided, but these are especially approximate.
2

Draft Waste Management Plan-Short Version
Wastes generated in the course of the normal operations of the Hamlet, NC
Tie Conversion Facility include the following non-exhaustive list:
Metal Components from Tie Processing-n/a
In the course of crushing ties in preparation for pyrolysis,various metal wastes are
generated.
TO SCRAP YARD
Landscape Ties--28,750 tons per year
Approximately 25% of ties are classified as landscape (able to be reused).
I ! WE'S HOME IMPROVEMENT
Misc.Shipping Materials--20 tons per year
Generated from receiving or shipping materials from the facility. Includes crates,
fiberglass bags, etc..
I LANDFILL
3

Draft Waste Management Plan-Short Version
Dust bag collection systems-n/a
Dust generated during the crushing of the finished Biochar byproduct is collected in a
filtration system.
TO LANDFILL
Septic f Human Waste-n/a
Removed biweekly.
TO WASTEWATER TREATMENT PLANT
Paper products and Cardboard--2 ton per year
Generated by workforce and small orders.
TO RECYCLING

Draft Waste Management Plan-Short Version
Biochar-Est. 30,000 tons per year
The main product generated by the facility.
TO VENDORS
5

ROY COOPER a stNF4o-'`
I✓s°1
Govenror ?�
ELIZABETH S.BISER
Secretary
MCHAEL A.ABRACZIN WAS NORTH CAROLINA
Director Environmental Quality
November 24, 2021
Mr. Basil Polivka II
Business Development
International Tie Disposal,LLC-Project Tie
13700 Providence Road
Suite 200
Weddington,NC 28104
Subject: Air Permit No. 10676RO l
International Tie Disposal,LLC -Project Tie
Hamlet,Richmond County,North Carolina
Permit Class: Synthetic Minor
Facility ID#7700101
Dear Mr.Polivka II:
In accordance with your completed application received November 15,2021,we are
forwarding herewith Permit No. 10676ROI to International Tie Disposal,LLC-Project Tie,
Hamlet,Richmond County,North Carolina for the construction and operation of air emissions
sources or air cleaning devices and appurtenances. Additionally,-any emissions activities
determined from your air permit application as meeting the exemption requirements contained in
15A NCAC 2Q.0102 have been listed for information purposes as an "ATTACHMENT"to the
enclosed air permit. Please note the records retention requirements are contained in General
Condition 2 of the General Conditions and Limitations.
If any parts,requirements,or limitations contained in this permit are unacceptable to you,
you have the right to request a formal adjudicatory hearing within 30 days following receipt of this
pei:init, identifying the specific issues to be contested. Such a request will stay the effectiveness of
the entire permit. This hearing request must be in the form of a written petition,conforming to G.S.
150B-23 of the North Carolina General Statutes,and filed with the Office of Administrative
Hearings, 6714 Mail Service Center,Raleigh,NC 27699-6714. The form for requesting a formal
adjudicatory hearing may be obtained upon request from the Office of Administrative Hearings.
Unless a request for a hearing is made pursuant to G.S. 150B-23,this air permit shall be final and
binding.
You may request modification of your air permit through informal means pursuant to G.S.
150B-22. This request must be submitted in writing to the Director-and must identify the specific
provisions or issues for which the modification is sought.Please note that the permit will become
final and binding regardless of a request for informal modification unless a request for a hearing is
also made under G.S. 150B-23.
�D E
Q
�North Carolina Department of Environmental 4uatdy I Division of Air Quality
®JJ Fayetteville Regional Office 1226 Green Street,Suite 714 1 Fayetteville,NC 26301-6094
RSMOM1RrAW4
910.433.3300 T 1 910.466.7467 F

Basil Polivka H
November 24,2021
Page 2
Unless exempted by a condition of this permit or the regulations,construction of new
air pollution sources or air cleaning devices,or modifications to the sources or air cleaning
devices described in this permit must be covered under a permit issued by the Division of Air
Quality prior to construction.Failure to do so is a violation of G.S. 143-215.108 and may
subject the Permittee to civil or criminal penalties as described in G.S. 143-215.114A and 143-
215114B.
Note that initial source testing is required to be conducted no later than 90 days after
startup of the biochar kiln operations. See permit Specific Condition and Limitation A.10 for
details on the testing and notification requirements.
Note that subsequent source testing is required to be conducted no more than
13 months after the previous performance test. See permit Specific Condition and Limitation
A.I1 for details on the testing and notification requirements.
Note also that a notification of biochar kiln operation startup is required. See permit
Specific Condition and Limitation A.14 for details.
This permit shall be effective from November 24,2021 until March 31,2029,is
nontransferable to future owners and operators, and shall be subject to the conditions and limitations
as specified therein.
Changes have been made to the permit stipulations. The Permittee is responsible for
carefully reading the entire permit and evaluating the requirements of each permit
stipulation.The Permittee shall comply with all terms,conditions,requirements,limitations
and restrictions set forth in this permit.Noncompliance with any permit condition is grounds
for enforcement action, for permit termination, revocation and reissuance, or modification,or
for denial of a permit renewal application.Should you have any questions concerning this matter,
please contact Jeffrey D. Cole at 910-433-3300.
Sincerely,
,c a, Heather Carter,Regional Supervisor
Division of Air Quality,NC DEQ
JDC
Enclosures
c: Fayetteville Regional Office

i
NORTH CAROLINA ENVIRONMENTAL MANAGEMENT COMMISSION
DEPARTMENT OF ENVIRONMENTAL QUALITY
DIVISION OF AIR QUALITY
AIR PERMIT NO. 10676R01
Issue Date:November 24, 2021 Effective Date: November 24, 2021
Expiration Date. March 31, 2029 Replaces Pen-nit: 10676R00
To construct and operate air emission source(s) and/or air cleaning device(s),and for the
discharge of the associated air contaminants into the atmosphere in accordance with the provisions
of Article 21 B of Chapter 143, General Statutes of North Carolina(NCGS) as amended, and other
applicable Laws,Rules and Regulations,
International Tie Disposal,LLC-Project Tie
174 Marks Creek Church Road
Hamlet, Richmond County,North Carolina
Permit Class: Unknown
Facility ID#7700101
(the Pertnittee) is hereby authorized to construct and operate the air emissions sources and/or air
cleaning devices and appurtenances described below:
Emission Emission Source !� Control ContrnI System
lEr
Sourcc:ID Desc�i Lion rj yste..m ID, Description
S
Biochar Kilns(426 Units)
each with integral Natural Afterburners(62 units)
Natural Gas/ Fired
ES-1 Gas/LPG-Fired Kiln Burner CD-1
(0.007$nuuBtu/lu maximum (O.I25 mmBtu/hr maximum
heat input each each)
heat input each)
in accordance with the completed application 7700101.20A received November 15, 2021 including
any plans, specifications,previous applications, and other supporting data, all of which are filed
with the Department of Environmental Quality, Division of Air Quality(DAQ) and are incorporated
as part of this permit.

Permit No. 10676ROI
Page 2
This permit is subject to the following specified conditions and limitations including any
TESTING,REPORTING, OR MONITORING REQUIREMENTS:
A. SPECIFIC CONDITIONS AND LIMITATIONS
1. Any air emission sources or control devices authorized to construct and operate above must
be operated and maintained in accordance with the provisions contained herein. The
Permittee shall comply with applicable Environmental Management Commission
Regulations,including Title 15A North Carolina Administrative Code (NCAC), Subchapter
2D .0202,2D .0501(c),2D .0515,2D .0516,2D .0521,2D .0535,213 .0540, 2D .0605,
2D .0611,2D .1806,2Q .0309, 2Q .0315,2Q .0317 (Avoidance) and 2Q .0711.
2. PERMIT RENEWAL AND EMISSION INVENTORY REQUIREMENT -The Permittee,
at least 90 days prior to the expiration date of this permit,shall request permit renewal by
letter in accordance with 15A NCAC 2Q .0304(d)and (f). Pursuant to 15A NCAC 2Q
.0203(i),no permit application fee is required for renewal of an existing air permit(without
a modification request). The renewal request(with application Form A) should be submitted
to the Regional Supervisor, DAQ. Also, at least 90 days prior to the expiration date of this
permit,the Permittee shall submit the air pollution emission inventory report(with
Certification Sheet) in accordatice with 15A NCAC 2D .0202,pursuant to N.C. General
Statute 143-215.65. The report shall be submitted to the Regional Supervisor,DAQ and
shall document air pollutants emitted for the 2027 calendar year.
3. COMPLIANCE WITH EMISSION CONTROL STANDARDS -As required by 15A
NCAC 2D .0501(c)any source of air pollution shall be operated with such control or in such
manner that the source shall not cause the ambient air quality standards pursuant to 15A
NCAC 02D .0400 to be exceeded at any point beyond the premises on which the source is
located. When controls more stringent than those named in the applicable emission
standards in this Section are required to prevent violation of the ambient air quality
standards or are required to create an offset,the permit shall contain a condition requiring
these controls.
a. Production Limitations -To establish compliance with 15A NCAC 02D .0501(c),the
Permittee shall be limited to kiln operations,which includes the operation of a
Natural Gas/LPG-Fired(0.125 mmBtu/hr maximum-heat input)Afterburner(CD ID
No. CD-1),under this scenario.
i. Facility is limited to no more than 62 kiln operations per hour.
b. Recordkeeping Requirements-The Permittee shall record,daily,the number of kiln
operations per hour.
c. Reporting Requirements-For compliance purposes,the Permittee shall submit to the
Regional Supervisor,DAQ, on or before January 30 of each calendar year for the
preceding six-month period between July and December and July 30 of each
calendar year for the preceding six-month period between January and June, a
summary report of emissions and/or operational data listed below:
i. Dates and times when more than 62 kiln operations per hour occurred.

Permit No. 10676ROl
Page 3
4. PARTICULATE CONTROL REQUIREMENT-As required by 15A NCAC 2D .0515
"Particulates from Miscellaneous Industrial Processes,"particulate matter emissions from
the emission sources shall not exceed allowable emission rates. The allowable emission rates
are,as defined in 15A NCAC 2D .0515,a function of the process weight rate and shall be
determined by the following equation(s),where P is the process throughput rate in tons per
hour(tons/hr)and E is the allowable emission rate in pounds per hour(lbs/hr).
E=4.10 * (P) 0.61 for P<=30 tons/hr,or
E=55 * (P) 0-" -40 for P>30 tons/hr
5. SULFUR DIOXIDE CONTROL REQUIREMENT-As required by 15A NCAC 213 .0516
"Sulfur Dioxide Emissions from Combustion Sources," sulfur dioxide emissions from the
combustion sources shall not exceed 2.3 pounds per million Btu heat input.
6. VISIBLE EMISSIONS CONTROL REOUIREMENT-As required by 15A NCAC 2D
.0521 "Control of Visible Emissions," visible emissions from the emission sources,
manufactured after July 1, 1971, shall not be more than 20 percent opacity when averaged
over a six-minute period,except that six-minute periods averaging not more than 87 percent
opacity may occur not more than once in any hour nor more than four times in any 24-hour
period.However, sources which must comply with a visible emissions standard in 15A
NCAC 2D .0524"New Source Performance Standards" or.I 110 "National Emission
Standards for Hazardous Air Pollutants" shall meet that standard instead of the 2D .0521
visible emissions standard.
7. NOTIFICATION REQUIREMENT-As required by 15A NCAC 2D .0535,the Permittee of
a source of excess emissions that last for more than four hours and that results from a
malfunction,a breakdown of process or control equipment or any other abnormal
conditions, shall:
a. Notify the Director or his designee of any such occurrence by 9:00 a.m. Eastern time
of the Division's next business day of becoming aware of the occurrence and
describe:
i. the name and location of the facility,
ii. the nature and cause of the malfunction or breakdown,
iii. the time when the malfunction or breakdown is first observed,
iv. the expected duration, and
V. an estimated rate of emissions.
b. Notify the Director or his designee immediately when the corrective measures have
been accomplished.
This reporting requirement does not allow the operation of the facility in excess of
Environmental Management Commission Regulations.

Permit No. 10676R01
Page 4
8. FUGITIVE DUST CONTROL REQUIREMENT-As required by 15A NCAC 2D .0540
"Particulates from Fugitive Dust Emission Sources," the Permittee shall not cause or allow
fugitive dust emissions to cause or contribute to substantive complaints or excess visible
emissions beyond the property boundary. If substantive complaints are received or excessive
fugitive dust emissions from the facility are observed beyond the property boundaries for six
minutes in any one hour(using Reference Method 22 in 40 CFR,Appendix A),the owner or
operator may be required to submit a fugitive dust plan as described in 2D .0540(f).
"Fugitive dust emissions" means particulate matter that does not pass through a process
stack or vent and that is generated within plant property boundaries from activities such as:
unloading and loading areas,process areas stockpiles, stock pile working,plant parking lots,
and plant roads(including access roads and haul roads).
9. EQUIPMENT LABELING-Under the provisions of North Carolina General Statute
143-215.108 and in accordance with I SA NCAC 2D .0605,All onsite permitted equipment
shall be labeled with the emission source ID number listed in the Emission Source Table of
this permit and a numerical sequence number that differentiates each biochar kiln from the
others onsite and each afterburner from the others onsite. This shall be completed upon
startup of the sources and control devices.
10. INITIAL TESTING REQUIREMENT-Under the provisions of North Carolina General
Statute 143-215.108 and in accordance with 15A NCAC 2D .0605,the Permittee shall verify
emission factors as submitted in the permit application and establish the minimum and/or
maximum operating temperatures of the afterburners by testing the emission sources for the
specified pollutant(s) as follows:
�~...�.1'w�Y♦i C` ' I, FEr ..�. ssTY w..k.C� .V....Y�.i. ] `.
PM(Filterable and
Condensable Particulate
Matter) DAQ Approved
Biochar Kilns(426 Units) NOx Methods
each with integral CO
Natural Gas/LPG-Fired Kiln VOC
Burners (0.0078 mmBtu/hr
maximum heat input each) HAPs/TAPs emitted Method 320
(F'IR)
Visible Emissions(VE) DAQ Approved
Method
a. The Permittee shall conduct the testing within 90 days after startup of the biochar
kiln operations for each raw material type.
b. Testing shall include PM(Filterable and Condensable Particulate Matter),NOx, CO,
VOC,Visible Emissions(VE),and HAPs/TAPs emitted.

Permit No. 10676R0l
Page 5
c. The source testing shall be conducted on the exhaust stacks of four(4)different kilns
and afterburners for each raw material type,creosote treated railroad ties and
untreated lumber, for a total of eight(8)different kilns and afterburners being tested.
d. Unless otherwise specified by federal rules,the Permittee shall perform such testing
in accordance with 15A NCAC 02D .2600.
e. The Permittee shall arrange for air emission testing protocols to be provided to the
DAQ prior to testing. Testing protocols are not required to be pre-approved by the
DAQ prior to testing. The DAQ shall review testing protocols for pre-approval prior
to testing if requested by the Permittee at least 45 days before conducting the test.
f. To afford the Regional Supervisor,DAQ,the opportunity to have an observer
present,the Permittee shall PROVIDE the Regional Office,in WRITING,at least
15 days'notice of any required performance test(s).
g. During the source testing effort each kiln will be charged to it's maximum capacity
and be weighed to establish the lb/ton emission factors.
h. Two copies of the test results must be submitted to the Regional Supervisor,DAQ, in
accordance with the requirements of 15A NCAC 02D .2600 no later than 3 0 days
after the testing is completed. The results shall include a table listing,side-by-side,
all criteria, HAP and TAP emission factors derived during initial testing and,for
comparision,all criteria,HAP and TAP emission factors used in the initial
permitting process. The results shall also include the identification number of the
kilns and afterburners being tested,as specified in Permit Stipulation A.9. At the
same time the two copies of the initial test results are submitted to the Regional
Supervisor,DAQ,the Permittee shall submit a permit modification application
pursuant to 15A NCAC 02Q .0316 to incorporate the minimum and/or maximum
combustion zone temperature, established during source testing,into the permit.
i. The Permittee shall develop, and submit to the DAQ for approval no later than
30 days after the initial testing is completed,a Continuous Parametric Monitoring
Plan establishing the minimum and/or maximum combustion zone operating
temperature of the Afterburners(CD-1)with respect to the specific pollutants. The
minimum and/or maximum combustion zone operating temperature for the
afterburners shall be based upon average temperature data over the span of the test
runs. Documentation for the minimum and/or maximum combustion zone operating
temperature shall be submitted to the DAQ as part of the initial compliance test
report.
j. This permit may be revoked,with proper notice to the Permittee, or enforcement
procedures initiated,if the results of the tests indicate that the facility does not meet
applicable limitations.
k. The source shall be responsible for ensuring,within the limits of practicality,that the
equipment or process being tested is operated at or near its maximum normal
production rate,or at a lesser rate if specified by the Director or his delegate.
1. All associated testing costs are the responsibility of the Permittee.

. I
Permit No. 10676R0I
Page 6 i
11. SUBSEQUENT TESTING REQUIREMENT- Under the provisions of North Carolina
General Statute 143-215.108 and in accordance with 15A NCAC 2D .0605,the Permittee
shall verify emission factors as submitted in the permit application and confirm or
reestablish operating temps of the afterburners by testing the emission sources for the
specified pollutant(s)as follows:
PM(Filterable and
Condensable Particulate
Matter) DAQ Approved
Biochar Kilns (426 Units) NOx Methods
each with integral
Natural Gas/LPG-Firdd Kiln VOC
Burners(0.0078 mmBtu/hr _
maximum heat input each) Method 320
HAPs/TAPs emitted (FTIIZ)
Visible Emissions(VE) DAQ Approved
Method
a. Testing shall include PM (Filterable and Condensable Particulate Matter),NOx, CO,
VOC,Visible Emissions(VE), and all HAPs/TAPs emitted.
b. Subsequent performance tests must be completed no more than 13 months after
the previous performance test.
c. The Permittee may request that the performance tests be conducted less often for a
given pollutant if the performance tests for at least 3 consecutive years show
compliance with the emission limit. If the request is granted,the Permittee shall
conduct a performance test no more than 37 months after the previous performance
test for the given pollutant. If a performance test shows noncompliance with an
emission limit for a given pollutant,the Permittee shall return to conducting annual
performance tests(no later than 13 months after the previous performance test)for
that pollutant.
d. The source testing shall be conducted on the exhaust stacks of four(4) different kilns
and afterburners for each raw material type, creosote treated railroad ties and
untreated lumber,for a total of eight(8)different kilns and afterburners that have not
been previously tested.

i
Permit No. 10676R01
Page 7
e. The Permittee may re-establish any parametric operating value during periodic
testing. Compliance with previously approved parametric operating values is not
required during periodic required testing or other tests undertaken to re-establish
parametric operating values by the Permittee. If the new parametric operating values
re-established during periodic testing are more stringent, the Permittee shall submit a
permit modification application to revise the value(s)in the permit at the same time
the test report required pursuant to General Condition 17 is submitted. The permit
modification will be processed pursuant to 15A NCAC 02Q .0316. If, during
performance testing,the new parametric operating values are less stringent,the
Permittee may request to revise the value(s) in the permit pursuant to 15A NCAC
02Q .0309.
f. The Permittee shall comply with applicable emission standards at all times including
during periods of testing.
g. Unless otherwise specified by federal rules,the Permittee shall perform such testing
in accordance with 15A NCAC 02D .2600.
h. The Permittee shall arrange for air emission testing protocols to be provided to the
DAQ prior to testing.Testing protocols are not required to be pre-approved by the
DAQ prior to testing.The DAQ shall review testing protocols for pre-approval prior
to testing if requested by the Permittee at least 45 days before conducting the test.
i. To afford the Regional Supervisor,DAQ,the opportunity to have an observer
present,the Permittee shall PROVIDE the Regional Office,in WRITING, at least
15 days'notice of any required performance test(s).
j. During the source testing effort each kiln will be charged to it's maximum capacity
and be weighed to establish the lb/ton emission factors.
k. Two copies of the test results must be submitted to the Regional Supervisor,DAQ,
in accordance with the requirements of 15A NCAC 02D .2600 no later than 30 days
after the testing is completed. The results shall also include
the identification number of the kilns and afterburners being tested as specified in
Permit Stipulation A.9.
1. This permit may be revoked,with proper notice to the Permittee,or enforcement
procedures initiated, if the results of the tests indicate that the facility does not meet
applicable limitations.
m. The source shall be responsible for ensuring,within the limits of practicality,that the
equipment or process being tested is operated at or near its maximum normal
production rate,or at a lesser rate if specified by the Director or his delegate.
n. All associated testing costs are the responsibility of the Permittee.

i
Permit No. 10676R01
Page 8
I
I
12. AFTERBURNER REQUIREMENTS -As required by 15A NCAC 2D .0611,VOC and CO 1
emissions shall be controlled as described in the permitted equipment list.
a. Inspection and Maintenance Requirements -The Permittee shall properly operate,
inspect and maintain the control devices at all times. To comply with the provisions
of this permit and ensure that emissions do not exceed the regulatory limits,the
Permittee shall perform periodic inspections and maintenance(I&M)as
recommended by the manufacturer.At a minimum,the Permittee shall perform an
annual (for each 12-month period following the initial inspection)internal inspection
of each afterburner unit and calibration of continuous monitoring instrumentation.
b. Monitoring Requirements -The Permittee shall ensure the proper performance of
each afterburner by monitoring the following operational parameters;
i. Until testing establishing minimum/maximum temperature(s) for the
afterburner is approved by DAQ,all afterburners shall maintain
a 3-hour rolling average temperature at or above 1,650 degrees F.
ii. The minimum and/or maximum combustion zone operating temperature in
the Afterburners (CD-1)shall be maintained at the minimum and/or
maximum combustion zone operating temperature established during the
initial source test(based on a rolling 3-hour average)during operation. The
3-hour rolling averages for each afterburner shall be calculated using a
minimum of one(1) data point every 15-minute period. Each 15-minute data
point shall be calculated by averaging all the valid data values recorded by
the continuous monitoring system (CMS)for that 15-minute period. CMS
downtime shall not exceed 3%of the time each kilns is operational,per semi-
annual period.
c. Recordkegping Requirements
i. The results of all inspections and any variance from manufacturer's
recommendations or from those given in this permit(when applicable)shall
be investigated with corrections made and dates of actions recorded in a
logbook.Records of all control device maintenance activities shall be
recorded in the logbook.
ii. The Permittee shall continuously record the rolling 3-hour average minimum
and/or maximum combustion zone operating temperature in each afterburner.
iii. The Permittee shall document all periods, including date and duration,during
which the CMS was not operational and the reason for each CMS downtime
event(in reference to Section 12.a.ii.b above).
iv. The Permittee shall document each batch start and end times, defined as
when the kiln's burner is turned on(startup) and when the afterburner is
removed from the kiln(shutdown).
V. The logbook(in written or electronic form)shall be kept on-site and made
available to DAQ personnel upon request.

Permit No. 10676RO1
Page 9
d. Reportinix Requirements—The Permittee shall submit to the Regional Supervisor,
DAQ, on or before January 30 of each calendar year for the preceding six-month
period between July and December and July 30 of each calendar year for the
preceding six-month period between January and June, a summary report of
emissions and/or operational data listed below:
i. Report the percentage of CMS downtime per kiln including specific dates,
durations and reasons for each CMS downtime event(in reference to Section
12.a.ii.b above).
13. CONTROL AND PROHIBITION OF ODOROUS EMISSIONS -As required by 15A
NCAC 2D .1806"Control and Prohibition of Odorous Emissions" the Permittee shall not
operate the facility without implementing management practices or installing and operating
odor control equipment sufficient to prevent odorous emissions from the facility from
causing or contributing to objectionable odors beyond the facility's boundary.
14.NOTIFICATION REQUIREMENT-In accordance with 15A NCAC 2Q .0309,this permit
may be revoked unless Kilns(ID No.ES-1) and appurtenances are constructed in
accordance with the approved plans,specifications, and other supporting data. Within
15 days after start-up of the new or modified facilities,the Permittee shall provide written
notice of the-start-up to the Regional Supervisor, DAQ.
15. LIMITATION TO AVOID 15A NCAC 2Q .0501 —Pursuant to 15A NCAC 2Q .0315
"Synthetic Minor Facilities,"to avoid the applicability of 15A NCAC 2Q .0501 "Purpose of
Section and requirement for a Permit,"as requested by the Permitee,facility-wide emissions
shall be less than the following:
NOx - 100
CO 100
VOC 100
a. Operations Restrictions-To ensure emissions do not exceed the limitations above,
the following restrictions shall apply:
i. No more than 58,400 kiln operations shall be conducted per 12 consecutive
month period.
ii. No more than 58,400 tons of raw material will be processed in the kilns per
12 consecutive month period.
iii. The Permittee shall perform inspections and maintenance per the
requirements of 15A NCAC 2D .0611 "Afterburner Requirements."

Permit No. 10676R01
Page 10
b. Recordkeeying Requirements
i. The Permittee shall record monthly and total annually the following:
a. Number of kiln operations per month on each type of raw material.
b. The amounts of each raw material processed in the kilns per month,in
tons.
c. Emissions of NOx, CO and VOC, in tons.
ii. The Permittee shall comply with the recordkeeping requirements in the
15A NCAC 2D .0611 "Afterburner Requirements" permit condition.
c. Reporting Requirements—The Permittee shall submit to the Regional Supervisor,
DAQ,on or before January 30 of each calendar year for the preceding six-month
period between July and December and July 30 of each calendar year for the
preceding six-month period between January and June,a summary report of
emissions and/or operational data listed below:
i. The data shall include monthly and 12-month rolling totals for the previous
12-month period.
a. Number of kiln operations on each type of raw material.
b. The amounts of each raw material processed, in tons.
c. Emissions of NOx, CO and VOC,in tons.

Permit No. 10676RO I
Page 11
16. LIMITATION TO AVOID 15A NCAC 2D .0530 "PREVENTION OF SIGNIFICANT
DETERIORATION" - In accordance with 15A NCAC 2Q .0317,to comply with this permit
and avoid the applicability of 15A NCAC 2D .0530 'Prevention of Significant
Deterioration," as requested by the Permittee, emissions shall be limited as follows:
Emission Lintti - -- -
' Cansecutrve 12 month Period)
u F. .3§`#�"15b` F. ,.
Facility Wide NOx 250
Facility Wide VOC -- 250
a. Operations Restrictions,Recordkeeping Requirements, and Reporting_Requirements
To ensure emissions do not exceed the limitations above, the following restrictions
shall apply:
i. By complying with the operations restrictions,recordkeeping requirements,
and reporting requirements in the 15A NCAC 2Q .0315 "Synthetic Mirror
Facilities" permit condition,the Permittee shall have also complied with the
operations restrictions, recordkeeping requirements,and reporting
requirements for 15A NCAC 2Q .0317,Limitation to Avoid 15A NCAC 2D
.0530.

Permit No. 10676R01
Page 12
17. TOXIC AIR POLLUTANT EMISSIONS LIMITATION REQUIREMENT- Pursuant to
15A NCAC 2Q .0711 "Emission Rates Requiring a Permit," for each of the below listed
toxic air pollutants (TAPS), the Permittee has made a demonstration that facility-wide actual
emissions, where one or more emission release points are unobstructed and vertically
oriented, do not exceed the Toxic Permit Emission Rates(TPERs) listed in 15A NCAC 2Q
.0711(b). The facility shall be operated and maintained in such a manner that emissions of
any listed TAPS from the facility,including fugitive emissions, will not exceed TPERs listed
in 15A NCAC 2Q .071 I(b).
a. A permit to emit any of the below listed TAPs shall be required for this facility if
actual emissions from all sources will become greater than the corresponding
TPERs.
b. PRIOR to exceeding any of these listed TPERs,the Permittee shall be responsible
for obtaining a permit to emit TAPS and for demonstrating compliance with the
requirements of 15A NCAC 2D .1100 "Control of Toxic Air Pollutants".
c. In accordance with the approved application,the Permittee shall maintain records of
operational information demonstrating that the TAP emissions do not exceed the
TPERs as listed below:.
—
chronic
arciaes Ioxicants
IAcate Systei Acute Irrit
ants
(b/yr) Toxicants_(1b/hr) (lb/hr)C m
a (lb/day) `
Acetaldehyde(75-07-0) �Y— I 28.43
Acrolein(107-02-8) 0.08
Ammonia(as NH3)(7664-41-7) ! � �____ 2.84
Arsenic&Compounds(total mass of
elemental AS,arsine and all inorganic 0.194
compounds)(ASC(7778394))
Aenzn(a)pyrene{Component of 3.044
83329/POMTV&56553/7PAH){50-32-8} i
Beryllium Metal(unreacted)(Component
of EEC)(7440-41-7) 0.378 �—
Cadmium Metal,elemental,unreacted 0.507
(Component of CDC)(7440-43-9) III
Carbon tetrachloride(56-23-5) 618.006
r6hlorine(7782-50-5) F_
Chlorobenzene(108-90-7) 92.7 —
Chloroform 67-66-3 396.631
Chromium(VI)Non-Specific Compounds,
as Chrom(VI)(Component CRC) 0,008
(NSCR6)
-- ------ --------
Cresol(mixed isomers)(1319-77-3)
DEHP(Di(2-ethylhexyl)phthalate)(117- 1.3 -�— --
81-7)
Dichlorobenzene(p), 1,4-(106-46-7) _� 69.50��

Permit No. 10676RO1
Page 13
Ethylene dichloride(1,2-dichloroethane) 350.511
(107-06-2)
:F
Formaldehyde(50-00-0) 0.16
Hexane,n-(110-54-3) 46.3
]Hydrogen chloride(hydrochloric acid) 0.74
(7647-01-0)
Manganese&compounds(MN 1.3
Mercury,vapor(Component of HGC)
(7439-97-6) 0.025
Methylene chloride(75-09-2) i 2213.752 1.79 ^~
. _
[Nickel metal(Component of NIC)(7440- 0.3
02-0
PCB(polychlorinated biphenyls)(1336- 7,656
36-3)
Pentachlorophenol(87-86-5) 0.1 0.03
Phenol(1.08-95-2) 1.00
Styrene(10042-5) 11.16
TCE(trichloroethylene)(79-01-6) 5442.140
Tetrachlorodibenzo-p-dioxin,2,3,7,8-
(Component ofCLDC&83329/POMTV) 0.0002767
(1746-01-6)
Toluene(108-89-3) 197.96 58.97
Vinyl_.chloride(75-014) 35.051
..
Xylene(mxed isomers)(1330-20-7) �r 1.13.7 68.44

Permit No. 10676RO I '
Page 14
B. GENERAL CONDITIONS AND LIMITATIONS
1. In accordance with G.S. 143-215.108(c)(1),TWO COPIES OF ALL DOCUMENTS
REPORTS,TEST DATA,MONITORING DATA,NOTIFICATIONS, REQUESTS FOR
RENEWAL,AND ANY OTHER INFORMATION REQUIRED BY THIS PERMIT shall
be submitted to the:
Regional Supervisor
North Carolina Division of Air Quality
Fayetteville Regional Office
Systel Building
225 Green Street, Suite 714
Fayetteville,NC 28301-5094
910-433-3300
For identification purposes, each submittal should include the facility name as listed on the
permit,the facility identification number, and the permit number.
2. RECORDS RETENTION REQUIREMENT-In accordance with 15A NCAC 2D .0605,
any records required by the conditions of this permit shall be kept on site and made available
to DAQ personnel for inspection upon request. These records shall be maintained in a form
suitable and readily available for expeditious inspection and review. These records must be
kept on site for a minimum of 2 years,unless another time period is otherwise specified.
3. ANNUAL FEE PAYMENT-Pursuant to 15A NCAC 2Q .0203(a),the Permittee shall pay
the annual permit fee within 30 days of being billed by the DAQ. Failure to pay the fee in a
timely manner will cause the DAQ to initiate action to revoke the permit.
4. EQUIPMENT RELOCATION-In accordance with 15A NCAC 2Q .0301,a new air permit
shall be obtained by the Permittee prior to establishing,building,erecting,using,or
operating the emission sources or air cleaning equipment at a site or location not specified in
this permit.
5. REPORTING REQUIREMENT-In accordance with 15A NCAC 2Q .0309,any of the
following that would result in previously unpermitted,new,or increased emissions must be
reported to the Regional Supervisor, DAQ:
a. changes in the information submitted in the application regarding facility emissions;
b. changes that modify equipment or processes of existing permitted facilities; or
c. changes in the quantity or quality of materials processed.
If appropriate,modifications to the permit may then be made by the DAQ to reflect any
necessary changes in the permit conditions. In no case are any new or increased emissions
allowed that will cause a violation of the emission limitations specified herein.

Permit No. 10676R0I
Page 15
- i
6. In accordance with 15A NCAC 2Q .0309,this permit is subject to revocation or
modification by the DAQ upon a determination that information contained in the application
or presented in the support thereof is incorrect, conditions under which this permit was
granted have changed,or violations of conditions contained in this permit have occurred. In
accordance with G.S. 143-215.108(c)(1),the facility shall be properly operated and
maintained at all times in a manner that will effectuate an overall reduction in air pollution.
Unless otherwise specified by this permit,no emission source may be operated without the
concurrent operation of its associated air cleaning device(s) and appurtenances.
7. In accordance with G.S. 143-215.108(c)(1),this permit is nontransferable by the Permittee.
Future owners and operators must obtain a new air permit from the DAQ.
8. In accordance with G.S. 143-215.108(c)(1),this issuance of this permit in no way absolves
the Permittee of liability for any potential civil penalties which may be assessed for
violations of State law which have occurred prior to the effective date of this permit.
9. In accordance with G.S. 143-215.108(c)(1),this permit does not relieve the Permittee of the
responsibility of complying with all applicable requirements of any Federal, State, or Local
water quality or land quality control authority.
10. in accordance with 15A NCAC 2D .0605,reports on the operation and maintenance of the
facility shall be submitted by the Permittee to the Regional Supervisor,DAQ at such
intervals and in such form and detail as may be required by the DAQ. Information required
in such reports may include,but is not limited to,process weight rates, firing rates,hours of
operation,and preventive maintenance schedules.
11. A violation of any term or condition of this permit shall subject the Permittee to enforcement
pursuant to G.S. 143-215.114A, 143-215.114B, and 143-215.114C,including assessment of
civil and/or criminal penalties.
12. Pursuant to North Carolina General Statute 143-215.3(a)(2),no person shall refuse entry or
access to any authorized representative of the DAQ who requests entry or access for
purposes of inspection,and who presents appropriate credentials,nor shall any person
obstruct,hamper,or interfere with any such representative while in the process of carrying
out his official duties.Refusal of entry or access may constitute grounds for permit
revocation and assessment of civil penalties.
13. In accordance with G.S. 143-215.108(c)(1),this permit does not relieve the Permittee of the
responsibility of complying with any applicable Federal, State, or Local requirements
governing the handling,disposal,or incineration of hazardous,solid, or medical wastes,
including the Resource Conservation and Recovery Act(RCRA) administered by the
Division of Waste Management.
14. PERMIT RETENTION REOUIREMENT- In accordance with 15A NCAC 2Q .0110,the
Permittee shall retain a current copy of the air permit at the site. The Permittee must make
available to personnel of the DAQ,upon request,the current copy of the air permit for the
site.

Permit No. 10676ROI
Page 16
15. CLEAN AIR ACT SECTION 112W REQUIREMENTS -Pursuant to 15A NCAC 2D .2100
"Risk Management Program," if the Permittee is required to develop and register a risk
management plan pursuant to Section 112(r)of the Federal Clean Aix Act,then the
Permittee is required to register this plan with the USEPA in accordance with 40 CFR Part
68.
16. PREVENTION OF ACCIDENTAL RELEASES - GENERAL DUTY-Pursuant to Title I
Part A Section I I2(r)(1)of the Clean Air Act"Hazardous Air Pollutants-Prevention of
Accidental Releases-Purpose and General Duty," although a risk management plan may not
be required,if the Permittee produces,processes;handles,or stores any amount of a listed
hazardous substance, the Permittee has a general duty to take such steps as are necessary to
prevent the accidental release of such substance and to minimize the consequences of any
release.This condition is federally-enforceable only.
17. GENERAL EMISSIONS TESTING AND REPORTING REQUIREMENTS-If emissions
testing is required by this permit, or the DAQ, or if the Permittee submits emissions testing
to the DAQ in support of a permit application ox to demonstrate compliance, the Permittee
shall perform such testing in accordance with 15A NCAC 2D .2600 and follow all DAQ
procedures including protocol approval,regional notification,report submittal,and test
results approval. Additionally,in accordance with 15A NCAC 21) .0605,the Permittee shall
follow the procedures for obtaining any required audit sample and reporting those results.
Permit issued this the 201 of November,2021.
NORTH CAROLINA ENVIRONMENTAL MANAGEMENT COMMISSION
,z H th r Carter
Regional Supervisor
By Authority of the Environmental Management Commission
Air Permit No. 10676RO1

ATTACHMENT to Permit No. 10676RO1,November 24,2021
Insignificant 1 Exempt Activities
iggq K
"Source of Source of Title V.
n
Pollutants?
TES-EX-1
and Kiln Loading2Q .0102 (h)(5) Yes Yes
Crusher
IES-EX-2
Product Handling and Packaging
(System housed in intermodal
I shipping containers equipped 2Q .0102(h)(5) Yes Yes
with dust collection vents that
vent to one of two external
cartridge-type bagfilters [3,048
square feet of filter area, each].) _
Haul RoadF2Q IES-EX-3 .0102 (h)(5) ND Yes
— _�
IES-EX-4 2Q .0102 (h)(5) Yes F Yes --
Diesel Storage Tank
IES-EX-5 2Q .0102 (h)(5) Yes Yes
Maintenance Welding
1. Because an activity is exempted from being required to have a permit or permit modification
does not mean that the activity is exempted from an applicable requirement or that the owner
or operator of the source is exempted from demonstrating compliance with any applicable
requirement.
2. When applicable, emissions from stationary source activities identified above shall be
included in determining compliance with the permit requirements for toxic air pollutants
under 15A NCAC 2D .1100 "Control of Toxic Air Pollutants" or 2Q .0711 "Emission Rates
Requiring a Permit."
3. Sample permit conditions showing the regulatory requirements for exempt sources subject to
NESHAP,NSPS, and NCAC rules may be found here:
ht(ps://deq.nc.gov/agpern-Litconditions

USDAUnited States w cooperation Polycyclic Aromatic
Department of with the
Agriculture
United States Mi ration
Forest Service Department ofHydrocarbon
Transportation
Forest
Products Federal Laboratory Highway From Creosote-Treated
Administration
Research
Paper Railway Ties Into
FPL-RP-617
U�S
Ballast and Adjacent
Wetlands
Kenneth M.Brooks
0
�l} 4,
k

Abstract from the weathered ties at this time.No significant PAH
loss was observed from ties during the second summer.A
Occasionally,creosote-treated railroad ties need to be small portion of PAH appeared to move vertically down into
replaced,sometimes in sensitive environments such as the ballast to approximately 60 cm.Small amounts of PAH
wetlands.To help determine if this is detrimental to the may have migrated from the ballast into adjacent wetlands
surrounding environment,more information is needed on during the second stammer,but these amounts were not
the extent and pattern of creosote,or more specifically poly- statistically significant.These results suggest that it is rea-
cyclic aromatic hydrocarbon(PAH),migration from railroad sonable to expect a detectable migration of creosote-derived
ties and what effects this would have on the surrounding PAH from newly treated railway ties into supporting ballast
environment.This study is a report on PAH level testing during their first exposure to hot summer weather.The PAH
done in a simulated wetland mesocosm.Both newly treated rapidly disappeared from the ballast during the fall and
and weathered creosote-treated railroad ties were placed in winter following this initial loss.Then statistically insignifi-
the simulated wetland.As a control,untreated ties were also cant vertical and horizontal migration of these PAH suggests
placed in the mesocosm. Samples were taken of the ballast, that they either evaporated or were degraded in the ballast.
wetland sediments,groundwater,stormwater,and soil cores. Effects of PAH on the environment are discussed in the
Ballast and sediment samples were taken at intervals during Appendix.
the 18 months of the study.Results of the study showed that
there was an initial pulse of PAH moving from the treated Keywords: creosote, leaching,railway ties,wetlands,
railway ties into the ballast during the first summer of the polycyclic aromatic hydrocarbons
study. More PAH moved from the newly treated ties than
June 2004
Brooks,Kenneth M.2004.Polycyclic aromatic hydrocarbon migration from
creosote-treated railway ties into ballast and adjacent wetlands.Res.Pap.
FPL-RP-617.Madison,WI:U.S.Department of Agriculture,Forest Service,
Forest Products Laboratory.53 p.
A limited number of free copies of this publication are available to the
public from the Forest Products Laboratory,One Gifford Pinchot Drive,
Madison,WI 53726-2398.This publication is also available online at
www.fpl.fs.fed.us.Laboratory publications are sent to hundreds
of libraries in the United States and elsewhere.
The Forest Products Laboratory is maintained in cooperation with the
University of Wisconsin.
The use of trade or firm names in this publication is for reader information
and does not imply endorsement by the U.S.Department of Agriculture of
any product or service.
The United States Department of Agriculture(USDA)prohibits discrimina-
tion in all its programs and activities on the basis of race,color,national
origin,sex,religion,age,disability,political beliefs,sexual orientation,or
marital or familial status.(Not all prohibited bases apply to all programs.)
Persons with disabilities who require alternative means for communication
of program information(Braille,large print,audiotape,etc.)should contact
the USDA's TARGET Center at(202)720-2600(voice and TDD).To file a
complaint of discrimination,write USDA,Director,Office of Civil Rights,
Room 326-W,Whitten Building,1400 Independence Avenue,SW,Wash-
ington,DC 20250-9410,or call(202)720-5964(voice and TDD).USDA is
an equal opportunity provider and employer.

Contents
Page Page
Background........................................................................... 1 Appendix—Occurrence and Toxicity of PAH in the Envi-
Introduction........................................................................... 1 ronment...............................................................................34
Methods 2 Sources of PAH in Aquatic Environments.....................34
.............................................................................
Mesocosm Site Description..............................................2 Observed Levels of PAH in Terrestrial Environments...35
Mesocosm Design and Construction.................................2 Observed Concentrations of PAH in Aquatic Environ-
ments...............................................................................36
Sample Collection,Schedule,and Location.....................6
Fate of PAH in the Environment.....................................36
Transect Locations and Sample Dates..............................6
PAH From Different Sources..........................................37
Sampling Equipment and Protocols..................................6
Biological Effects Associated With PAH........................41
Quality Assurance Requirements......................................8 Recommended Numerical Benchmarks for Evaluating
Photographic Record.........................................................8 Environmental Risks Associated with PAH...................51
DataAnalysis....................................................................8
Results...................................................................................9
Baseline PAH Levels........................................................9
10-Day Postconstruction PAH Levels..............................9
3-Month PAH Levels........................................................9
6-Month PAR Levels...................................................... 11
9-Month PAH Levels...................................................... 12
12-Month PAH Levels.................................................... 12
15-Month PAH Levels.................................................... 14
18-Month PAH Levels.................................................... 15
Distribution of TPAH as Function of Depth in
Ballast and Sediments at End of Study........................... 16
Hydrologic Profile and Storm and Groundwater
PAH Concentrations....................................................... 17
Discussion........................................................................... 18
Data Quality Assurance.................................................. 18
PAHin Ballast................................................................ 19
PAH in Wetland Sediments............................................20
Summary.........................................................................23
Biological Assessment........................................................23
Conclusions.........................................................................26
Recommendations...............................................................27
Literature Cited...................................................................27

Polycyclic Aromatic Hydrocarbon Migration
From Creosote-Treated Railway Ties Into
Ballast and Adjacent Wetlands
Kenneth M.Brooks, Owner and Principal Scientist
Aquatic Environmental Sciences, Port Townsend, Washington
Background emerald dragonfly(Somatochlora hineana).This rail line,
built in the 1950s,has been infrequently used in the last
Creosote has been widely used to protect wood from attack 30 years.In 1996,Commonwealth Edison replaced unserv-
by fungi,marine borers,and insects in the United States iceable creosote-treated ties supporting the rails with newly
since 1865.It is a distillate derived from coal tar produced treated ties,raising concerns within the U.S.Fish and Wild-
by the carbonization of bituminous coal.Creosote is a com- life Service that creosote preservative might migrate from
plex mixture of at least 160 detectable hydrocarbon com- ties,through the ballast,and into adjacent wetlands used by
pounds,and all 18 major components are cyclic and aro- the endangered dragonfly.Unfortunately,predicting the
matic.According to Environment Canada(1992),80%of amount of creosote that might enter the wetland from the
creosote is composed of polycyclic aromatic hydrocarbons new ties is not possible with the current knowledge base.
(PAH).Although PAH occur naturally in the environment, More information on this subject is needed to make accurate
they are potentially harmful to a broad range of organisms environmental assessments.
(Eisler 1987).Thus,deposition of PAH in the environment
may be a concern,especially if endangered species are One element that confuses the issue is that there are many
present. potential sources of PAH associated with railway rights-of-
way(Wan 1991).These include coal and coal dust from
The preservative treatment of railway ties with creosote is cargo entering a coal-fired plant,herbicides used to control
accomplished in accordance with the American Wood- vegetation along rights-of-way,diesel exhaust from diesel—
Preservers'Association(AWPA)Standard C2.For durabil- electric locomotives,and heated lubricating oils and greases.
ity,most railway ties are cut from hardwoods,particularly With all these sources,it is very difficult to determine the
red or white oak(Quercus spp.).AWPA(1996)requires an specific contribution from creosote-treated railway ties.Coal
average retention of 96 kg creosote per m3 of treated red oak is a potential source of PAH along the Midwest Generation
with a minimum penetration depth equal to 65%of the an- rail line because this line carries coal into the Will County
nual rings or to refusal.Because the cells in white oak are power station.
filled with tyloses,this species is typically treated to refusal.
Treatment to refusal is achieved when no more than 2% This paper reports on a mesocosm study of a simulated rail
additional preservative is taken up by the wood in two line running through a wetland.The extent of PAH migra-
consecutive half-hour periods of treatment. tion from creosote-treated railway ties into the adjacent
environment was examined.A mesocosm design was chosen
The life expectancies of creosote-treated railway ties depend in an attempt to minimize the other sources of PAH and to
on rail traffic,tie placement,and environmental hazards. focus on those released from new and used creosote-treated
The service life of creosote-treated railway ties is typically railway ties.The mesocosm design is intended to very
30 years in southern regions,46 years in eastern regions, closely mimic the railway passing through the Des Plaines
and 51 years in western regions of the United States River wetland of concern.This study analyzed PAH in the
(Zarembski 1990). ballast,adjacent wetland soils,shallow groundwater,and
stormwater at quarterly or annual intervals,depending on the
Introduction type of railway tie treatment,for 2 years.
Commonwealth Edison(Chicago,Illinois)operates a spur Three PAH migration pathways were examined:direct con-
railroad line,the Midwest Generation rail line,that crosses tamination from surface stormwater,infiltration into shallow
the Des Plaines River wetlands in Will County,Illinois. groundwater and then laterally into the wetland,and lateral
These wetlands are inhabited by the endangered Hines movement out of right-of-way ballast.

In this study,weathered,newly treated,and untreated ties The mean TPAH value reported from Des Plaines River
were each placed in the wetland mesocosm.Samples were wetland samples by Brooks(1997b)was 0.833 f 0.520 µg
taken of groundwater,stormwater,sediment,ballast rock, TPAH/g.The mesocosm was isolated from the underlying
and cores.All samples were analyzed for PAH content. soils by an impermeable 6 mil polypropylene liner.This
Ballast and sediment samples were taken at 10 days,and evaluation suggested that there were no significant sources
3,6,9, 12, 15,and 18 months after the ties were placed in of PAH to this upland site and that it was suitable from this
the mesocosm. perspective.
Methods Mesocosm Design and Construction
Mesocosm Site Description A plan view of the mesocosm is provided in Figure 1 and a
cross-sectional view in Figure 2.The Corps of Engineer's
Several wetland sites were evaluated as potential locations permit condition required only a comparison of used railway
for the mesocosm study.An upland site near the town of ties with untreated ties.However,a third mesocosm contain-
Romeoville,Illinois,was chosen where there was minimal ing new creosote-treated ties was also constructed.Figure 3
potential for overtopping during high water.The chosen site shows the basic excavation at the mesocosm site.
was located in a relatively undisturbed area of Material
Service Corporation's property.It lies at an elevation of Mesocosm Liners and Subsurface
approximately 8.7 in above the Des Plaines River wetland. Irrigation System
The mesocosm soils were originally 504D(Sogn Loam).
However,overburden from the Material Service Corpora- Each mesocosm was isolated from the native soils with a
6 mil polypropylene liner with welded seams to ensure that
tion's gravel quarry of mixed and unknown soil type had
been deposited at this site.Wetland soils were excavated PAH in water percolating down through the mesocosm was
with an appropriate Corps of Engineers Section 404 permit. contained.This allowed for an understanding of the bulk
These wetland soils are 316(Romeo Silty Clay Loam).Soil loss of PAH from the railway ties to underlying groundwa-
types are those listed in the Soil Conservation Service Soils ter. In addition,the impermeable membrane prevented shal-
Inventory for Will County. low groundwater,or stormwater,from transporting PAH
laterally out of the mesocosms. The liner was bedded in sand
Baseline PAH concentrations were determined in three to prevent underlying rocks from compromising it.
random surficial soil samples collected at the mesocosm site
on May 6, 1997,and submitted to National Environmental These mesocosms were constructed in upland areas but
Testing(NET)(Bartlett,Illinois)for PAH analysis using needed to function as wetlands.The impermeable membrane
U.S.Environmental Protection Agency(EPA)Method 8310 was incorporated to help retain natural rainfall.However,
following Soxhlet extraction.Harkey and Young(2000) additional water was made available through an underground
have suggested that Soxhlet extraction overestimates bio- delivery system mimicking the groundwater that flows in the
logical effects because aromatic compounds are released Des Plaines River wetland.To accomplish this,the design
from sediments that would not normally be bioavailable. included a 3.8-kL water tank,supply lines,and float valves
They recommended a supercritical fluid extraction as more to maintain saturation at a level mimicking that found in the
representative of actual toxicity.To be conservative,and in wetland adjacent to the Midwest Generation rail line.Each
light of its long use,Soxhlet extraction was used throughout valve floated in its own sump connected to a 51-mm,perfo-
these studies.The results for baseline total PAH(TPAH)are rated polyvinyl chloride(PVC)pipe,which extended around
summarized in Table 1. the perimeter of the bottom of the mesocosm in contact with
the impermeable membrane.Because PVC will absorb PAH,
this PVC water distribution pipe was placed on the perimeter
of each mesocosm and it did not extend under,or immedi-
Table 1—Summary report of baseline PAH levels ately adjacent to,any area that was sampled for PAH.The
observed in surficial soils taken from the meso- liner and subsurface irrigation system are shown in Figure 4.
cosm study site right before construction.
Reported values have been corrected for the To assist in determining the level of water in the natural
surrogate(p-Terphenyl)recovery in each analysis. wetland adjacent to the actual rail line,a similar sump(con-
Replicate Detected PAH(µg/g) structed of PVC instead of stainless steel)was installed at a
distance of 30 cm from the right-of-way.This facilitated
1 none determination of natural wetland saturation levels and corre-
2 0.09 sponding adjustment of the float valves in the mesocosms.
3 0.14 Water was added to the mesocosms several times during the
Mean±95%CIO 0.08±0.17 summer of 1998,and wetland hydrology was maintained
"Cl,confidence interval. during the entire testing period.
2

72 ft
Groundwater sample sump.typ. 5ft 16 ft 7 ft
0.5 ft
5ft Top of 2 596 TOC topsoil 5ft 1.5 ft
Top of berm elev. 1
c N a=
' N
O
bill1 1 0 1 0
2 in. perforated PVC Weathered New ties Untreated
pipe and fittings = ties = 1 i Ues i
. 1
s s 1
1 1 1 1 l N
! i
0 � 0
a=
� N
Uo
Meet existing ground 3ft 3ft 2f 3ft 3ft
2 in.PVC pipe and fittings Q Float valves
Water tank
Figure 1—Detailed plan view of the mesocosms(1 In.=25.4 mm; 1 ft=0.3 m).
Railroad ballast 3/4 in.to
1-12 in.diameter 66 ft rail tie Groundwater
4 cm of 2 5%TOC topsoil sample sump
5
2 ;. - y ,k N lverston nn
CA
2 in.PVC
2 in. 1 in.sand bedding layer
perforated Wetland soils 6 mil polypropylene
PVC 3ft ft lines,welded seams 3
Oft Ott
5ft 3ft 3ft eft 2ft 3ft 3ft
0.66 ft rail ties
I
Existing �.Y i ;�' P�T� Yr} Oive ion berm r
ground - •�; N
N
2 in.perforated
PVC pipe typ.
1 in.sand bedding layer
Wetland soils
Figure 2—Cross sections of one of three mesocosm compartments(one cross section each direction
across mesocosm) (1 in.=25.4 mm; 1 ft=0.3 m).
3

IL
r, s'
x
Figure 3-Basic mesocosm excavation. Figure 5—Mesocosms after placement of wetland soils.
00
Figure 4—Impermeable liner and subsurface irrigation Figure 6—Mesocosm after placement of broken
system installed to maintain and control wetland limestone ballast in an identical configuration with the
hydrology. right-of-way crossing the Des Plaines River wetland.
Placement of Wetland Soils Baseline ballast samples were collected from random loca-
Fallowing installation of the liner and subsurface irrigation tions in each mesocosm just prior to placing the treated
system,each mesocosm was filled to a depth of 60 cm with crossties.Baseline ballast samples were collected in the
native wetland soil,excavated from the adjacent area. untreated tie mesocosm within 1 h of placing the untreated
Figure 5 shows the mesocosms following placement of the ties.The laboratory conducting the PAH analysis(NET)
wetland soils. Wetland soils were tested for PAH and total purchased large Soxhlet extractors allowing retrieval of PAH
organic carbon(TOC)content prior to placement in the from ballast of the specified size without further mechanical
mesocosms. reduction.
Placement of Limestone Ballast Railway Tie Installation
Broken limestone ballast(19 to 38 mni)was added to the Newly treated and weathered ties,removed from the Mid-
mesocosms from May 12 to 14, 1998,using a tractor- west Generation rail line,were installed in two of the meso-
mounted backhoe.Both the backhoe and the dump truck cosms on May 18, 1998. Untreated hardwood ties,of the
used to transport the ballast to the mesocosm site were thor- same tree species(red oak)were place in the third mesocosm
oughly pressure-washed prior to use.Railway ballast ex- as a control.The weathered ties were cut to the same length
tended to the edges of each subsection,along the length of as the new ties and the untreated ties prior to installation.
the mimicked railway,to model the infinitely long aspect of Each mesocosm contained three standard-sized crossties
the typical railroad right-of-way. Figure 6 shows the meso- placed in a fashion identical to the actual right of way.
cosms following placement of the ballast.
4

Y..
Figure 7—Completed wetland mesocosms. Figure 8—Mesocosm study site in the fall of 1998,
approximately 6 months following construction.
Table 2—Measured creosote retention for new Table 3—Number of plant species and wetness values
and old railway ties used in the mesocosm study, observed in mesocosms containing new and weathered
Each measurement is the mean of 12 borings. creosote-treated ties and untreated red oak ties.
New ties(kg1m3) Old ties(kglm3) Number of Overall average
plant value of
44.64 55.52 Mesocosm species wetness'
28 84.96
57.28 84. 6 Untreated red oak ties 24 -0.9
Newly treated creosote ties 38 —1.0
Weathered creosote ties 28 —1.0
Each tie was identified with a plastic label. Day 0 samples aWetness values range from obligate wetland species(-5)
were collected on the day the ties were placed in the ballast. to obligate upland species(5).
The completed mesocosms are shown in Figure 7.
Actual creosote retentions in randomly selected new ties wetland soils,making sampling difficult,The native wetland
were determined by Kerr McGee(Oklahoma City,Okla- soils were scalped to a depth sufficient to exclude any viable
homa),the producer of the newly treated ties.Used ties, roots of this plant(30 to 40 cm).Wetland vegetation did
previously taken out of service and stored at Commonwealth grow in the mesocosm during 1998. However,the plant
Edison were assayed for retention on site by personnel from community did not include reed canary grass and it did not
Kerr McGee,Twelve 7.6-cm-long cores were taken from become heavy enough to warrant the use of an herbicide.
each tie(three per longitudinal surface).The target retention Following completion of all construction,a 2-m-high chain-
specified by AWPA Standard C6(AWPA 1996)for oak link fence,equipped with a locked gate,was installed around
crossties is 112 kglm3 or treatment to refusal. Oak is a diffi- the mesocosm to enhance security. Figure 8 shows the meso-
cult to treat hardwood,and ties are usually treated to refusal. cosms in the fall of 1999.
The actual retentions measured in new and old ties are
provided in Table 2. Volunteer Mesocosm Vegetation
The mean retention for the three new ties(43 kg/m3)was Mesocosm vegetation was inventoried by Christopher B.
less than the mean for the three old ties(60 kg/m3),but Burke Engineering Ltd.(CBBEL, Rosemont, Illinois)on
the differences were not statistically significant June 29, 1999. Vegetation grew in the wetland areas of the
(a=0.05 (t«;,=2.78 and t,,,,= 1.09)). mesocosm located on either side of the ballast.The plants
growing within each cell were identified and assigned wet-
Vegetation Management land indicator values(Tn.These values range from W=-5,
The area where wetland sails were acquired was covered indicative of obligate wetland species occurring in wetlands
with reed canary grass(Phalaris arundivacea),which is with a probability of>99%to th=5, representing species
aggressively invasive. It was important to minimize intro- that are obligate upland species with a probability of being
duction of this species into the mesocosm because the addi- found in wetland areas of<1%. Wetland indicator values
tional organic matter contributed by a heavy growth of reed were those given in Swink and Wilhelm(1994).The results
canary grass would greatly complicate the measurement of of this inventory are summarized in Table 3.
TOG and PAH. In addition,the hardy roots would bind the
5

No attempt was made in this report to analyze the vegetation Each mesocosm was identified by a sign,located on the
data provided by CBBEL and Swink and Wilhelm(1994).It outside edge of the sampling area,designating it as either
is apparent that the hydrology created and maintained in new tie,weathered tie,or untreated tie.
these mesocosms was able to sustain a community of plants
that included many obligate wetland species and that on Sample Collection, Schedule,
average would meet the requirements of a regulated wetland. and Location
The number of different plant species and wetness factors
observed in the mesocosms containing creosote-treated Stormwater
railway ties exceeded that observed in the untreated tie Three stormwater samples from the untreated mesocosm and
mesocosm.This suggests that the presence of creosote- five samples each from the newly treated and weathered tie
treated ties in the ballast did not adversely affect the plant mesocosms were collected during this study to evaluate the
community.However,no quantitative assessment was migration of PAH from ballast in surface flows using gas
attempted and none should be inferred. chromatography/mass spectroscopy(GC/MS)(EPA 2003a).
A total of 13 stormwater samples were analyzed for PAH.
Groundwater Sampling
Groundwater sampling was attempted through a 15-cm- Sediment
diameter stainless steel sump installed at full depth in the Samples for PAH analysis in mesocosm wetland soils at
wetland soils.The sump was covered with a stainless steel distances of 0.0,0.25,0.50,and 0.75 in from the edge of the
cover when not in use.The bottom of the sump had four ballast along three transects(one transect adjacent to each
orthogonal holes,each 5.0 cm in diameter,that were tie)(high-pressure liquid chromatography(HPLC);EPA
screened with 500-µm stainless steel screens.The sump was 2003b). In total,229 surficial wetland sediment samples
located on the opposite side of the mesocosm from the wet- (upper 2 cm)were collected and analyzed for PAH analysis.
land water delivery system.No perforated PVC pipes were
located in the vicinity of the sump.The tops of these sumps Ballast Rock
can be seen in Figure 8. Ballast rock was collected for PAH analysis at distances of
Water did not migrate vertically in these Des Plaines River 5,20,and 30 cm from the east or west face of each tie
wetland soils,and the sumps collected insufficient amounts (HPLC;Modified EPA Method 8310).In total, 174 ballast
of water for sampling during this study,even though the samples were collected and analyzed from the surface of the
soils remained saturated during the entire study and wetland mesocosms.
portions of the mesocosms were periodically inundated Core Samples
during heavy rainfall.Beginning in the summer of 1998,
stormwater was collected in deep glass beakers inserted into Core samples were collected at 10-cm increments to the full
the wetland soils with their tops flush with the surrounding depth of the ballast and wetland sediments at the end of the
wetland soils. study.These core sections were analyzed individually for
PAH to determine the potential for vertical migration
Construction Notes (HPLC;EPA Method 8310).In each mesocosm,36 ballast
All excavation,transportation of construction materials,and core samples were collected from two locations,and I 1
other mesocosm work was accomplished using equipment wetland sediment core samples were collected from the
that had been thoroughly pressure-washed and checked for edge of the ballast in the new tie mesocosm.
oil and hydraulic leaks prior to use.All equipment was Transect Locations and Sample Dates
serviced at a minimum distance of 30 in from the mesocosm.
All nonessential hydrocarbons,not part of the design,were The position of transects for each sampling period is pro-
kept a minimum of 30 m from the mesocosm. vided in Table 4 along with the date on which samples were
Approximately 0.4 m3 of additional ballast was set aside, collected.Transect positions are relative to either the east
inside the fenced area,and covered with a tarp.This addi- end of individual railway ties or to the south end of the
tional ballast rock was used to replace that taken from the simulated railway line in each mesocosm.These relation-
mesocosms during sampling. Likewise,approximately ships are shown in Figure 9.
0.1 in of wetland soil was set aside to replace surficial Sampling Equipment and Protocols
wetland soils removed during sampling.The sampling
schedule is designed so as not to sample in the same location Gloves and Booties
twice.However,it was important to maintain the geomor- New latex gloves and synthetic booties were worn for all
phology of the mesocosms'surface throughout the study, sampling except the final event.A single pair of booties
and therefore,replacement of sampling material was were dedicated to each mesocosm.A new pair of gloves was
necessary. worn for each transect.
6

Table 4—Transect location in centimeters from the origin described in Figure 9
Sample event Untreated tie Weathered tie New tie Wetland
Baseline(5/18/98) N401N120/N80 N01S801S160 S2001S60/S120 E20/E1101W80
Post construction(5128198) S201N601N240 N1001S601N240 N901S240/S180 W1201W601W20
Quarter 2(8/18/98) N1601S1001S200 S100/S1801N40 NO/S140/N220 E40/W50/E30
Quarter 3 (11/18198) SO1N2001S160 N1401N601S240 N40/N2001N80 E101E90/E100
Quarter 4 (2/18/99) N20/N240/S180 S140/N1801N80 S0/S160N140 E70M7OM30
Quarter 5 ((5/24/99) S120/S140/N180 N201S201S120 S801S160/1\1240 W130/W901W10
Quarter 6 (8/24/99) NO/S2201S80 S200/N1601N220 N10O/S201S100 E140/E601W100
Quarter 7 (11/24/99) N2201N1101N60 N120/SO/S40 N120/N180/N60 E120/E501E130
Increasing distance along wetland transects Sediment Sample Containers
Sediment sample containers for PAH analysis were made of
--- -•- _ - 4W,,,Origin for glass and held 500 mL of wetland soil. Larger,2-1,wide-
all transect mouth glass containers were used for the ballast rock.All
; - _ ' locators sample containers were washed with a phosphate-fret deter-
w gent solution,followed by a thorough rinse with hot tap
cV) water and analyte-free water.This was followed by an ace-
tone rinse and a final rinse using high-purity methylene
o m chloride. Lids were placed on the sample containers during
c'2 the final rinse step.Firing of glass containers at approxi-
mately 350°C for 4 h was allowed as a substitute for the final
v o solvent rinse only if precautions were taken to avoid con-
ro tamination as the container was dried and cooled.
Water Sample Containers
Water sample containers for PAH analysis were made of
C B A glass and held a minimum sample size of 1 L.Containers
Transect letter designations were precleaned as described for sediment sampling
North South equipment.
Sample Containers for Total Organic
Figure 9—Location of randomly chosen transects for Carbon and Sediment Grain Size
the mesocosm study.Three numbers are provided for
each date and mesocosm, corresponding to each of the Sample containers for TOC and sediment grain size analysis
three transects.The letter N or S,associated with the tie were made of either glass or low-density polyethylene.They
transects, refers to the north or south face of the tie. were first washed with a phosphate-free detergent solution,
Likewise,the E or W letter associated with wetland followed by a thorough rinse with hot tap water and
transects refers to the east or west side of the analyte-free water.
mesocosm.
Wetland Sediment Sampling Equipment
Wetland sediment sampling equipment was constructed of
stainless steel.A separate spatula was used for each transect
Sample Site Access (nine required).These spatulas were precleaned with a phos-
Clean wooden planks(one for each mesocosm)were used to phate-free detergent solution,followed by a thorough rinse
span the wetland soils located between the ballast and the with hot tap water and analyte-free water.Before use,
mesocosm's berm. Any disturbance could redistribute equipment was rinsed with solvent(acetone,hexane,or
accumulating PAH,confounding the results. All human methanol)and air-dried.The spatulas were transported into
trespass was avoided in the simulated wetland areas.The the field in sealed polyethylene bags. Samples were taken in
entire mesocosm was protected with a cyclone fence and order of least anticipated contamination(furthest from the
locked gate. ballast to closest to the ballast),and field cleaning was not
required.
7

Ballast Sediment Sampling Equipment Total Organic Carbon
Stainless steel tongs,one for each transect,were precleaned One certified reference material standard was required per
and transported as described for wetland sediment sampling survey.Five percent of the samples or a minimum of one
equipment. sample was required to be run in triplicate,and one blank
sample was required at the same interval.
Stormwater and Groundwater Sampling
A field(battery-operated)peristaltic pump was used for all Sediment Grain Size Analyses
water sampling.All tubing,excepting a short section of Triplicate samples were conducted on one,or a minimum of
tubing for the pump was made of Teflon(Dupont Corp., 5%,of the samples.The root square deviation was 520%for
Wilmington,Delaware)or glass.Glass was recommended these triplicate samples.
because it is easy to clean,using the same procedures as
described for sediment sample containers. Separate tubing Field
was used for each mesocosm groundwater sample(three
required)or for each stormwater sample(three required). One randomly chosen field replicate for groundwater sam-
Replicate samples within the same mesocosm were obtained pling in each mesocosm and one random field replicate for
using the same tubing. the wetland soil sampling were required during each sample
period.No field replicates were collected for the ballast
Sample Documentation and Handling samples because this would require too many sample loca-
tions,resulting in resampling of the same location during the
Samples were tightly capped in prelabeled bottles and stored study.Container blanks,field blanks,preservation blanks,
on ice in the field.Samples were kept at<4°C until arrival at rinsate blanks,and trip blanks were not required for this
the analytical laboratory.Water samples for PAH analysis study.A temperature blank was included in each cooler,and
were held at 4°C for a maximum of 7 days prior to analysis. the temperature of the cooler was determined on receipt
Sediment samples for PAH analysis were held for a maxi- at NET.
mum of 14 days at 4°C.Longer holding times,such as for
archiving samples or sample residues,required freezing at Chain of Custody
<-18°C.Frozen samples can be held for one or more years
before extraction.Extracted samples should be analyzed Chain of custody procedures complied with American
within 40 days(PSWQA 1996). Society for Testing and Materials(ASTM)D4840-88.
Testing Laboratory
QA requirement Data qualifier criteria
National Environmental Testing is an Illinois State accred-
ited laboratory,and they proposed the special detection Method blank(1 per batch) None detected in blanks
limits for this study.All of the detection limits provided by Replicates(1 per batch) 5100%relative percentage
NET were less than,or equal to,the recommended detection difference
limits provided in PSWQA(1996)for the Puget Sound Matrix spike(1 per batch) 50%to 150%matrix spike
Ambient Monitoring Program Marine Sediment Monitoring recovery
Task(0.020 to 0.100 µg/g).
Surrogate in all samples and ±95%confidence interval
Quality Assurance Requirements QA samples
The following quality assurance(QA)program was required
according to Brooks(1997c)for each batch of samples Photographic Record
(batches not to exceed 20 samples).
A photographic record of the project was created. Specific
PAH Analysis photographic requirements were defined in the study
The following QA tests and data qualification criteria were protocols.
stipulated for PAH analysis.Most of these QA requirements Data Analysis
could be met using standard protocols. However,the matrix
spike of ballast(2-to 4-cm stones)is an unusual require- The experimental design used in this study includes suffi-
ment.National Environmental Testing verified their extrac- cient replicates to enable statistical tests of the difference
tion procedures for ballast using spiked samples prior to between samples collected at control(untreated ties)and
evaluating samples collected from the mesocosms during the treatment(new and weathered tie)sites.The design is such
baseline evaluation. that statistical significance can be examined using either
regression analysis of values at varying distances along
transects,t-tests,or analysis of variance(ANOVA).
8

Results 10-Day Postconstruction PAH Levels
Baseline PAH Levels Replicate ballast and sediment samples were collected from
each mesocosm to determine PAH levels 10 days following
Before the mesocosms were constructed,nine random sam- completion of construction.
ples of wetland soil were collected and composited in three
samples that were analyzed by NET for total volatile solids Ballast
(TVS),TOC,and 16 EPA priority PAH. Polycyclic aromatic Significant increases in PAH concentrations were not ob-
hydrocarbons were not observed above the method detection served in the untreated wooden tie mesocosm 10 days fol-
limits in any of these samples.The sum of half the detection lowing tie placement.Low levels of PAH were observed in
limit for each compound was 0.257 f 0.026 µg TPAH/g dry all ballast samples adjacent to creosote-treated wood ties
sediment weight.Total organic carbon was measured at 24.6 (Table 5).The PAH clines,particularly in ballast next to the
f 9.7%.These TOC values are suspect because TVS were newly treated railway ties,suggest that the source of the
measured at 18.3 f 3.0%and TOC is normally about 60%of PAH was in fact the ties.This observation is further sup-
TVS.In either case,these wetland soils have high organic ported by the lack of PAH observed in ballast adjacent to
carbon content that will bind PAH released from the railway untreated wooden ties.Furthermore,it appeared that more
ties.Nine subsamples of this material were analyzed for PAH had migrated from the newly treated ties into adjacent
TVS by Aquatic Environmental Sciences(Port Townsend, ballast than from the weathered ties. However,the high
Washington)at the end of the study.The percentage TVS variance to mean ratios suggested that the distribution of
varied between 14.19%and 21.32%suggesting a range in PAH was very patchy.
TOC of 8.5%to 12.8%.The mean TOC value of 11.9%is
typical of organic soils found in wetlands. Wetland Sediments
Ballast Wetland sediments were sampled at 0.0,25,50,and 75 cm
from the toe of the ballast 10 days after construction
Polycyclic aromatic hydrocarbons were not observed above (Table 6).Excepting a single high sample at the closest
the method detection limits in any of the ballast samples. distance(0.0 cm)in the weathered tie mesocosm,significant
The sum of the detection limits for all 16 PAH was 0.51 µg increases in wetland sediment PAH concentrations were
TPAH/g dry ballast. not observed.
Wetland Soils The single high sample collected from the weathered tie
mesocosm sediments(11.2 µg TPAH/g dry sediment weight)
Polycyclic aromatic hydrocarbons were observed above did not contain a PAH profile consistent with creosote.
detection limits in five of six baseline wetland soil samples. Polycyclic aromatic hydrocarbon profiles in ballast were
Total PAH concentrations ranged from 0.183 to 0.893 µg high in acenaphthene,fluoranthene,fluorene,phenanthrene,
TPAH/g dry soil with a mean and 95%confidence interval and pyrene—a mixture consistent with creosote following
of 0.430 f 0.183.These values are within the range of values treatment.The sediment sample in question consisted mainly
reported by Brooks(1997b)for reference sediments in the of high molecular weight(HMW)compounds including
River South PAH study(0.833 f 0.520). benzo(a)anthracene,benzo(a)pyrene,benzo(ghi)perylene,
chrysene,and pyrene.This profile is more characteristic of
Surrogate Recovery creosote contamination that has weathered for many years or
Analysis of the rocks comprising ballast was accomplished of another PAH source.Other than the single elevated sam-
using a protocol developed by Aquatic Environmental Sci- ple,PAH did not appear to be migrating from the ballast into
ences and NET. Surrogate(p-Terphenyl)recovery was the wetland.
excellent for ballast samples analyzed to date with a mean
recovery of 93.8%,median of 98.1%,and a range of 56%to 3-Month PAH Levels
122%.These results are more consistent than surrogate
recovery in the wetland soils that averaged 81.2%with a Replicate samples were collected from ballast and sediments
median of 90.2%and a range of 11.5%to 119.5%.The in the newly treated and untreated railway tie mesocosms
surrogate compound was masked in 3 of 45(7%)ballast 3 months after placement of the ties. Samples were not
samples and 22%of wetland soil samples.Analytical results collected in the weathered tie mesocosm at this time.
have not been corrected for surrogate recovery.This would Ballast
have required invoking uncertain assumptions regarding the
corrections to be applied to the samples in which surrogate Concentrations of PAH were elevated(814.7 µg TPAH/g
recovery was masked. dry ballast)in a single ballast sample collected immediately
adjacent(5.0 cm station)to an untreated railway tie.There
is no source of PAH in the untreated tie mesocosm and this
result suggests that care must be exercised when evaluating
9

Table 5-Concentrations of PAH observed in railway Table 7-Concentrations of PAH observed in railway
right-of-way ballast at distances of 5,20,and 30 cm right-of-way ballast at distances of 5,20,and 30 cm from
from new and weathered creosote-treated railway ties new creosote-treated railway ties and untreated ties
and untreated ties 10 days following tie placement. 3 months following tie placement.The detection limit
The detection limit was used as a minimum value for was used as a minimum value for each compound
each compound
Mean
Distance Mean TPAH 95% Distance TPAH ±95%
Mesocosm (cm) (µg/g) confidence Mesocosm (cm) (µg/g) SD confidence
Untreated 5 0.153 0.014 Untreated 5 271.6 470.4 532.3
Untreated 20 0.173 0.052 Untreated 20 0.0 0.0 0.000
Untreated 30 0.153 0.014 Untreated 30 0.0 0.0 0.000
New 5 2.498 1.931 New 5 942.3 907.4 1,026.8
New 20 1.330 1.179 New 20 1,052.1 683.0 772.9
New 30 0.578 0.332 New 30 373.0 325.7 368.6
Weathered 5 0.668 1.605
Weathered 20 0.175 0.483
Weathered 30 0.358 2.502 Table 8-Concentrations of PAH observed in mesocosm
wetland sediments at distances of 0,50,and 75 cm from
Table 6-Concentrations of PAH observed in wetland new and weathered creosote-treated railway ties and
sediments at distances of 0,25,50,and 75 cm from the untreated ties 3 months following tie placement.
toe of right-of-way ballast in mesocosms containing The detection limit was used as a minimum value for
newly treated,weathered,and untreated railway ties. each compound
Samples were collected 10 days following completion Mean
of construction.The detection limit was used as a Distance TPAH 95%
minimum value for each compound Mesocosm (cm) (µg/g) SD confidence
Distance Mean TPAH ±95% Untreated 0 0.356 0.057 0.065
Mesocosm (cm) (µg/g) confidence Untreated 50 0.744 0.851 0.963
Weathered 0 3.964 7.065 Untreated 75 0.366 0.120 0.136
Weathered 25 1.108 1.549 Weathered 0 0.712 0.168 0.190
Weathered 50 0.378 0.132 Weathered 50 6.743 10.8 12.248
Weathered 75 0.274 0.012 (0.320) (0.247) (0.280)
Untreated 0 0.292 0.024 Weathered 75 0.534 0.506 0.572
Untreated 25 0.325 0.022 New 0 0.444 0.168 0.190
Untreated 50 0.425 0.290 New 50 0.743 0.413 0.467
New 75 0.314 0.029 New 75 0.407 0.065 0.074
New 0 0.727 0.722
New 25 0.456 0.050 Wetland Sediments
New 50 0.376 0.171
New 75 0.319 0.085 Similar to the first sampling period,a single high sample
(19.2 µg TPAH/g dry sediment)was collected 50 cm from
the toe of the ballast in the weathered tie mesocosm.
the meaning of a single high result in replicated PAH Elevated PAH concentrations were not observed in other
studies. wetland sediments.The other two samples collected at
50 cm in the weathered tie mesocosm were low(4.3 µg/g).
All 10 ballast samples collected from the area adjacent to the In addition,like the previous sample,this one was also rich
newly treated ties contained elevated levels of PAH with a in HMW compounds and contained low concentrations of
profile characteristic of creosote.These values ranged from those compounds characteristic of creosote,particularly
80 to 1,984 µg TPAH/g dry ballast weight.Creosote was phenanthrene and fluoranthene,which were not observed
clearly migrating from the ties into the adjacent crushed above the detection limits. However,the detection limits
limestone rock ballast(Table 7).The variance to mean ratios were very high in this sample,further confounding the
in those samples where PAH was detected were>1.0,indi- analysis.When this sample is excluded from the analysis,
cating a very patchy PAH distribution.This distribution is the results(provided in parentheses in Table 8)indicate
consistent with the particulate PAH transport hypothesis no movement of PAH from the right-of-way into the
developed by Goyette and Brooks(1999). wetland environment during the first 3 months following
construction.
10

Table 9—Concentrations of PAH observed in railway All nine ballast samples collected from the area adjacent to
right-of-way ballast at distances of 5,20,and 30 cm the newly treated ties contained elevated levels of PAH with
from new and weathered creosote-treated railway ties a profile characteristic of creosote.These values declined
and untreated ties 6 months following tie placement. from a high of 54.6 mg/kg dry weight immediately adjacent
The detection limit was used as a minimum value for to the tie(5.0 cm)to 32.9 mg/kg at 20 cm and 8.8 mg/kg at
each compound 30 cm from the newly treated ties. Creosote was clearly
Mean migrating from these ties into the adjacent ballast.Total
Distance TPAH 95% PAH concentrations observed in the weathered tie mesocosm
Mesocosm (cm) (µg/g) SD confidence were lower than those observed in the new tie mesocosm but
Untreated 5 0.661 1.145 1.295 were significantly higher than observed in the untreated tie
Untreated 20 0.000 0.000 0.000 mesocosm.
Untreated 30 0.000 0.000 0.000 The variance to mean ratios in those samples where PAH
New 5 54.561 80.740 91.364 was significantly elevated were>1.0,indicating a patchy
New 20 32.928 50.529 57.178 distribution.This is shown in Figure 10,which provides box
and whisker plots(mean f 1.0 and 1.96 standard errors of
New 30 8.782 3.218 3.641 the mean)for the data as a function of both distance and
Weathered 5 1.082 1.874 2.121 treatment.Analysis of variance indicates that differences
Weathered 20 0.088 0.152 0.172 between the treatments were marginally significant
Weathered 30 1.489 2.578 2.918 (p=0.0518).Post hoc testing using Duncan's test with
multiple ranges indicates that TPAH concentrations in the
new tie mesocosm ballast were significantly higher than in
either the weathered tie(p=0.036)or the untreated tie
6-Month PAH Levels (p=0.041)mesocosms but that TPAH concentrations in the
weathered tie and untreated tie mesocosm's were not signifi-
Replicate samples were collected from ballast in the newly cantly different at a=0.05(p=0.963).Differences in
treated and untreated railway tie mesocosms and from sedi- TPAH concentrations were not significantly a function of
ments in all three mesocosms 6 months after placement of distance(p=0.62).This is because single high TPAH con-
the ties(Table 9). centrations were observed at distances of 5 and 20 cm from
the face of one newly treated tie 6 months after placement of
Ballast the ties.
Polycyclic aromatic hydrocarbons were observed in a single
ballast sample collected 5 cm from a tie in the untreated Wetland Sediments
mesocosm.However,the mean TPAH concentration in the Wetland sediment concentrations of polycyclic aromatic
untreated tie mesocosm ballast was not significantly differ- hydrocarbons observed 6 months after placement of the ties,
ent((x=0.05)than observed in reference area sediments are summarized in Table 10.No sample was significantly
from the Des Plaines River wetland. elevated above Des Plaines River baseline PAH levels.
180
140 5 cm 20 cm 30 cm
100
60 ❑
20
-20
-60
N U W N U W N U W
Figure 10—Box and whisker plots describing the concentrations of all PAH observed in ballast rocks
at distances of 5.0,20.0,and 30.0 cm from the faces of newly treated railway ties(N),untreated
railway ties(U),and weathered creosote-treated ties(W)in the mesocosm study.These data were
collected 6 months after placement of the ties.
11

Table 10-Concentrations of PAH observed in Table 11-Concentrations of PAH observed in railway
mesocosm wetland sediments at distances of 0, right-of-way ballast at distances of 5,20,and 30 cm
50,and 75 cm from new and weathered creosote- from new creosote-treated railway ties and untreated
treated ties and untreated ties 6 months following ties 9 months following tie placement.Each value is the
placement of the ties.The detection limit was used mean of three replicates.The detection limit was used
as a minimum value for each compound as a minimum value for each compound
Mean Mean
Distance TPAH 95% Distance TPAH
Mesocosm (cm) (µg/g) SD confidence Mesocosm (cm) (µg/g) SD Variance
Untreated 0 0.476 0.257 0.675 Untreated 5 0.313 0.165 0.000
Untreated 50 0.438 0.127 0.030 Untreated 20 0.307 0.005 0.000
Untreated 75 0.542 0.300 0.239 Untreated 30 0.301 0.000 0.000
New 0 0.581 0.204 0.291 New 5 1.974 2.124 4.512
New 50 0.434 0.097 0.144 New 20 1.950 1.426 2.034
New 75 0.335 0.017 0.339 New 30 0.872 0.466 0.218
Weathered 0 0.708 0.597 0.675
Weathered 50 0.363 0.026 0.030 Wetland Sediments
Weathered 75 0.399 0.211 0.239
One replicate at the 75-cm station in the new tie mesocosm
was excluded from the analysis.Detection limits in this
treatments or distances.The null hypothesis that wetland sample were exceptionally high,ranging from 0.75 to 3.4 µg
sediment PAH concentrations were equal in all treatments PAH/g dry sediment.Compounds typical of creosote were
and/or at all distances was not rejected at a=0.05.There not detected but benzo(a)anthracene,benzo(b)fluoranthene,
is no evidence in the 27 sediment samples collected at benzo(a)pyrene,chrysene,and pyrene were.The TPAH
6 months that polycyclic aromatic hydrocarbons were (including the value of the detection limit where PAH were
moving from the ballast into the adjacent wetland. not detected)was 75.8 µg/g.The TPAH for the other two
replicates at this distance in this mesocosm on this date were
9-Month PAH Levels 0.64 and 0.78 µg TPAH/g.The sample was deleted because
of the abnormally high detection limits,because compounds
Nine months after tie placement,three replicates of ballast associated with creosote were not detected,and because the
rock were collected from each of three distances located 5, compounds detected were not typical of creosote. Summary
20,and 30 cm from the face of untreated and newly treated statistics for PAH in the remaining sediment samples are
ties.In addition,three replicate wetland soil samples were provided in Table 12.Variance to mean ratios were all less
collected in each mesocosm at distances of 0.0,25,50,and than one,suggesting a rather uniform PAH distribution.
75 cm from the toe of the ballast carrying the ties. Analysis of variance indicated that the null hypothesis(that
all means were equal as a function of distance or treatment)
Ballast was not rejected with p=0.88.These results suggest that
Polycyclic aromatic hydrocarbon concentrations in ballast PAH had not migrated from the ballast into adjacent wetland
rock continued to decline rapidly between 6 and 9 months sediments up to this point in the study.The observed means
after tie placement(Table 11).The variance to mean ratios in are similar to those reported by Brooks(1997b)for River
the untreated mesocosm were all<1 suggesting an even South reference sediments(0.833 µg TPAH/g dry sediment).
distribution of PAH consistent with atmospheric deposition.
In contrast,the variance to mean ratios in the two ballast 12-Month PAH Levels
stations closest to the newly treated ties(5 and 20 cm)were Ballast
approximately 2.0, indicating a moderately patchy distribu-
tion.The distribution of individual PAH at the five elevated Fluoranthene,phenanthrene,chrysene,and pyrene were
stations in the newly treated tie mesocosm remained high in detected at low levels in 6 of 27 ballast samples 12 months
phenanthrene and fluoranthene with only minor contribu- after tie placement.These compounds are characteristic of
tions from the HMW compounds.The results for TPAH in creosote.No sample was excluded for QA reasons on this
ballast rock are summarized in Table 11 and Figure 11.The date.The results are summarized in Table 13.The variance
concentration of TPAH observed in the newly treated tie to mean ratios were all<1.0,suggesting a homogeneous
mesocosm had declined from a mean of 789 µg TPAH/g dry distribution of the PAH.That is,in part,because detection
ballast at 3 months to 1.598 µg TPAH/g dry sediment at limits were used where PAH was not detected.The null
9 months. hypothesis that ballast concentrations of PAH were equal in
all treatment and at all distances was not rejected
(a=0.05(ANOVA,F= 1.72,p=0.16)),
12

5
Newly treated ties Untreated ties
4
f° 3 = ±1.96*Std.Err.
m
±1.00*Std.Err.
rn 2 13 o
o Mean
a>
a 1
0
76
0
-1
5 20 30 5 20 30
Distance(cm)
Figure 11-Box and whisker plots describing the concentrations of all PAH observed in ballast rocks
at distances of 5.0,20.0,and 30.0 cm from the faces of newly treated railway ties(N)and untreated
railway ties(U)in the mesocosm study.These data were collected 9 months after placement of the ties.
Table 12-Concentrations of PAH observed in meso- Table 13-Concentrations of PAH observed in railway
cosm wetland sediments at distances of 0,25,50,and right-of-way ballast at distances of 5,20,and 30 cm
75 cm from new and weathered creosote-treated ties from new and weathered creosote-treated railway ties
and from untreated ties 9 months following placement and untreated ties 12 months following tie placement.
of the ties.The detection limit was used as a minimum Each value is the mean of three replicates.The detec-
value for each compound tion limit was used as a minimum value for each
Mean compound
Distance TPAH 95% Mean
Mesocosm (cm) (µg/g) SD confidence Distance TPAH
Untreated 0 0.797 0.183 0.033 Mesocosm (cm) (µg/g) SD Variance
Untreated 25 0.756 0.124 0.015 Untreated 5 0.640 0.000 0.000
Untreated 50 0.687 0.081 0.007 Untreated 20 0.640 0.000 0.000
Untreated 75 0.702 0.018 0.000 Untreated 30 0.735 0.164 0.027
New 0 0.789 0.340 0.116 New 5 1.024 0.437 0.191
New 25 0.724 0.058 0.003 New 20 0.643 0.005 0.000
New 50 0.658 0.078 0.006 New 30 0.672 0.027 0.001
New 75 0.694 0.077 0.006 Weathered 5 0.640 0.000 0.000
Weathered 0 0.795 0.380 0.144 Weathered 20 0.640 0.000 0.000
Weathered 25 0.760 0.352 0.124 Weathered 30 0.735 0.183 0.027
Weathered 50 1.046 0.557 0.310
Weathered 75 0.934 0.270 0.073
13

Table 14-Concentrations of PAH observed in meso- Table 15-Concentrations of PAH observed in railway
cosm wetland sediments at distances of 0,25,50,and right-of-way ballast at distances of 5,20,and 30 cm
75 cm from new and weathered creosote-treated ties from new and weathered creosote-treated railway ties
and from untreated ties 12 months following placement and untreated ties 12 months following tie placement.
of the ties.The detection limit was used as a minimum Each value is the mean of three replicates.The detec-
value for each compound tion limit was used as a minimum value for each
Mean compound
Distance TPAH 95% Mean
Mesocosm (cm) (µg/g) SD confidence Distance TPAH
Untreated 0 4.160 3.487 12.160 Mesocosm (cm) (µg/g) SD Variance
Untreated 25 4.213 3.699 13.679 Untreated 5 0.640 0.000 0.000
Untreated 50 1.520 0.215 0.046 Untreated 20 0.640 0.000 0.000
Untreated 75 1.347 0.220 0.049 Untreated 30 0.640 0.000 0.000
New 0 1.136 0.147 0.022 New 5 0.840 0.010 0.000
New 25 1.439 0.464 0.215 New 20 0.887 0.427 0.183
New 50 1.610 0.646 0.417 New 30 0.747 0.185 0.034
New 75 1.319 0.287 0.082 Weathered 5 0.640 0.000 0.000
Weathered 0 1.503 0.203 0.041 Weathered 20 0.640 0.000 0.000
Weathered 25 1.187 0.049 0.002 Weathered 30 0.640 0.000 0.000
Weathered 50 1.313 0.159 0.025
Weathered 75 1.232 0.097 0.009
creosote,these were presumed to be unassociated with the
weathered ties.
Wetland Sediments Ballast
Table 14 summarizes PAH concentrations observed in sedi- At 15 months,PAH were detected only in the ballast of the
ments at 12 months after placement of the ties.The elevated new tie mesocosm.The suite of PAH dominated by fluoran-
PAH concentrations observed in sediments from the un- thene,phenanthrene,and pyrene was characteristic of creo-
treated mesocosm must be interpreted with caution.They are sote.Much higher levels of PAH were anticipated due to
associated with moderately high detection limits(0.075 to summer heating of the ties. However,the increases observed
0.530 µg PAH/g)created by low solids in the samples.Only in the summer of 1998 were not repeated in 1999,and it
fluoranthene was actually detected at a concentration of appears that the initial loss from newly treated ties was
0.100 µg/g in the 12 samples collected in this mesocosm. associated only with their first exposure to hot summer
Phenanthrene and benzo(ghi)perylene were detected at low temperatures. It is possible that the volatile,lighter weight
levels in sediments from the new tie mesocosm.Only phe- compounds were lost in the first year and that the residual
nanthrene was consistently detected at low concentrations in creosote remaining in the ties was not as susceptible to
the weathered tie mesocosm.These data suggest that low migration associated with high ambient air temperatures.The
levels of PAH have migrated from the ballast into adjacent results for ballast are summarized in Table 15.Differences
wetlands.As will be discussed in a later section,the ob- as a function of treatment and/or distance were not statisti-
served PAH concentrations are below those associated with tally significant at a=0.05(ANOVA,F= 1.22,p=0.34).
any biological effects and the highest TPAH concentrations
were observed in the untreated tie mesocosm where there Wetland Sediments
is no known source of PAH,other than atmospheric
Poly-
deposition. The results of these analyses are provided in Table 16. Poly-
cyclic aromatic hydrocarbons were not observed above
15-Month PAH Levels detection limits in sediments from the untreated tie meso-
cosm.A single sample at the 75-cm station in the weathered
A single sediment sample from the weathered tie mesocosm tie mesocosm contained a TPAH of 4.87 µg/g.The PAH
was excluded from the analysis on this date.The exclusion spectrum was not dominated by fluoranthene or phenan-
was based on high detection limits(1.6 µg PAH/g for all threne but instead contained 13 compounds,all at low levels.
compounds).The only compounds detected were
benzo(b)fluoranthene and benzo(k)fluoranthene. Because This sample might be associated with aged creosote-derived
of the absence of phenanthrene,fluoranthene,and other PAH or with another source.A single sample in the new tie
intermediate-weight PAH compounds associated with mesocosm contained 9.83 µg TPAH/g with a suite of PAH
characteristic of creosote. This is the first sediment sample
14

Table 16--Concentrations of PAH observed in meso- Table 17-Concentrations of PAH observed in rail-
cosm wetland sediments at distances of 0,25,50, way right-of-way ballast at distances of 5,20,and
and 75 cm from new and weathered creosote-treated 30 cm from new and weathered creosote-treated
ties and from untreated ties 12 months following railway ties and untreated ties 18 months following
placement of the ties tie placement.Each value is the mean of three repli-
cates.The detection limit was used as a minimum
Mean Distance TPAH 95% value for each compound
Mesocosm (cm) (µg/g) SD confidence Mean
Untreated 0 2.277 1.215 1.476 Distance TPAH
Mesocosm (cm) (µg/g) SD Variance
Untreated 25 1.499 0.114 0.013
Untreated 50 1.813 0.562 0.316 Untreated 5 0.304 0.000 0.000
Untreated 75 1.328 0.080 0.006 Untreated 20 0.305 0.002 0.000
New 0 1.045 0.049 0.002 Untreated 30 0.305 0.001 0.000
New 25 1.168 0.122 0.015 New 5 0.595 0.139 0.019
New 50 1.076 0.073 0.005 New 20 0.638 0.516 0.266
New 75 3.945 5.100 6.015 New 30 0.937 0.693 0.481
Weathered 0 1.353 0.317 0.101 Weathered 5 0.303 0.000 0.000
Weathered 25 1.058 0.067 0.004 Weathered 20 0.303 0.000 0.000
Weathered 50 1.040 0.068 0.005 Weathered 30 0.303 0.000 0.000
Weathered 75 2.327 2.202 4.849
Table 18-Concentrations of PAH observed in meso-
cosm wetland sediments at distances of 0,25, 50,and
observed in this study that shows evidence of creosote- 75 cm from new and weathered creosote-treated ties
derived PAH migrating from the ballast into adjacent and from untreated ties 18 months following place-
ment of the ties
wetland sediments.
Mean
18-Month PAH Levels Distance TPAH 95%
Mesocosm (cm) (µg/g) SD confidence
Two samples collected on the final sampling date were Untreated 0 1.060 0.397 0.158
excluded from the analysis.One of these was a 75-cm sedi- Untreated 50 1.589 1.317 1.735
ment sample collected in the weathered tie mesocosm. The
sample contained elevated concentrations of the HMW Untreated 75 1.191 0.662 0.439
compounds benzo(a)anthracene(2.7 µg/g), New 0 1.357 0.436 0.190
benzo(b)fluoranthene(1.1 µg/g),benzo(k)fluoranthene(1.2 New 50 1.306 0.753 0.557
µg/g),benzo(a)pyrene(2.0 µg/g),and chrysene(3.4 µg/g) New 75 0.747 0.286 0.052
plus 2.1 µg/g of naphthalene. Fluoranthene(0.41 µg/g)and Weathered 0 3.437 2.528 6.388
phenanthrene(0.598 µg/g)were observed at low levels,and Weathered 50 1.959 1.147 1.317
the suite of PAH is not characteristic of creosote.The second Weathered 75 1.708 0.312 0.138
sample excluded from the analysis was collected in the
untreated tie mesocosm.The TPAH in this sample was
36.555 µg TPAH/g,of which 35.6 µg/g was naphthalene. hypothesis that all of the means(as a function of distance
National Environmental Testing confirmed the results.How- and treatment)were equal was not rejected at a=0.05
ever,it appears likely that this sample was contaminated (ANOVA,F= 1.85,p=0.13).
during handling or analysis.The results for the remaining
101 samples collected at 18 months are presented below. Wetland Sediments
Ballast Sediment concentrations of PAH are summarized in
Significant increases in the concentration of PAH in ballast Table 18.A single high sample(6.26 µg TPAH/g)was
were not observed in any of the mesocosms on the final day observed in one of three replicates collected at the 0.0-cm
of the study.The initial pulse of PAH that apparently station in the weathered tie mesocosm.Benzo(a)anthracene
migrated from the newly treated ties into the ballast during (0.99 µg/g),benzo(b)fluoranthene(0.500 µg/g),
the summer of 1998 had weathered and/or dispersed from benzo(k)fluoranthene(0.650 µg/g),benzo(a)pyrene
the ballast by the 6-month testing.The observed mean (0.930 µg/g),and chrysene(1.300 µg/g)dominated the suite
concentrations are summarized in Table 17.The null of PAH. In this sample,fluoranthene was not detected and
15

Table 19-Concentrations of PAH observed in core Table 20-Concentrations of PAH observed in core
samples in mesocosm limestone ballast immediately samples in mesocosm sediments immediately adja-
adjacent to treated and untreated ties.These samples cent to ballast carrying the newly treated ties.These
were collected 18 months following placement of samples were collected 18 months following place-
the ties ment of the ties
Mean Mean
Depth TPAH 95% Depth TPAH 95%
Mesocosm (cm) (µg/g) SD confidence Mesocosm (cm) (µg/g) SD confidence
Newly treated 0 0.311 0.000 0.000 Newly treated 0 1.207 0.039 0.001
Newly treated 10 0.430 0.000 0.000 Newly treated 10 1.640 1.338 1.790
Newly treated 20 0.448 0.000 0.000 Newly treated 20 0.720 0.000 0.000
Newly treated 30 0.308 0.000 0.000 Newly treated 30 0.614 0.202 0.041
Newly treated 40 0.745 0.000 0.000 Newly treated 40 0.642 0.296 0.088
Newly treated 50 0.681 0.000 0.000 Newly treated 50 0.650 0.000 0.000
Newly treated 60 0.802 0.000 0.000
N Newly treated 60 0.482 0.000 0.000
Newly treated 70 0.626 0.000 0.000
Newly treated 80 0.585 0.000 0.000
Untreated 0 0.452 0.210 0.044
Untreated 10 0.432 0.182 0.033 0.85
Untreated 20 0.478 0.238 0.057 Model: 7b*eOx C:423
Untreated 30 0.670 0.000 0.000 �, 0.75
Untreated 40 0.778 0.165 0.027 Untreated 50 1.223 0.000 0.000 0.65c:02a�' C:a25Untreated 60 1.291 0.000 0.000 0.55Untreated 70 0.656 0.000 0.000 =Q 0.45 C.4iUntreated 80 0.679 0.000 0.000 0 0Weathered 0 0.724 0.533 0.284 Q'� 0.35 :
Weathered 10 0.605 0.427 0.182 C 417 0
Weathered 20 0.654 0.495 0.245 0.250 20 40 60 80
Weathered 30 0.969 0.941 0.885 Depth(cm)
Weathered 40 0.490 0.264 0.070
Weathered 50 0.812 0.000 0.000 Figure 12-Distribution of the sum of observed concen
Weathered 60 0.617 0.000 0.000 trations of PAH after 18 months in railway ballast under
Weathered 70 0.500 0.000 0.000 newly treated crossties.
3.0
phenanthrene was detected at a low level(0.410 µg/g),
which was not characteristic of creosote.However,the 2.6 0
sample was included in the analysis because phenanthrene 2.2
was detected.The null hypothesis that these means were
all equal was not rejected at a=0.05(ANOVA,F= 1.41, Q 1.8
p=0.26). o, 1.4
1 1.0
Distribution of TPAH as Function 0 6 ° ° ° °
of Depth in Ballast and Sediments °
at End of Study 0'2-10 0 10 20 30 40 50 60 70
Depth (cm)
Core samples were collected at 10-cm-depth increments Figure 13-Distribution of the sum of observed concen-
from the surface to the plastic mesocosm liner on the last day trations of PAH after 18 months in wetland sediments
of this study.The results are summarized in Table 19 and adjacent to the ballast carrying newly treated crossties.
Figure 12 for ballast and in Table 20 and Figure 13 for
16

sediments.A broad spectrum of PAH compounds was ob- 85
served at very low levels in most samples.Linear and Monthly precipitation at
nonlinear regression analysis gave significant coefficients 30 Romeoville, Illinois
for the constant term and the independent variable depth in 25
ballast.The nonlinear result given in Figure 12 explained
more of the variation(RZ=0.55)than did the linear regres- _ 20
sion(R2=0.40).However,the residuals were not normally 15
distributed in either regression.The results are presented
without further transformation because regression analysis is 10 Sample dates
fairly robust with respect to departures from normality and 5
because the observed PAH concentrations are at,or below,
baseline PAH levels observed in the Des Plaines River wet- 0
OC) co co CO 00 CO 00 co rn rn rn M rn rn rn 0) 0) M M
land and are of no biological consequence.Having said that rn T T rn rn rn °' T °' a' rn am rn T e' rn CP T T
it appears that either small amounts of PAH migrated down- � n c� O z° p ca ti C - Q to O z
ward in the ballast during the 18 months of the study or that
rates of PAH degradation are higher on the surface,which is Month of study
exposed to more sunlight.Also,the highest TPAH concen- Figure 14—Rainfall reported at the Romeoville, Illinois,
trations in ballast were found in the untreated tie mesocosm NOAA station located—0.8 km from the mesocosm study
at depths of 50 and 60 cm. site.The smooth line is a fourth order polynomial fit to
the data(1 in.=25.4 mm).
In contrast,as seen in Table 20 and Figure 13,little,if any,
PAH migrated from the new tie ballast into adjacent sedi-
ments and the coefficient describing TPAH as a function of The untreated tie mesocosm was frequently observed to have
sediment depth was not significantly different from zero. standing water.Excess surface water was pumped out of the
The PAH that did migrate into the sediments at the toe of the untreated tie mesocosm on July 10 and 11, 1998.No
ballast appear to be bound in the top 10 cm,and there is little pumping was required in either the new or weathered tie
evidence of vertical migration downward into this high mesocosms.
organic carbon matrix.Mean sediment values at all depths
below 10 cm are somewhat lower but close to baseline Significant quantities(enough to sample)of water were not
sediment TPAH concentrations found in the Des Plaines observed in the groundwater monitoring ports,even when
River wetland. the wetlands were inundated.It appears that Des Plaines
River wetland soils are so finely textured that water did not
Hydrologic Profile and Storm and percolate downward into the groundwater sumps.Rainwater
Groundwater PAH Concentrations remained perched on top of the wetland,and water added at
the floor of the mesocosm,simulating water flowing in the
Rainfall recorded at the National Oceanic and Atmospheric fractured limestone under the Des Plaines wetland,may have
Association(NOAA)Romeoville,Illinois,station located flowed to the surface between the impermeable barrier and
approximately 0.8 km from the mesocosm site is summa- the wetland soils.The wetland soils were saturated during
rized in Figure 14 for the period of this study.A total of the entire study.
2.6 in of precipitation fell during this study. Heaviest pre-
cipitation occurred in January 1999 when 75.1 cm of rain Surface water was collected from the mesocosms at about
and snow were recorded.Temperatures were near or below 10 days and 2,3, 12, 15,and 18 months after tie placement.
freezing,and the creosote would have been in a solidified Polycyclic aromatic hydrocarbons were not detected in any
almost glass-like state that is insoluble and immobile. Other of these 16 samples at the analytical detection limits on any
date except the
than the late winter of 1998-1999,precipitation was rela- final sample when nanogram per liter quanti-
tively evenly spread out over the year.The area experienced ties of five PAH were detected in all three mesocosms.The
frequent storm events throughout the summer,and surface results for 18 months are presented in Table 21,which also
water was generally present following these events. Storm- includes the results of a biological assessment using the
water contamination was most likely after rain showers on methodology of Swartz and others(1995). Swartz and others
warm summer days when the creosote was more mobile. (1995)recommended a TU benchmark of 0.186 for the
protection of biological resources.All of the reported values
The water tank supplying the subsurface irrigation system for mesocosm stormwater were less than this value.This
was installed on June 1 and 2, 1998.Water was added to the assessment is considered conservative because both particu-
new and weathered tie mesocosms using this system on June late and dissolved PAH were measured in this mesocosm
4, 1998,and again on August 18, 1998. Wetland soils in the study. However,the analysis assumed that all of the reported
mesocosms remained saturated throughout the study period PAH were in the dissolved phase.
and the subsurface irrigation system functioned as designed.
17

Table 21—Dissolved and particulate PAH observed This mesocosm study may provide a mechanism for the
in mesocosm stormwater at 18 months after tie study of water movement through hydric soils in the Des
installations Plaines River area.Based on observations to date,it appears
Un- that water does not move vertically in these soils.Hypotheti-
treated New Weath- cally,groundwater is moving primarily through the fractured
ties ties ered ties limestone,which is capped by the hydric wetland soils.
Compound (mg/L) (mg/L) (mg/L)
Acenaphthene ND ND ND Discussion
Acenaphthylene ND ND ND The mesocosms were constructed without significant PAH
Anthracene ND ND ND contamination. In other words,this study started with a
Benzo(a)anthracene 0.00016 0.00019 ND relatively clean PAH slate.Polycyclic aromatic hydrocar-
Benzo(b)fluoranthene ND ND ND bons,in a profile characteristic of creosote,were observed in
Benzo(k)fluoranthene ND ND ND ballast immediately adjacent to the newly treated ties within
Benzo(a)pyrene ND ND ND 10 days.A single sample of ballast from the untreated tie
Benzo(ghi)perylene ND ND ND mesocosm also contained significantly elevated levels of
PAH at about 3 months.Since there were no known sources
Chrysene ND ND ND of PAH in the untreated tie mesocosm,this suggested that
Dibenzo(a,h) ND ND ND care must be taken in evaluating PAH data to not give too
anthracene much weight to single samples that are different from trends
Fluoranthene ND ND 0.0013 or other replicates.
Fluorene ND ND ND
Ideno(1,2,3-cd)pyrene ND ND ND Data Quality Assurance
Naphthalene ND ND ND Goyette and Brooks(1999)documented changes in the
Phenanthrene ND 0.00066 0.00058 distribution of the proportions of individual PAH com-
Pyrene ND ND 0.00082 pounds during the treatment of wood with creosote and in
Swartz and others 0.059 0.075 0.104 the weathering of creosote following its loss from treated
(1995)TPAH toxic units wood structures in marine environments.These results dem-
Swartz and others 0.186 0.186 0.186 onstrated a dramatic shift in PAH composition from one rich
(1995)benchmark in LMW compounds in raw creosote oil to one rich in inter-
'ND, no data. mediate-weight compounds in treated wood(particularly
phenanthrene,anthracene,fluoranthene,and pyrene).Ini-
tially,the distribution of PAH in sediments associated with
The lack of observable PAH in water adjacent to the simu- losses from creosote-treated wood was similar to that found
lated railway right-of-way in this mesocosm study was ex- in the wood.However,physicochemical and biological
pected. Colwell and Seesman(1976),Wade and others degradative processes appeared to preferentially degrade the
(1987, 1988),and Goyette and Brooks(1999)have all ob- remaining LMW compounds during the first 6 months to 1
served very low(biologically inconsequential)levels of year leaving a higher proportion of the intermediate and
PAH in the water column adjacent to creosote-treated wood HMW compounds in aged deposits.The result was that new
projects,even when surface sheens were present and high deposits of PAH associated with creosote-treated wood were
concentrations of PAH were observed in sediments.Bestari dominated by intermediate-weight compounds and historic
and others(1998a)examined water column concentrations (>1-to 3-year-old)deposits,while still dominated by phe-
of PAH migrating from creosote-treated piling immersed in nanthrene and fluoranthene,contained increasing propor-
microcosms(I2,000-L tanks).They concluded that"The tions of the HMW compounds(four through seven ring
rapid loss of creosote from water in conjunction with the structures).This information is useful because PAH are
slow rate of leaching from the pilings suggests that risks ubiquitous with many natural and anthropogenic sources. In
associated with the use of creosote-impregnated pilings in studies such as these,it is informative to be able to distin-
aquatic environments may be minimal."This accumulated guish between historic deposits of PAH from unknown
evidence fully supports the conclusion of Brooks(1997a) sources and newly lost PAH associated with creosote-treated
that water column concentrations of PAH associated with Food. In this study,five of the 450 PAH analyses(L I%)
were excluded from the database because the observed
creosote-treated wood are simply not of biological signifi- distribution of individual compounds was not characteristic
be ma It is the accumulation of PAH in sediments that must of the suite of PAH compounds observed in association with
be managed. creosote-treated wood products.One sediment sample in the
untreated tie mesocosm contained 35 µg naphthalene/g dry
18

50
45 ■ Creosote
m SWO
40 ❑ SW50
i SN75
35 8 SW75
r' 30
c
C
25
U
20
v
m
a 15
10
5
0
a
C C C C C = C C C C m C C C C
a7 a) L L} N Q) y a) a) G 0 a) `3
J L QEL @ (p IL
CO COal N C 7 (0 O O c6 U
z U Q d Q � w N o
Q C Y N N O C
m O O a1 W m
a m L :2
O ❑
hF
C
N
O7
Figure 15—Comparison of 44-month-old creosote-derived mixtures of PAH in sediments with
the PAH spectrum observed in samples excluded from the mesocosm study database.
sediment with no other PAH observed. This sample was PAH in Ballast
probably contaminated during collection or analysis.The
spectra of PAH compounds observed in the other four ex- Polycyclic aromatic hydrocarbons appeared to migrate from
cluded samples is compared with the suite of PAH observed the new creosote-treated ties into adjacent ballast during the
in several-year-old creosote deposits in Figure 15.Three of first summer following placement.The maximum concentra-
the remaining four samples were collected in the weathered lion in ballast reached:=1,000 µg TPAH/g dry ballast within
tie mesocosm,and one sample was collected in the new tie 5 cm of the tic face by 3 months.Concentrations declined
mesocosm. Dominant compounds in creosote,including with distance but remained high at 20 cm.The initially high
phenanthrene,anthracene,and tluoranthene were either ballast PAH concentrations declined significantly during the
absent or detected at low levels in these samples.The spec- remainder of the study.A second pulse of PAH was not
trum of PAH in the excluded samples was dominated by observed during the second summer of this study and sig-
benz(a)anthracene,chrysenc,benzo(b or k)fluoranthene, nificant PAH loss from the ties appeared restricted to the
benzo(a or e)pyrene,and/or benzo(ghi)perylene. As noted in first period of high temperatures.Creosote-treated wood is
the Appendix,this spectrum is more likely to be associated black and is expected to absorb a broad spectrum of solar
with crankcase oil or with very old(>5 to 10 years)creosote- radiation.Temperatures high enough to volatilize the LMW
derived PAH.They are not associated with 1-to 3-year-old compounds could be achieved during hot summer weather.
creosote deposits.The remainder of this analysis excludes
these five samples.
19

1200 —tM 2.0
=1000 z 1.6
IQ 800
1 600 1.2
E 400 E 0.8
0 200 m
a 0 C 0.4
w 32 0
21
26 i8 32 26 1821
���4 g 6 8 ���`�Gti`on btsta�Ce 14 8 2 6 8 �'S Dior
f�c��m 2 2 s��nyt�J allaSt( CJm 2 pas ar5t��
Figure 16—Spatial and temporal trends in the con- Figure 17—Spatial and temporal trends in the con-
centration of PAH observed in ballast adjacent to centration of PAH observed in ballast adjacent to aid,
newly treated railway ties during the first 18 months weathered railway ties during the 18 months following
following construction.Analysis of 16 PAH was construction.Analysis of 16 PAH was accomplished
accomplished in broken limestone ballast at distances in broken limestone ballast at distances of 5,20, and
of 5,20,and 30 cm from the face of the ties. 30 cm from the face of the ties.
This may explain the elevated ballast concentrations ob- detection limit.That assumption is probably overly conser-
served in August of the first year of the study(3 months). vative and will be discussed in a subsequent section of this
Poiycyclic aromatic hydrocarbons migrating into the crushed report.The spatial and temporal profiles associated with
limestone ballast would most likely evaporate and be chemi- PAH in wetland sediments are described in Figure 18 for the
tally and photochemically degraded in the dry,porous bal- untreated,weathered,and newly treated tie mesocosms.
last environment.Little microbial degradation was expected In general,the concentration of PAH increased during the
in ballast.As discussed in a previous section of this report,it summer of the second year of the study.Wetland sediment
is also possible that a small portion of the creosote-derived concentrations then declined in the new tie and untreated
PAH moved vertically downward in the ballast and/or was tie mesocosms but remained slightly elevated at the zero
washed out of ballast into the surrounding wetland. meter(1.708 f 0,421 µg TPAH)g)and 0.75 meter
Figure 16 is a three-dimensional contour plot constructed (3.435±2.860 jug TPAH/g)stations. Values are mean
using a distance-weighted least squares algorithm. It de- t 95%confidence intervals.
scribes the spatial and temporal distribution of PAH in lime-
stone ballast supporting newly treated railway ties during the The highest sediment concentration(3,945 ug TPAH/g)was
18 months of this study. observed in the newly treated tie mesocosm after 15 months
at the furthest station from the ballast(75 cm).The variance
Other than one sample,significantly elevated concentrations to mean ratio for these three samples was 1.46,suggesting a
of PAH were not observed in the untreated tie mesocosm.As slightly more patchy distribution than would be expected
shown in Figure 16,a small pulse of PAH was also observed from a randomly distributed variable.At 18 months,sedi-
in ballast immediately adjacent to the weathered ties during ment concentrations had declined to between 0.209 and
the first summer. However,the PAH concentrations were 1.357 µg TPAI I/g dry sediment.The 18-month sediment
Iow with a maximum observed mean concentration of concentrations observed in the new tie mesocosm were less
1.489±2.918 ug TPAH/g ballast,Figure 17 is a three- than those observed in the untreated tie mesocosm
dimensional contour plot describing ballast concentrations of (0.486 to 1.541).However,the lower value was not
TPAH as a function of time and distance from the faces of significant at of=0.05.
weathered ties in this study.
Goyette and Brooks(1999)presented evidence suggesting
PAH in Wetland Sediments that the creosote remains in a particulate form in sediments
and that these particles gradually work their way deeper into
Concentrations of TPAH varied with time and distance in all sediments or that they adhere to inorganic and organic sur-
three mesocosms.The TPAH values used in this analysis faces such as cobbles and gravel.Brooks(unpublished data)
assume that undetected compounds were present at the has observed that microspheres or particles of creosote oil
20

2.0
Untreated ties
1.6
28 Untreated
14 ties 1.2
¢ 2.a 0.8 ❑ °
°- 1.6 °
0 1.2 0.4
0.8
a 0.4 0
g 90 0 25 50 75
70 1$21
50
e3010 5 81 oft o� 2.0 = t1.96"Std.Err. New
S��ohJ�i -10 2 05o��vC 1.6 n'Std.Err.
0 Mean
Q Q 1.2
0 o.a � ❑ ❑
0.4
6'2.8 4Weahered
2 4 0
Q 2.0 0 25 50 75
U< 1.6
0 1.2 2.0
p 8 Weathered ties
a 0.4 1.B
7Q 1.2
21 °s 1518�dii 912 o.a�Te 0. 1 a 0 3 6Qyts`°o s JGI,Q 0.4
Q 0
0 25 50 75
Distance(cm)
4.5 Newly treated Figure 19—Box and whisker plots describing the
= 3.5 ties nonsignificant differences in mean TPAH concentrations
2 5 in sediments as a function of distance from railway tie
faces and tie treatment.
0 15
m 0.5
m
remain intact in ground oyster shell and/or white sand for up
�-75 to 2 years.The patchy distribution of PAH observed in this
6�sn� 50 study(variance to mean ratios much mil)is consistent with
25 observations in Sooke Basin and supports the particulate
o� 151821
51821 transport hypothesis for creosote-derived PAH.
D 3 6 Months
postconstruction Observed differences in mean TPAH values were not sig-
nificantly different as a function of the sample's distance
Figure 18—Spatial and temporal distribution of the from the face of the tie(ANOVA,F=0.33,p=0,96).These
TPAH observed in sediments from the untreated tie, relationships are described in Figure 19.Mean TPAH values
weathered tie,and newly treated tie mesocosms. were also not significantly different between treatments
(ANOVA,F=0.76,p=0.72). However,these differences
were significantly different as a function of day(ANOVA,
F= 12.46,p=0.000).These differences are described in
Figure 20 using box and whisker plots for each treatment as
a function of time.This suggests that seasonal changes in
21

3.5 1.8 �-Detected PAH
3.0 Untreated ties -•4
1.6 --&••Detected plus PAH
2.5 aci 1.4 detection limit ?•-•
2. E
1.5 1 � 1.2 ••-•a
1.0 l7 1.0
0. 0.8 .•a
0.00
-0.5 ¢ 0.6 °•-
0 0.3 3 6 9 12 15 18 a- ••°•:
c;) 0.4
3.5 0.2
3.0 = t1.96'Std.Err, New
+1.00'Std.Err. ties 0
2.5 -
3 6 9 12 15 18
= 2.0 D Mea Months postconstruction
a 1.5 n D Figure 21-Relationship between sum of the detected
0 1.0 PAH and the detected PAH plus the analytical detection
0.5 q limit for each compound.Each value is the mean for all
(0 0.0 treatments and distances on a particular day in the
-0.5 J study.
0 0.3 3 6 9 12 15 18
0.40
3.5
0.35
3.0 Weathered ties
2.5 0.30
2 0 0.25
1.5 CMP t7 o jai 0.20
1.0 0.15
0.5 -17 �[ m a 0.10
0.0 0.05
c
-0.5 cj 0
0 0.3 3 6 9 12 15 18 -0.05
Months postconstruction -0.10
Figure 20-Box and whisker plots describing significant 3 6 9 12 15 18
(ANOVA,P=0.000)differences in mean TPAH concen- Months postconstruction
trations in sediments as a function of time following Figure 22-Differences in detected PAH between meso-
placement of untreated oak ties and newly treated or cosms containing creosote-treated railway ties
weathered creosote treated oak ties. and a mesocosm containing Identical untreated oak ties.
wetland sediment concentrations of PAH were not associ- These results strongly suggest that seasonally varying st-
ated with the presence of the ties but rather with atmospheric mospheric PAH deposition is a major source of the observed
deposition,which would affect all mesocosm treatments and low levels of PAH.The question of whether or not the creo-
all distances equally,as was observed. sote-treated railway ties contribute PAH to adjacent wetlands
remains.This question is explored in Figure 22 which sum-
The preceding summary was based on the conservative marizes the mean concentrations of the sum of PAH ob-
assumption that undetected PAH compounds were present at served in the weathered and new tie mesocosms less the
the analytical detection limit. Figure 21 shows the relation- mean observed in the untreated tie mesocosm.This summary
ship between the reported TPAH concentrations and only the suggests that the concentrations of PAH in treated tie
detected PAH.The apparent seasonal trend in observed mesocosm sediments were not elevated above that
differences may be associated with the proportion of solids observed in the untreated tie mesocosm during the first
in the samples,which changes with water content and there- 9 months of the study.However,it also appears that during
fore with season.This analytical phenomenon was not inves- the last three sample periods,the concentrations of detected
tigated as part of the study. Each value is the mean for all PAH were elevated by;z0.35 µg PAH/g dry sediment in the
treatments and distances on a particular day.This is consid- mesocosms containing creosote-treated ties compared with
ered a valid grouping because significant differences were the untreated mesocosm.The significance of these increases
not observed as a function of either of these variables.
22

was investigated using a new variable equal to the detected • It appears that atmospheric deposition of PAH contributes
PAH in creosote-treated wood mesocosm samples less the much of the observed baseline to Des Plaines River wet-
mean detected PAH concentration observed in sediment land sediments.
samples collected from the untreated mesocosm on the same
day.This variable was subjected to ANOVA using a nested • Small amounts of PAH may have migrated from the bal-
design with treatment,day,and distance as dependent vari- last into adjacent wetlands during the second summer of
ables.Increases in detected PAH observed in the weathered this study.The PAH spectrum in these samples and a
and new tie mesocosms were not significantly different as a comparison of PAH concentrations in the untreated meso-
function of treatment(p=0.47),day(p=0.10),or distance cosm with the creosote treatments suggests that these in-
(p=0.86).Increases in the TPAH would have been signifi- creases(--0.3 µg/g)were real.However,the observed in-
cant for day at a=0.10. creases were not statistically significant as a function of
distance,treatment,or day of the study.
Summary • PAH were detected in 1 of 16 water samples.Those sam-
The results from this study suggest the following: ples were collected on the final day of the study.
Benzo(a)anthracene was observed in the untreated and
• An initial pulse of PAH was observed moving from the new tie mesocosms. Phenanthrene was detected in the new
treated railway ties into their supporting ballast during the tie mesocosm,and fluoranthene,phenanthrene,and pyrene
summer of the first year following construction.More were detected in stormwater from the weathered tie meso-
PAH migrated from the newly treated ties into ballast than cosm.The PAH concentrations were all very low,and an
from the weathered ties during this first summer. assessment using the sum of TU described by Swartz and
• Creosote oil,containing PAH,is heated during the sum- others(1995)indicated that none of the samples ap-
proached the benchmark recommended by those authors
mer.Creosote-treated wood surface temperatures were not for the protection of aquatic life.
measured.However,the black surface of the railway ties
probably attracts sunlight,and high temperatures are quite These results suggest that it is reasonable to expect a detect-
possible. able migration of creosote-derived PAR from newly treated
• At sufficiently high temperatures,the expansion of the railway ties into supporting ballast during their first exposure
wood forces creosote oil to the surface where it coalesces to hot summer weather.The PAH rapidly disappeared from
to form droplets that may run down the face of the treated the ballast during the fall and winter following this initial
wood into ballast.Alternately,these droplets may form loss.The statistically insignificant vertical and horizontal
blisters that pop,projecting minute particles of creosote an migration of these PAH suggests that they either evaporated
unknown distance(probably within 30 cm). or where chemically and/or photochemically degraded.
• Polycyclic aromatic hydrocarbons,particularly the inter- Biological Assessment
mediate and HMW compounds are hydrophobic with
solubilities ranging from 0.07 mg/L for anthracene to Much of the preceding discussion focused on the migration
0.00026 mg/L for benzo(g,h,i)perylene.They adhere to of PAH from creosote-treated railway ties into supporting
most dry surfaces(like ballast rocks)and are immobilized. ballast and from the ballast into the adjacent wetland envi-
ronment.Regardless of the source of PAH,it is the cumula-
• Railway ballast contains little organic material,and it is five effect of all observed PAH that contribute to potential
unlikely that bacterial communities capable of metabo]iz- stress and at low concentrations to chronic toxicity.The
ing PAH would thrive in this environment.However,PAH following assessment will assume that individual PAH com-
ing),degraded by photo-and chemical oxidation(weather- pounds were present at the analytical detection limit when
ing),and these processes probably represent the primary they were not detected.This is a very conservative assess-
degradative pathways for creosote-derived PAH in railway ment,which probably overestimates the potential for adverse
ballast. effects.
• The sampling schedule was changed in an effort to deter-
mine if similar PAH losses would occur during the second As previously discussed,PAH were only observed in
summer of the study.No significant loss from ties in either stormwater on the final day of sampling.These compounds
mesocosm was observed during the second summer. were observed in all three mesocosms on that day at levels
below the sum of TU threshold defined by Swartz and others
• A small portion of these PAH appear to have moved verti- (1995). Biological stress, including that associated with
cally down into the ballast to a depth of approximately photo enhanced PAH toxicity,cannot reasonably be
60 cm.The observed TPAH concentrations,including the predicted at the observed concentrations. Brooks(1997a)has
value of the detection limit for undetected compounds was argued that dissolved concentrations of PAH found in asso-
less than 0.85 µg TPAH/g dry ballast at any depth. ciation with creosote-treated wood are not expected to create
23

150 anticipated in any species.The LC5o value represented the
140 concentration above which significant adverse affects should
130 always be anticipated,and the mean of these two values was
120
Lb 110 suggested as representative of the concentration above which
a 100 adverse affects were likely to be observed in sensitive spe-
800 ties. In sediments containing 1 1.9%TOC,the TPA14 mix-
5 70 ture LC50is 251.8 µg TPAH/g dry sediment and the mean
60 valuers 149.3 µg TPAH/g.The sediment PAH concentra-
E 50 tions observed in this study were between one and two or-
Z 40 30 ders of magnitude lower than these levels.Tables 22 and 24
20 compare the observed sediment concentrations of PAH in
10 r 11 1 1 t I I I I I the highest weathered tie and newly treated tie mesocosms
0 1.0 1.5 2.0 3.0 4.0 5.0 6.0 7.0 with their respective toxicity thresholds.
Total PAH concentration(mg/kg)
None of the PAH compounds exceeded their toxic threshold,
Figure 23—Number of mesocosm sediment samples nor did any of the classes of mixtures.No toxicity could be
as a function of the observed TPAH in the sample. expected in association with either of these two highest
samples,and therefore,no toxicity can reasonably be ex-
pected with the several hundred samples in which the TPAH
environmental stress. It is sedimented PAH that must be compounds were in the range of 1 to 2 µg TPAHIg dry
managed to ensure the integrity of plants and animals living sediment.Aside from the lack of evidence of toxicity,there
in the vicinity of treated wood. Swartz(1999)was chosen as are several interesting points in Tables 22 and 24,
a conservative benchmark for use in evaluating the biologi-
cal response to sedimented PAH in this study. • Consistent with the Sooke Basin study(Goyette and
Brooks 1999),phenanthrene was the most problematic
Polycyclic aromatic hydrocarbons are hydrophobic and bind compound associate]with the new tie mesocosm. The
with organic molecules in aquatic environments. This re- phenanthrene concentration in the single highest sample
duces their bioavailability and potential toxicity. In recogni- collected from the new tie mesocosm represented
tion of this,most organic contaminant benchmarks are based 0,657 toxicity threshold units.
on the concentration of the contaminant expressed in micro-
grams of contaminant per gram of organic carbon. Des • Low molecular weight PAH compounds made up 34.7%
Plaines River wetland sediments used in this study were of the observed PAH in the highest newly treated tie
analyzed for TOC and/or TVS at the beginning and end of mesocosm sediment sample but only 14.5%of the PAH in
the study,A mean TOC value of 11.91%was determined. the highest sediment sample from the weathered tie meso-
cosm.This is consistent with the preferential loss of LMW
Figure 23 is a histogram describing the number of sediment compounds as creosote-treated wood ages,
samples as a function of observed TPAH in the sample
(including the detection limit for undetected compounds). • Similarly,the LMW compounds resulted in a higher TU
Of the 234 samples, 140 contained PAH concentrations value(0.310)than did the HMW compounds(0.166 TU)
<1.0 µg TPAH/g.Concentrations in an additional 80 sam- in the new tie mesocosm sample. In contrast,the LMW
ples were between 1.0 and 2.0 µg TPAHIg.Only 2 of the compounds were represented by a very low TU value
234 sediment samples exceeded 3.93 µg TPAH/g, the toxic- (0.070)in comparison with the HMW compounds
ity threshold for TPAH given by Swartz(1999)in 1%TOC (0.122 TU) in the weathered tic mesocosm.
sediments.None of the samples exceeded the Swartz(1999) This discussion should not be misunderstood.The preceding
benchmark for TPAH in 1 1.9%TOC sediments.The two analysis focuses on the two sediment samples with the high-
samples higher than 3.93 µg TPAHIg were chosen for an est PAH concentrations in a dataset consisting of 234 sam-
evaluation of individual compounds because one was from ples,most of which contained less than 2.0 µg TPAH/g dry
the weathered tie mesocosm(6.26 µg TPAH/g)and the other sediment.The reason for belaboring these two samples is
from the newly treated tie mesocosm(9.83 l.tg TPAH/g).The that they show spectra similar to that expected from creosote
results of computing the sum of TU at the mean sediment and to demonstrate the lack of toxicity in even the highest
TOC are presented in Table 22.Three benchmarks were samples.There is no indication in this study that PAH lost
presented for each compound in constructing Table 23. from either the newly treated or weathered ties presents any
However,in this case,the PAH levels are so low that the potential stress for dragonflies or any other sensitive species
observed TU calculations will be compared only with the in this wetland.
toxic threshold benchmark.Recall that this is the value
below which no adverse biological affects should be
24

Table 22-Summary of the TPAH toxicity threshold and the observed concentration of PAH
compounds and classes of compounds in the newly treated tie mesocosm sample with the high-
est concentration of PAH.These sediments contained a mean of 11.9%total organic carbon
TPAH toxicity threshold Observed concentration
PAH compound (µg PAH/g dry sediment) (µg PAH/g dry sediment Toxic units'
Naphthalene 1.548 0.062 0.040
Acenaphthylene 0.357 0.062 0.174
Acenaphthene 0.476 0.150 0.315
Fluorene 2.025 0.220 0.109
Phenanthrene 3.454 2.270 0.657
Anthracene 2.501 0.450 0.180
Fluoranthene 8.218 2.220 0.270
Pyrene 10.719 1.400 0.131
Benz(a)anthracene 2.501 0.680 0.272
Chrysene 3.692 0.630 0.171
Benzo(b)fluoranthene 3.930 0.350 0.089
Benzo(k)fluoranthene 3.454 0.340 0.098
Benzo(a)pyrene 3.930 0.430 0.109
Low molecular weight PAH 10.362 3.214 0.310
High molecular weight PAH 36.445 6.050 0.166
Total PAH 46.806 9.264 0.198
'Number of toxic units(Swartz 1999)associated with each compound.
Table 23--Summary of freshwater and estuarine benchmarks for PAH''b
PAH level(µg/g) Benchmark type Jurisdiction Source
Freshwater
100(TPAH) SLCA severe effects level British Columbia BCMOELP(1994)
110(TPAH) SLCA severe effects level Ontario Persaud and others(1992)
13.3(TPAH) Recommended threshold concentration United States Ingersoll and others(1996)
2.0(TPAH) OMOE provincial SQG-lowest effect level Ontario Persaud and others(1992)
22.0(TPAH) AETA apparent effects threshold British Columbia BCMOELP(1994)
4.0(TPAH) WEA effects range low British Columbia BCMOELP(1994)
2.9(TPAH-OC) Threshold effects concentration Swartz(1999)
18.0(TPAH-OC) Median effects concentration Swartz(1999)
Marine and estuarine
205(TPAH) AET(estuarine) Mississippi Lytle and Lytle(1985)
4.0(TPAH) Effects range-low NOAA Jones and others(1997)
44.8(TPAH) Effects range-median NOAA Jones and others(1997)
13.3(LPAH&HPAH) AET(estuarine and marine) Washington WAC 173-204
'United Nations University(2001).
bTPAH,total PAH;OC,organic carbon; LPAH, low molecular weight PAH; HPAH, high molecular weight PAH;SLCA,
screening level concentration approach; OMOE,Ontario Ministry of the Environment;SQG,sediment quality guideline;
AET apparent effects threshold;AETA, apparent effects threshold approach;WEA,weight of evidence approach; NOAA,
National Oceanic and Atmospheric Association;WAC,Washington Administrative Code.
25

Table 24-Summary of the TPAH toxicity threshold and the observed concentration of PAH com-
pounds and classes of compounds in the weathered tie mesocosm sample with the highest
concentration of PAH.These sediments contained a mean of 11.9%total organic carbon'
TPAH toxicity threshold Observed concentration
PAH compound (µg PAH/g dry sediment) (µg PAH/g dry sediment) Toxic units°
Naphthalene 1.548 0.037 0.024
Acenaphthylene 0.357 0.089 0.249
Acenaphthene 0.476 0.030 0.063
Fluorene 2.025 0.100 0.049
Phenanthrene 3.454 0.410 0.119
Anthracene 2.501 0.059 0.024
Fluoranthene 8.218 0.190 0.023
Pyrene 10.719 0.430 0.040
Benz(a)anthracene 2.501 0.990 0.396
Chrysene 3.692 1.300 0.352
Benzo(b)fluoranthene 3.930 0.500 0.127
Benzo(k)fluoranthene 3.454 0.650 0.188
Benzo(a)pyrene 3.930 0.930 0.237
Low molecular weight PAH 10.362 0.725 0.070
High molecular weight PAH 36.445 4.990 0.137
Total PAH 46.806 5.715' 0.122
'The TPAH for these samples given in Tables 23 and 24 is slightly lower than determined in this study
because the model of Swartz(1999)considers only 13 PAH compounds and,in this study, 16 PAH
compounds were evaluated.This is not considered a significant flaw in the analysis because the PAH
not considered by Swartz(1999)were not detected or detected at low levels in these samples.
bNumber of toxic units(Swartz 1999)associated with each compound.
Conclusions • Creosote-derived PAH probably migrated from newly
treated railway crossties into supporting ballast during the
Brooks(1996)assessed the potential impact of this railway summer of the first year.In this study,this pulse was not
right-of-way on the Hines emerald dragonfly(Somatochlora observed during the second summer.However,other site-
hineana)and concluded that,based on the limited data avail- specific behavior will depend on the wood species,creo-
able at that time,"There was no indication that the past use sote retention,and solar insolation and ambient air
of creosote ties,or their current replacement(new ties)had temperatures.
compromised the biological integrity of wetland plants or
animals(including Somatochlora hineana)."The completion • Creosote oil,containing PAH,is heated during the sum-
of the River South PAH study(Brooks 1997b)and the re- mer because the black surface of the railway ties absorbs
sults from this study have added significantly to the database sunlight.However,creosote-treated wood surface tem-
on biological effects associated with creosote-treated railway peratures were not measured.
ties.The following conclusions are substantiated by the • At sufficiently high temperatures,the expansion of the
results presented herein: wood forces creosote oil to the surface where it coalesces
to form droplets that may run down the face of the treated
• The PAH spectrum associated with creosote changes with wood into ballast.Alternately,these droplets may form
time.The proportion of HMW compounds increases as the blisters that burst,projecting minute particles of creosote
LMW compounds are degraded or evaporate.However, an unknown distance(probably up to 30 cm).
creosote-derived PAH mixtures are dominated by phenan-
threne and fluoranthene for at least the first 2 to 3 years • Polycyclic aromatic hydrocarbons,particularly the inter-
following migration from the wood.The PAH spectra mediate and HMW compounds are hydrophobic,with
provided in this report give insight into discriminating solubilities ranging from 0.07 mg/L for anthracene to
sources of PAH.However,mixtures of PAH derived from 0.00026 mg/L for benzo(ghi)perylene.They adhere to
creosote and other sources may not be as amenable to most dry surfaces(like ballast rocks)and are immobilized.
simple analysis.
26

• Railway ballast contains little organic material,and it is atmospheric deposition of PAH contributes a significant
unlikely that bacterial communities capable of metaboliz- portion of the baseline observed throughout the Des Plaines
ing PAH would thrive in this environment.However,PAH River wetland.It also appears that on average,the use of
are degraded by photo-and chemical oxidation(weather- creosote-treated railway ties may add an additional 0.3 µg
ing),and these processes probably represent the primary TPAH/g dry sediment within half a meter of the toe of the
degradative pathways of creosote-derived PAH in railway ballast. Even the two highest observed PAH concentrations
ballast. did not reach toxic threshold levels in these wetland
sediments.
• A small portion of these PAH appeared to have moved
vertically down into the ballast to a depth of approxi-
mately 60 cm.The observed TPAH concentrations,in-
cluding the value of the detection limit for undetected This study suggests that newly treated railway ties pose
compounds,was less than 0.85 µg TPAH/g dry ballast. minimal environmental risk,even in sensitive wetland envi-
• It appears that atmospheric deposition of PAH contributes ronments.However,experience from this study suggests the
much of the observed baseline to the Des Plaines River following three management practices to ensure that risks
wetland sediments. are minimized:
• Small amounts of PAH may have migrated from the bal- 1.Numerous derelict railway crossties were observed after
last into adjacent wetlands during the second summer of having been discarded alongside this right-of-way in the
this study.The PAH spectrum in these samples and a Des Plaines River wetland.Ties taken out of service
comparison of PAH concentrations in the untreated meso- should be properly disposed of.
cosm with the creosote treatments suggests that these in- 2.The early loss of creosote from treated wood during first
creases(-0.3 µg/g)were real.However,the observed in- exposure to summer heat was observed in this study and
creases were not statistically significant as a function of has been reported by Brooks(2000)in association with
distance,treatment,or day of the study. creosote-treated timber bridges.The temporary storage of
• PAH were detected in 1 of 16 water samples.Those sam- newly treated railway crossties in sensitive environments
ples were collected on the final day of the study. while awaiting installation should be avoided.Ties should
Benzo(a)anthracene was observed in the untreated and be stored on the ballast or on railway cars.
new tie mesocosms.Phenanthrene was detected in the new 3.Railway ties should be produced using management prac-
tie mesocosm,and fluoranthene,phenanthrene,and pyrene tices that reduce the probability of significant creosote loss
were detected in stormwater from the weathered tie meso- from deep checks in the wood or from excess surface de-
cosm.The PAH concentrations were all very low,and an posits.The ties used in this study were randomly selected.
assessment using the sum of TU described by Swartz and They were relatively clean and free from surface creosote
others(1995)indicated that none of the samples ap- deposits.
proached the benchmark recommended by those authors
for the protection of aquatic life. Literature Cited
• The PAH concentrations observed in the highest wetland Ames,B.W.,McCann,J.;Yanasaki,E. 1975.Methods for
sediment samples collected in the newly treated tie or detecting carcinogens and mutagens with the Salmo-
weathered tie mesocosms are not predicted to be stressful nella/mammalian-microsome mutagenicity test.
using the consensus sediment benchmark methodology of Mutation Research.31: 347-363.
Swartz(1999).No adverse biological affects can reasona-
bly be predicted at the observed levels of PAH.This as- Ankley,G.T.;Erickson,R.J.; Phipps,G.L. land others].
sessment assumed that undetected PAH compounds were 1995.Effects of light intensity on the phototoxicity of
present at the analytical detection limit.This makes this fluoranthene to a benthic macroinvertebrate.Environmental
assessment,particularly the biological assessment,very Science and Technology.29:2828-2833.
conservative because the reported TPAH concentrations
probably overestimate those present. AWPA. 1996.Book of standards.Woodstock,MD:
American Wood-Preservers'Association.
As discussed in the introduction to this study,there are many
sources of PAH associated with railway transportation sys- Axelman,J.;Naes,K.;Naf,C.; Broman,D. 1999.Accu-
tems.These include diesel exhaust,lubricating oils,cargo mulation of polycyclic aromatic hydrocarbons in semiper-
(coal and oil),and herbicides.A mesocosm study was de- meable membrane devices and caged mussels(Mytilus edulis
signed to minimize these compounding sources of PAH and L.)in relation to water column phase distribution.Environ-
to focus on those associated with creosote-treated railway mental Toxicology and Chemistry. 18(11):2454-2461.
ties.These results suggest that seasonally variable
27

Baekken,T. 1994.Effects of highway pollutants on a small Broman,D.;Naf,C.N.; Lundbergh,I.;Zebuhr,Y. 1990.
Norwegian lake.Hamilton,R.S.;Revitt,D.M; Harrison, An in situ study on the distribution,b iotrans formation and
R.M;Monzon de Caceres,A.,eds.Highway-Pollution. flux of polycyclic aromatic hydrocarbons(PAHs)in an
146-147:131-139. aquatic food chain(Seston Mytilus edulis-Somateria mollis-
Basu,D.K.; Saxena,J.;Stoss,F.W. [and others]. 1987. lima)from the Baltic:an ecotoxicological perspective.
Comparison of drinking water mutagenicity with leaching of Environmental Toxicology and Chemistry. 9:429-442.
polycyclic aromatic hydrocarbons from water distribution Brooks,K.M. 1996.Risk assessment for Hines emerald
pipes.Chemosphere CMSHAF. 16(10-12):2592-2612. dragonfly(Somatochlora hineana)associated with the use
BCMOELP. 1994.Approved and working criteria for water of creosote treated railway ties.Chicago IL:Commonwealth
quality-1994. Victoria,British Columbia: British Columbia Edison Company,Environmental Services Department.
Ministry of Environmental Lands and Parks,Water Quality 22 p.plus appendices.
Branch,Environmental Protection Department.45 p. Brooks,K.M. 1997a.Literature review,computer model
Bender,M.E.;Roberts,M.H.; deFur,P.O. 1987.Unavail- and assessment of the potential environmental risks associ-
ability of polynuclear aromatic hydrocarbons from coal ated with creosote treated wood products used in aquatic
particles to the Eastern oyster.Environmental Pollution. environments.Vancouver,WA:Western Wood Preservers
44(4): 243-260. Institute. 139 p.
Bestari,K.T.J.;Robinson,R.D.;Solomon,K.R. [and Brooks,K.M. 1997b.PAH sediment sampling study in
others]. 1998a.Distribution and composition of polycyclic River South Parcel-July 17, 1996 to August 26, 1997. Final
aromatic hydrocarbons within experimental microcosms report.Chicago IL: Commonwealth Edison Company,Envi-
treated with creosote-impregnated Douglas Fir pilings.Envi- ronmental Services Department.22 p.plus appendices.
ronmental Toxicology and Chemistry. 17(12): 2369-2377. Brooks,K.M.2000.Assessment of the environmental ef-
Bestari,K.T.; Robinson,R.D.;Solomon,K.R.[and oth- fects associated with wooden bridges preserved with creo-
ers]. 1998b.Distribution and composition of polycyclic sote,pentachlorophenol or chromated-copper-arsenate.
aromatic hydrocarbons within experimental microcosms Res. Pap.FPL-RP-587.Madison,WI: U.S.Department
treated with liquid creosote.Environmental Toxicology and of Agriculture, Forest Service,Forest Products Laboratory.
Chemistry. 17(12):2359-2368. 100 P.
Bogan,B.W.;Lamar,R.T. 1995. One-electron oxidation in Burns,W.A.;Mankiewicz,P.J.;Bence,A.E. [and others].
the degradation of creosote polycyclic aromatic hydrocar- 1997.A principal-component and least-squares method for
bons by Phanerochaete chrysosporium. Applied and Envi- allocating polycyclic aromatic hydrocarbons in sediment to
ronmental Microbiology.61(7): 2631-2635. multiple sources.Environmental Toxicology and Chemistry.
16(6): 1119-1131.
Boldrin,B.;Tiehm,A.; Fritasche,C. 1993.Degradation of Caldwell,R.S.;Caldarone,E.M.; Mallon,M.H. 1977.
phenanthrene,fluorene,fluoranthene and pyrene by a Myco- Effects of a seawater-soluble fraction of Cook Inlet crude oil
bacterium sp.Applied and Environmental Microbiology, and its major aromatic components on larval stages of the
59: 1927-1930. Dungeness crab,Cancer magister Dana.In:Wolfe,D.A.,ed.
Borthwick,P.W.; Patrick,J.M. 1982.Use of aquatic toxi- Fate and effects of petroleum hydrocarbons in marine eco-
cology and quantitative chemistry to estimate environmental systems and organisms.New York,NY: Pergamon Press:
deactivation of marine-grade creosote in seawater. Environ- 210-220.
mental Toxicology and Chemistry. 1:281-288. Carman,K.R.;.Fleeger,J.W.;Means,J.C.;Pomarico,
Bouloubassi,I.;Saliot,A. 1991. Composition and sources S.M.;McMillan,D.J. 1995.Experimental investigation of
of dissolved and particulate PAH in surface waters from the the effects of polynuclear aromatic hydrocarbons on an
Rhone Delta(NW Mediterranean).Marine Pollution estuarine sediment food web.Marine Environmental
Bulletin.22(12): 588-594. Research.40:289-318.
Bradley,L.J.N.;Magee,B.H.;Allen,S.L. 1994.Back- Catallo,W.J.;Gambrell,R.P. 1987.The effects of high
ground levels of polycyclic aromatic hydrocarbons(PAH) levels of polycyclic aromatic hydrocarbons on sediment
and selected metals in New England urban soils.Journal of physicochemical properties and benthic organisms in a
Soil Contamination.3(4):349-361. polluted stream.Chemosphere. 16(5):1053-1060.
Brisou,J. 1972.Lipids,sterols,terpenes and bacterial bio- Cerniglia,C.E. 1984.Microbial metabolism of polycyclic
synthesis of 3,4-benzopyrene.In:Mallet,L.,ed.Pollution aromatic hydrocarbons.Advanced Applied Microbiology.
des Mileaux Vitaux par les Hydrocarbures Polybenzeniques 30:31-71.
du Type Benzo-3,4-pyrene: 181-183. (In French).
28

Cerniglia,C.E.;Heitkamp,M.A. 1989.Microbial degrada- Eisler,R. 1987.Polycyclic aromatic hydrocarbon hazards to
tion of polycyclic aromatic hydrocarbons(PAH)in the fish,wildlife,and invertebrates:a synoptic review.Final
aquatic environment.p.41-68.In:Varanasi,U.ed.Metabo- report 11.Washington,DC:U.S.Department of the Inte-
lism of polycyclic aromatic hydrocarbons in the aquatic rior-Contaminant Hazard Reviews.Laurel,MD:U.S.Fish
environment.Boca Raton,FL:CRC Press,Inc. and Wildlife Service,Patuxent Wildlife Research Center.
Christensen,E.R.; Li,A.;Razak,I.A.[and others]. 1997. 81 p.
Sources of polycyclic aromatic hydrocarbons in sediments of Environment Canada. 1992.Creosote impregnated waste
the Kinnickinnic River,Wisconsin.Journal of Great Lakes materials.Background technical report.Konasewich,D.,N.
Research.23(l):61-73. Hutt,and G.E.Brudermann.ed.Edmonton,Alberta,Canada:
Colwell,R.R. 1986.Microbial ecology studies of biofouling Environment Canada,Western and Northern Region.
of treated and untreated wood pilings in the marine envi- I I I p.plus appendices.
ronment.Final Report.Office of Naval Research:U.S. EPA. 1980.Ambient water quality criteria for polynuclear
Navy;Contract.N00014-75-C-0340 P0003.22 p. aromatic hydrocarbons.Rep.440/5-80-069.Washington,
Colwell,R.R.;Seesman,R.A. 1976.Progress report on DC:U.S.Environmental Protection Agency. 180 p.
Roosevelt roads pilings project,preliminary work.Reston, EPA. 1993.Sediment quality criteria for the protection of
VA:American Wood Preservers Institute. benthic organisms:Fluoranthene.EPA-822-R-93-012.
Davenport,R.;Spacie,A. 1991.The acute phototoxicity of Washington,DC:U.S.Environmental Protection Agency,
Office of Science and Technology.
harbor and tributary sediments from lower Lake Michigan.
Journal of Great Lakes Research. 17(1): 51-56. EPA.2003a.Method 625-Base/nuetrals and acids.In:Meth-
DeLaune,R.D.;Gambrell,R.P.;Pardue,J.H.; Patrick, ods for organic and chemical analysis of municipal and
Jr.,W.H. 1990.Fate of petroleum hydrocarbons and toxic industrial wastewater.Washington,DC:U.S.Environmental
organics in LA coastal environments.Estuaries. Protection Agency.
13(l):72-80. http://www.epa.gov/waterscience/methods/guide/methods.ht
MI.
Dickhut,R.M.;Gustafson,K.E. 1995.Atmospheric wash- EPA.2003b.Method 8310-Polynuclear aromatic hydrocar-
out of polycylcic aromatic hydrocarbons in the southern bons.In:Test methods for evaluating solid wastes.Physical
Chesapeake Bay region.Environmental Science Technology. chemical methods.Washington,DC:U.S.Environmental
29: 1518-1525. Protection Agency.
Dobroski,C.J.;Epifanio,C.E. 1980.Accumulation of http://www.epa.gov/epaoswer/hazwaste/test/main.htm
benzo(a)pyrene in a larval bivalve via trophic transfer.Canadian Journal of Fisheries and Aquatic Sciences. Gagne,F.;Blaise,C. 1993.Hepathic metallothionein level
and mixed function oxidase activity in fingerling rainbow
37:2318-2322. trout(Onchorhynchus mykiss)after acute exposure to pulp
Driscoll,S.K.; Harkey,G.A.; Landrum,P.F. 1997.Ac- and paper mill effluents_Water Research.27: 1669-1682.
cumulation and toxicokinetics of fluoranthene in sediment Gala,W.R.; Giesy,J.P. 1992.Photo-induced toxicity of
bioassays with freshwater amphipods.Environmental anthracene to the green alga,Selenastrum capricornutum.
Toxicology and Chemistry. 16(4): 742-753. Arch.Environ.Contamination Toxicology 23: 316-323.
Dunn,B.P. 1980. Polycyclic aromatic hydrocarbons in Godsy,E.M.;Goerlitz,D.F.;Grbic GaW,D. 1992.
marine sediments,bivalves,and seaweeds:analysis by high- Methanogenic biodegradation of creosote contaminants in
pressure liquid chromatography In:Bjorseth,A.;Dennis, natural and simulated ground-water ecosystems.Ground
A.J.,eds.Polynuclear aromatic hydrocarbons:chemistry and Water GRWAAP.30(2):232-242.
biological effects.Columbus,OH:Battelle Press:367-377.
Dunn,B.P.;Stich,H.F. 1976.Monitoring procedures for Goyette,D.;Boyd,J. 1989.Distribution and environmental
Chemical carcinogens in coastal waters.Journal of the impact of selected benthic contaminants in Vancouver Har-
Fisheries Research Board of Canada.33:2040-2046. bour,BC. 1985-1987.Environment Canada,Environmental
Protection Pacific,and Yukon Regional Program Rep.
Eaton,P.;Zitko,V. 1978.Polycyclic aromatic hydrocar- 89-02.North Vancouver,British Columbia,Canada:Envi-
bons in marine sediments and shellfish near creosoted wharf ronment Canada.99 p.
structures in Eastern Canada.International Council for the Goyette,D.;Brooks,K.M. 1999.Creosote evaluation:
Exploration of the Sea.E:25: 1-6. phase II,Sooke Basin study-baseline to 535 days post
construction-1995-1996. Rep.PR98-04.North Vancou-
ver,British Columbia,Canada:Environment Canada.568 p.
29

Grifoll,M.;Selifonov,S.A.;Chapman,P.J. 1994.Evi- Ingram,L.L.;McGinnis,G.D.;Gjovik,L.R.;Roberson,
dence for a Novel Pathway in the Degradation of Fluorene G. 1982.Migration of creosote and its components from
by Pseudomonas sp.Strain F274.Applied and Environ- treated piling sections in a marine environment.In:Proceed-
mental Microbiology.60(7):2438-2449. ings of the American Wood-Preservers' Association.
Haitzer,M.;Abbt-Braun,G.;Traunspurger,W.;
78: 120-127.
Steinberg,C.E.W. 1999.Effects of humic substances on the Jackim,E.;Lake,C. 1978.Polynuclear aromatic hydrocar-
bioconcentration of polycyclic aromatic hydrocarbons: bons in estuarine and nearshore environments.In:Wiley,
correlations with spectroscopic and chemical properties of M.L.,ed.Estuarine interactions.New York,NY:Academic
humic substances.Environmental Toxicology and Chemis- Press:415-428.
try. 18(12):2782-2788. Johnsen,S. 1987.Interactions between polycyclic aromatic
Harkey,G.A.;Young,T.M.2000. Effect of soil contami- hydrocarbons and natural aquatic humic substances.Contact
nant extraction method in determining toxicity using the time relationship.The Science of the Total Environment.
Microtox®assay.Environmental Toxicology and 67: 269-278.
Chemistry. 19(2):276-282. Johnson,L.L.;Myers,M.S.;Goyette,D.;Addison,R.F.
Hart,J.L. 1973.Pacific fishes of Canada.Bulletin- 1994.Toxic chemicals and fish health in Puget Sound and
Fisheries Research Board of Canada.Vol. 180.730 p. the Strait of Georgia.In:Wilson,R.C.H.;Beamish,R.J.;
Hatch,A.C.;Burton,G.A.,Jr. 1998.Effects of photoin- Aitkens,F.;Bell,J.,eds.Review of the marine environment
and biota of Strait of Georgia,Puget Sound and Juan de
duced toxicity of fluoranthene on amphibian embryos and Fuca Strait:Proceedings of the BC/Washington symposium
larvae.Environmental Toxicology and Chemistry. 17(9): on the Marine environment; 1994 January 13 and 14.Cana-
1777-1785. dian Technical Report of Fisheries and Aquatic Sciences No.
Herbes,S.E.;Schwall,L.R. 1978.Microbial transformation 1948:304-329.
of polycyclic aromatic hydrocarbons in pristine and petro- Johnston,W.R.;Harrison,R.M. 1984.Deposition of
leum contaminated sediments.Applied and Environmental metallic and organic pollutants alongside the M6 motorway.
Microbiology.35:306-316. Science of the Total Environment.33: 119-127.
Hoffman,E.J.;Mills,G.L.;Latimer,J.S.;Quinn,J.G. Jones,D.S.; Suter,G.W.,II; Hull,R.N. 1997.Toxicologi-
1984.Urban runoff as a source of polycyclic aromatic hy- cal benchmarks for screening contaminants of potential
drocarbons to coastal waters. Environmental Science and concern for effects on sediment-associated biota: 1997 Rev.
Technology. 18:580-587. Rep.ES/ER/TM-95/R4.Oak Ridge,TN:U.S. Department of
Hoffman,E.J.;Latimer,J.S.;Hunt,C.D.land others]. Energy Office of Environmental Management under budget
1985. Stormwater runoff from highways.Water Air Soil and reporting code EW 20.31 p.
Pollution.25(4):349-364. Kanaly,R.A.; Bartha,R. 1999.Cometabolic mineralization
Horness,B.H.;Lomax,D.P.;Johnson,L.L.;Myers,M.S.; of benzo(a)pyrene caused by hydrocarbon additions to soil.
Pierce,S.M.;Collier,T.K. 1998.Sediment quality thresh- Environmental Toxicology and Chemistry. 18(10):2186-
olds:Estimates from hockey stick regression of liver lesion 2190.
prevalence in English sole(Pleuronecles velulus).Environ- Khalili,N.R.;Scheff,P.A.; Holsen,T.M. 1995.PAH
mental Toxicology and Chemistry. 17(5):872-882.
source fingerprints for coke ovens,diesel and gasoline en-
Huang,X.D.;Dixon,D.G.;Greenberg,B.M. 1993.Im- gines,highway tunnels and wood combustion emissions.
pacts of UV radiation and photomodification on the toxicity Atmospheric Environment.29(4):533-542.
of PAHs to the higher plant Lemna gibba(Duckweed). Krylov,S.N.;Huang,X.;Zeiler,L.F. land others]. 1997.
Environmental Toxicology and Chemistry. 12: 1067-1077. Mechanistic quantitative structure-activity relationship
Huggett,P.A.;Van Veld,P.A.;Smith,C.L.land others]. model for the photoinduced toxicity of polycyclic aromatic
1992.The effects of contaminated sediments in the Elizabeth hydrocarbons:I.Physical model based on chemical kinetics
River.In:Burton,G.A.,ed.Sediment toxicity assessment. in a two-compartment system.Environmental Toxicology
Lewis Publications:403-430. and Chemistry. 16(1)1:2283-2295.
Ingersoll,C.G.;Haverland,P.S.;Brunson,E.L.land Lamar,R.T.;Davis,M.W.;Dietrich,D.M.;Glaser,J.A.
others]. 1996.Calculation and evaluation of sediment effect 1994.Treatment of a pentachlorophenol-and creosote-
concentrations for the amphipod Hyalella azteca and the contaminated soil using the lignin-degrading fungus Phan-
midge Chironomus riparius. Journal of Great Lakes erochaete sordida-a field demonstration.Soil Biology and
Research.22:602-623. Biochemistry.26:1603-1611.
30

Landrum,P.F.;Giesy,J.P.; Oris,J.T.;Allred,P.M. 1987. Marcus,J.M.; Stokes,T.P. 1985. Polynuclear aromatic
Photoinduced toxicity of polycyclic aromatic hydrocarbons hydrocarbons in oyster tissue around three coastal marinas.
to aquatic organisms.In Vandermeulen,J.H.;Hrudy,S.,eds. Environmental Contamination Toxicology Bulletin.
Oil in freshwater:chemistry,biology,countermeasure tech- 35: 835-844.
nology. Elmsford,NY:Pergamon Press: 304-318. Maruya,K.A.; Risebrough,R.W.; Horne,A.J. 1997.The
Landrum,P.F.;Eadie,B.J.; Faust,W.R. 1992.Variation bioaccumulation of polynuclear aromatic hydrocarbons by
in the bioavailability of polycyclic aromatic hydrocarbons to benthic invertebrates in an intertidal marsh. Environmental
the amphipod Diporeia(spp.)with sediment aging.Envi- Toxicology and Chemistry. 16(6): 1087-1097.
ronmental Toxicology and Chemistry. It: 1197-1208. Masclet,P.; Hoyau,V.;Jaffrezo,J.L.;Legrand,M. 1995.
Larsen,P.F.;Gadbois,D.F.;Johnson,A.C. 1986.Poly- Evidence for the presence of polycyclic aromatic hydrocar-
cyclic armoatic hydrocarbons in Gulf of Maine sediments: bons in the polar ice of Greenland.Analusis.23:250-252.
distributions and mode of transport.Marine Environmental
Research. 18:231-244. McConkey,B.J.; Duxbury,C.L.; Dixon,D.G.;Green-
berg,B.M. 1997.Toxicity of PAH photooxidation product
Lawrence,J.F.;Weber,D.F. 1984.Determination of poly- to the bacteria Photobacterium phosphoreum and the
cyclic aromatic hydrocarbons in some Canadian commercial duckweed Lemna gibba: Effects of phenanthrene and its
fish,shellfish,and meat products by liquid chromatography primary photoproduct,phenanthrenequinone.Environmental
with confirmation by capillary chromatography-mass spec- Toxicology and Chemistry. 16(5): 892-899.
trometry.Journal of Agricultural and Food Chemistry.
32:789-794. Meador,J.P.;Stein,J.E.; Reichert,W.L.;Varanasi,U.
1995. Bioaccumulation of polycyclic aromatic hydrocarbons
Lipkin,R. 1993.Cosmic dust can ferry in organic mole- by marine organisms. Reviews of Environmental Contami-
cules.Science News. 144:278. nation and Toxicology. 143: 79-165.
Long,E.R.;MacDonald,D.D.;Smith,S.L.;Calder,F.D. Mikkelsen,P.S.; Haefliger,M.;Ochs,M. [and others].
1995.Incidence of adverse biological effects within ranges 1996. Experimental assessment of soil and groundwater
of chemical concentrations in Marine and Estuarine sedi- contamination from two old infiltration systems for road run-
ments.Environmental Management. 19(1): 81-97. off in Switzerland.In:Hamilton,R.S.;Harrison,R.M.,eds.
Long,E.R.;Fiel,L.J.;MacDonald,D.D. 1998.Predicting Highway and urban pollution. Science of the Total Envi-
toxicity in marine sediments with numerical sediment quality ronment. 189-190: 341-347.
guidelines.Environmental Toxicology and Chemistry. Millette,D.;Barker,J.F.;Comeau,Y. land others[. 1995.
17(4):714-727. Substrate interaction during aerobic biodegradation of creo-
Lowe,D.M.;Pipe,R.K. 1985.Cellular responses in the sote-related compounds:A factorial batch experiment.Envi-
mussel Mytilus edulis following exposure to diesel oil emul- ronmental Science and Technology. 29(8): 1944-1952.
sions: Reproductive and nutrient storage cells. In:Heath, Misitano,D.A.;Casillas,E.; Haley,C.R. 1994. Effects of
G.W.;Moore,M.N.;Stegeman,J.J.,eds.Responses of the contaminated sediments on viability,length,DNA and
marine organism to pollutants.Marine Environmental protein content of larval surf smelt,Hypomesus pretiosus.
Research,Special Issue. 17(2-4):234-237. Marine Environmental Research. 37: 1-21.
Lytle,T.F.;Lytle,J.S. 1985.Pollutant transport in Missis- Monson,P.D.;Call,D.J.;Cox,D.A. land others]. 1999.
sippi Sound.Ocean Springs,Mississippi:Gulf Coast Photoinduced toxicity of fluoranthene to northern leopard
Research Laboratory. 127 p. frogs(Rana pipiens).Environmental Toxicology and
Malins,D.C.;Krahn,M.M.; Myers,M.S. [and others]. Chemistry. 18(2): 308-312.
1985.Toxic chemicals in sediments and biota from a creo- Moore,M.N.,Livingston.D.R.;Widdows,J. 1989.Hy-
sote-polluted harbor:Relationships with hepatic neoplasms drocarbons in marine mollusks:biological effects and eco-
and other hepatic lesions in English sole Parophrys vetulus. logical consequences. In:Varanasi,U.,ed.Metabolism of
Carcinogenesis.6: 1463-1469. polycyclic aromatic hydrocarbons in the aquatic environ-
Mallet,L.;Priou,M.L.;Leon,M. 1972.Biosynthesis and ment.Boca Raton,FL: CRC Press,Inc.321 p.
biodegradation of the polycyclic aromatic hydrocarbon Mueller,J.G.;Chapman,P.J.;Pritchard,P.H. 1989.
benzo-3,4-pyrene in the sediments of the Bay of Saint- Creosote-contaminated sites-Their potential for bioreme-
Malo.In:Mallet,L.,ed.Pollution des Mileaux Vitaux par diation.Environmental Science and Technology.
les Hydrocarbures Polybenzeniques du Type Benzo-3,4- 23(10): 1197-1201.
pyrene: 159-163.(In French).
31

Mueller,J.G.; Middaugh,D.P.; Lantz,S.E.;Chapman, Payne,J.F.; Kiceniuk,J.; Fancey,L.F. [and others].
P.J. 1991.Biodegradation of creosote and pentachlorophe- 1988.What is a safe level of polycyclic aromatic hydrocar-
nol in contaminated groundwater: Chemical and biological bons for fish:subchronic toxicity study on winter flounder
assessment.Applied and Environmental Microbiology. (Pseudopleuronectes americanus).Canadian Journal of
57(5): 1277-1285. Fisheries and Aquatic Sciences.34: 1983-1993.
Munoz,M.J.;Tarazona,J.V. 1993.Synergisitic effect of Perdriau,J. 1964.Marine pollution by carcinogenic benzo-
two-and four component combinations of the polycyclic 3,4-pyrene-type hydrocarbons-biological incidences.Pt.II.
aromatic hydrocarbons:phenanthrene,anthracene,naphtha- Cahiers Ocenanographiques. 16:204-229.(In French.)
lene and acenaphthene on Daphnia magna.Bulletin of Envi- Persaud,D.;Jaagumagi,R.; Hayton,A. 1992.Guidelines
ronmental Contamination Toxicology.50:363-368. for the protection and management of aquatic sediment
Neff,J.M. 1979. Polycyclic aromatic hydrocarbons in the quality in Ontario.Toronto,Canada:Ontario Ministry of the
aquatic environment;sources,fates and biological effects. Environment.Water Resources Branch.
London:Applied Science Publishers LTD. Pierce,R.H.,Jr.; Brent,C.R.;Williams,H.P.;Reeve,
ISPN:0-85334-832-4. S.G. 1977. Pentachlorophenol distribution in a fresh water
Neff,J.M. 1982.Accumulation and release of polycyclic ecosystem. Environmental Contamination Toxicology
aromatic hydrocarbons from water,food,and sediment by Bulletin. 18(2):251-258.
marine animals.Duxbury,MA:Battelle New England Polisini,J.M. 1994.Toxicity of creosote to aquatic organ-
Marine Research Laboratory. isms.Sacramento,CA:California Department of Toxic
O'Connor,T.P. 1991.Concentrations of organic contami- Substances.2 p.
nants in mollusks and sediments at NOAA national status Prahl,F.G.;Crecellus,E.;Carpenter,R. 1984.Polycyclic
and trend sites in the Coastal and Estuarine United States. aromatic hydrocarbons in Washington coastal sediments:an
Environmental Health Perspectives.90:69-73. evaluation of atmospheric and riverine routes of introduc-
Olive,P.L. 1988.DNA precipitation assay: a rapid and tion.Environmental Science and Technology. 18:687-693.
simple method for detecting DNA damage in mammalian PSWQA. 1996. Recommended protocols for measuring
cells. Environmental and Molecular Mutagenesis. selected environmental variables in Puget Sound.Olympia,
11:487-495. WA: Puget Sound Water Quality Authority.
O'Malley,V.P.;Abrajano,T.A.,Jr.;Hellou,J. 1996. Roesijadi,G.;Anderson,J.W.;Blaylock,J.W. 1978.
Stable carbon isotopic apportionment of individual poly-
cyclic aromatic hydrocarbons in St.John's Harbour,New- Uptake of hydrocarbons from marine sediments contami-
foundland.Environmental Science and Technology. nated with Prudhoe Bay crude oil: Influence of feeding type
30(2):634-639. of test species and availability of polycyclic aromatic hydro-
carbons.Journal of Fisheries Research Board of Canada.
Ott,F.S.;Harris,R.P.;O'Hara,S.C.M. 1978.Acute and 35:608-614.
sublethal toxicity of naphthalene and three methylated Sayler,G.S.;Sherrill,T.W. 1981.Bacterial degradation of
derivatives to the estuarine copepoe,Eurytemora afnis.
Marine Environmental Research. 1:49-58. coal conversion by-products(polycyclic aromatic hydrocar-
bons)in aquatic environments.Final Report.Office of Water
Padma,T.V.; Hale,R.C.;Roberts,M.H.,Jr. 1998.Toxic- Research and Technology,U.S.Department of Interior
ity of water-soluble fractions derived from whole creosote matching grant program project B-040 TENN.Knoxville,
and creosote-contaminated sediments. Environmental TN: Department of Microbiology and the Graduate Program
Toxicology and Chemistry. 17(8): 1606-1610. in Ecology,University of Tennessee. 80 p.
Pastorok,R.A.;Peek,D.C.;Sampson,J.R.;Jacobson, Sing,A.K.; Gin,M.F.;Ni,F.; Christensen,E.R. 1993.A
M.A. 1994.Ecological risk assessment for river sediments source-receptor method for determining non-point sources of
contaminated by creosote.Environmental Toxicology and PAHs to the Milwaukee Harbor Estuary. In:Christensen,
Chemistry. 13(12): 1929-1941. E.R.;Edgington,D.N.;Giesy,J.P.,eds.Contaminated
Payne,J.F.;Fancey,L.F. 1989.Effect of polycyclic aro- Aquatic Sediments.28(8-9):91-102.
matic hydrocarbons on immune responses in fish: Change in Smith,S.L.; MacDonald,D.D.; Keenleyside,K.A. [and
melanomacrophage centers in flounder(Pseudopleuronectes others]. 1996.A preliminary evaluation of sediment quality
americanus)exposed to hydrocarbon-contaminated sedi- assessment values for freshwater sediments.Journal of Great
ments. Marine Environmental Research.28:431-435. Lakes Research.22:624-638.
32

Southworth,G.R.; Beauchamp,J.J.;Schmeider,P.K. Venkatesan,M.I. 1988.Occurrence and possible sources of
1978. Bioaccumulation potential of polycyclic aromatic perylene in marine sediments-a review.Marine Chemistry.
hydrocarbons in Daphnia pulex. Water Research. 25: 1-27.
12:973-977.
Vogelbein,W.K.;Fournie,J.W.;Van Veld,P.A.; Hug-
Stekoll,M.S.,Clement,L.E.;Shaw,D.G. 1980.Sublethal gett,R.J. 1990.Hepatic neoplasm's in the Mummichog
effects of chronic oil exposure on the intertidal clam, Fundulus heleroclitus from a creosote-contaminated site.
Macoma ballhica. Marine Biology.57: 51. Cancer Research.50:5978-5986.
Stringfellow,W.T.;Aitken,M.D. 1994.Comparative Wade,M.M.;Connor,M.S.;Jop,K.M. [and others].
physiology of phenanthrene degradation by two dissimilar 1987. Summary evaluation of the environmental impact
pseudomonads isolated from a creosote-contaminated soil. resulting from the use of creosoted pilings in the historic
Canadian Journal of Microbiology. 50(6):432-438. restoration of pier#2 at the Charleston Navy Yard. Final
Suter,G.W.,II;Tsao,C.L. 1996.Toxicological bench- Report.Boston,MA: U.S. Department of the Interior,Na-
marks for screening potential contaminants of concern for tional Park Service,North Atlantic Region.36 p.
effects on aquatic biota: 1996 Rev.Rep. ES/ER/TM-96/R2. Wade,M.J.;Costa,H.J.;Boehm,P.D. 1988. Exposure
Oak Ridge,TN:U.S.Department of Energy,Risk Assess- assessment of creosote in selected sediment and seawater
ment Program,Health Sciences Research Division. samples collected in the vicinity of Piers#2 and#4 at the
Swartz,R.C. 1999.Consensus sediment quality guidelines Charleston navy yard.Boston,MA: U.S.Department of the
for polycyclic aromatic hydrocarbon mixtures.Environ- Interior,National Park Service,North Atlantic Region.49 p.
mental Toxicology and Chemistry. 18(4):780-787.
plus appendices.
Swartz,R.C.;Kemp,P.F.;Schults,D.W. [and others]. Wade,T.L.; Kennicutt,M.C.,I1;Brook,J.M. 1989.Gulf
1989.Acute toxicity of sediment from Eagle Harbor,Wash- of Mexico hydrocarbon seep communities:Pt.III.Aromatic
ington,to the Infaunal Amphipod Rhepoxynius abronius. hydrocarbon concentrations in organisms,sediments and
Environmental Toxicology and Chemistry. 8: 215-222. water.Marine Environmental Research.27: 19-30.
Swartz,R.C.;Schultz,D.W.;Ozretich,R.J. [and others]. Wakeham,S.G.; Schaffner,C.;Giger,W. 1980.Poly-
cyclic aromatic hydrocarbons in recent lake sediments-1.
1995.�PAH: a model to predict the toxicity of polynuclear Compounds having anthropogenic origins.Geochimica
aromatic hydrocarbon mixtures in Feld-collected sediments. Com o Compounds
ha having
th 4 ogenic
Environmental Toxicology and Chemistry. 14: 1977-1987.
3-413.
Swink,F.A.;Wilhelm,G.S. 1994.Plants of the Chicago Wan,M.T. 1991. Railway right-of-way contaminants in the
region,4th ed.Indianapolis,IN:Indiana Academy of lower mainland of British Columbia:Polycyclic aromatic
Science. hydrocarbons.Journal of Environmental Quality.
20: 228-234.
Tagatz,M.E.; Plaia,G.R.;Deans,C.H.; Lores,E.M. Washington Department of Ecology. 1995.Elliott Bay
1983.Toxicity of creosote-contaminated sediment to field waterfront recontamination study-Volume 1:Field Investi-
and laboratory colonized estuarine benthic communities. gation Report.Publication No.95-335.Olympia,WA:
Environmental Toxicology and Chemistry.2:441-450.
Washington State Department of Ecology.
Tang,J.;Alexander,M. 1999.Mild extractability and Weinstein,J.E.;Oris,J.T. 1999.Humic acids reduce the
bioavailability of polycyclic aromatic hydrocarbons in soil. Bioaccumulation and photoinduced toxicity of fluoranthene
Environmental Toxicology and Chemistry. to fish. Environmental Toxicology and Chemistry.
18(12):2711-2714. 18(9):2087-2094.
United Nations University.2001.Table 11:A summary of Wendt,P.H.;Van Dolah,R.F.; Bobo,M.Y. [and others].
the available sediment quality criteria and guidelines for the 1994.A study of wood preservative leachates from docks in
protection of aquatic life.In:The water virtual learning an estuarine environment.Final Report.Charleston, SC:
center.Waterloo,Ontario,Canada:UNU-The International South Carolina Department of Health and Environmental
Network on Water Environment and Health and the Univer- Control,Office of Ocean and Coastal Resource
sity of Waterloo. Management.
http://wvlc.uwaterloo.ca/biology447/modules/module 1/seda
quat3.htm1. West,W.R.;Smith,P.A.; Booth,G.M. [and others].
Varanasi,U. 1989.Metabolism of polycyclic aromatic 1986a. Determination of genotoxic polycyclic aromatic
hydrocarbons in the aquatic environment. Boca Raton, FL: hydrocarbons in a sediment from the Black River(Ohio).
CRC Press. 321 p. Archives of Environmental Contamination and Toxicology.
15:241-249.
33

West,W.R.;Smith,P.A.;Stoker,P.W. [and others]. Appendix—Occurrence and
1986b.Analysis and genotoxicity of a PAC-polluted river Toxicity of PAH in the
sediment. In:Cooke,M.;Dennis,A.J.,eds.Polynuclear
aromatic hydrocarbons:mechanisms,methods and metabo- Environment
lism.Columbus,OH:Battelle Press: 1395-1411.
White,J.C.;Hunter,M.;Nam,K.[and others]. 1999. Sources of PAH in Aquatic
Correlation between biological and physical availabilities of Environments
phenanthrene in soils and soil humin in aging experiments. Polycyclic aromatic hydrocarbons(PAH)are formed by a
Environmental Toxicology and Chemistry. 18(8): 1720— variety of processes,including indirect and direct biosynthe-
1727• sis,fossil fuel production and distribution,and incomplete
Widdows,J.;Bakke,T.;Bayne,B.L. [and others]. 1982. combustion of organic matter associated with forest fires,
Responses of Mytilus edulis L.on exposure to the water transportation systems,home heating,and energy produc-
accommodated fraction of North Sea oil. Marine Biology. tion.Once formed,PAH can be transported into an aquatic
67: 15. environment by a number of pathways including fossil fuel
distribution,stormwater runoff,sewage effluent,and atmos-
Widdows,J.;Donkin,P.;Evens,S.V. 1985.Recovery of pheric deposition.These compounds have been ubiquitous in
Mytilus edulis L. from chronic oil exposure.Marine earth's biosphere for eons(Masclet and others 1995)and
Environmental Research. 17: 250-253. indeed are likely to be present throughout the cosmos
Wild,S.R.;Jones,K.C. 1995.Polynuclear aromatic hydro- (Lipkin 1993).
carbons in the United Kingdom environment.A preliminary Biosynthesis
source inventory and budget.Environmental Pollution.
88(1): 91-108. Indirect biosynthesis of PAH occurs when extended
quinones and related polycyclic materials(mostly plant and
Zarembski,A.M. 1990.Wood tie life:Pt.I—Average tie animal pigments)are exposed to the reducing conditions
life.Railway Track and Structures. 86: 17-18. found in anoxic sediments.The resulting PAH tend to accu-
mulate in the sediments where they were formed.De novo
biosynthesis of PAH by aerobic and anaerobic bacteria,
fungi,and plants is controversial.However,Mallet and
others(1972)and Brisou(1972)concluded that both aerobic
and anaerobic bacteria can biosynthesize benzo[a]pyrene
(B[a]P)and certain other PAH using fatty acids,sterols,
plant pigments,and aliphatic terpenes as substrates.In most
cases where PAH biosynthesis has been reported,accumula-
tion of PAH in the organisms purported to have synthesized
them could also have been attributed to uptake of PAH from
exogenous sources.
In light of all the literature reviewed,it appears that PAH
biosynthesis may occur to a limited extent under special
environmental conditions when necessary bacterial growth
substrates are present.Eisler(1987)suggested that,on a
global scale,biosynthesis annually contributes 2.7 Gg
(6 million lb)of PAH to aquatic environments.
Fossil Fuels
Fossil fuels including peat,coal,and petroleum are relatively
rich in complex assemblages of PAH.These compounds
reach aquatic environments through surface runoff,waste
water,and as a result of petroleum spillage.Eisler(1987)
estimates that spilled petroleum contributes 170 Gg(375
million lb)of PAH to aquatic environments each year.This
source overwhelms all others in terms of global inputs.
34

Pyrolysis Hoffman and others(1984)noted that stormwater runoff
Pyrolysis of organic matter at temperatures between 400°C from urban areas and highways accounted for 71%of the
and 2,000°C results in the generation of a wide variety of high molecular weight(HMW)PAH and 36%of the total
PAH.Reducing conditions(insufficient oxygen)in pyrolytic PAH loading to Narragansett Bay in Rhode Island. Hoffman
environments favor PAH production.Forest and grass fires, and others(1985)found that highway runoff contributed
industrial processes,heating,power generation,and petro- 96.3%of PAH loading to the Pawtuxet River in Rhode
leum refining release significant amounts of PAH into the Island while sewage contributed 3.67%and industry added
atmosphere.These products of combustion are subject to the remaining 0.03%.More than 30%of all pyrolytic PAH
chemical-and photo-oxidation.However,their residence in the coastal sediments of Washington State are supplied by
time in the atmosphere is long enough to allow wide disper- riverine transport of suspended particulate materials,while
sal,and they are a major source of PAH to aquatic and ter- direct atmospheric input accounts for a maximum of 10%
restrial environments.According to Eisler(1987),forest and (Prahl and others 1984).
prairie fires together with agricultural burning release nearly Observed Levels of PAH in
33 Gg(72 million lb)of PAH into the atmosphere each year.
This is three times the amount from all other pyrolytic Terrestrial Environments
sources combined. Wild and Jones(1995)and Bradley and others(1994)char-
Petrolytic acterized baseline and urban soil concentrations of PAH in
the United Kingdom and New England soils,respectively.
Johnston and Harrison(1984)reported that B[a]P deposition Bradley and others(1994)also reported significantly higher
along a United Kingdom motorway was 2.8 µg/M2/week. (u=0.05)concentrations of PAH near pavement(21.9 µg/g)
B[a]P is approximately 0.5%to 2.5%of some PAH mix- compared with areas not near pavement(8.3 µg/g).Their
tures,and a direct extrapolation suggests that the total PAH data are summarized in Table 25.
loading along a well-used highway may be 560 µg/M2/week.
Winter levels of PAH in coastal areas are higher than sum- Concentrations of PAH in rural soils were spread evenly
mer levels.This is attributed to increased pyrolytic input across the 10 individual compounds evaluated by Wild
from the burning of fossil fuels for power generation and and Jones(1995).The suite of PAH in urban and forest
heating(Bouloubassi and Saliot 1991). Broman and others soils was dominated by phenanthrene,fluoranthene,
(1990)suggested that primary PAH inputs in the Baltic benz(a)anthracene/chrysene,pyrene,benzo(b)fluoranthene,
region were from exhaust emissions associated with auto- and benzo(ghi)perylene.Minor amounts of anthracene,
mobiles,domestic heating,refuse incineration plants,ships, acenaphthene,fluorene,and naphthalene were observed.
and aircraft. Soil concentrations of PAH in New England cities were
dominated by benzo(b or k)fluoranthene(3.16 µg/g),
Neff(1979)reported that little-used(224 km)motor oil fluoranthene(3.047 µg/g),pyrene(2.398 µg/g),chrysene
contained 6.4 µg B[a]P/L equivalent to nearly 1.28 mg/L (1.841 µg/g),phenanthrene(1.838 µg/g),B[a]P,and
total PAH.Dunn and Stich(1976)found up to 22 mg/L benzo(a)anthracene in order of decreasing mean
B[a]P in well-used crankcase oil.This is equivalent to concentration.
4.4 parts per thousand(g/L)total PAH. In 1989,Washington
State had 4.2 million vehicles registered.These vehicles
produced 79 MIL(21 million gallons)of used crankcase oil
each year.That may represent as much as 284 Mg Table 25�VIean soil concentrations of PAH observed in
(625,000]b)of PAH available to the environment. terrestrial environments.All values are in micrograms
PAH per kilogram dry soil weight
Industrial and Domestic Storm and Wastewater Mean PAH Upper 95th percentile
Industrial and domestic storm and wastewaters are rich in Soil source concentration PAH concentration
PAH. Secondary sewage treatment removes some PAH,but Boston' 18.7 35.9
most are released to aquatic environments through sewage Providence' 16.8 23.5
treatment plant outfalls.Eisler(1987)notes that untreated, Springfield' 19.1 29.9
raw sewage contains 100 to 500 µg/L total PAH and sewage United Kingdomb
sludge contains 200 to 1,750 µg/L PAH.Goyette and Boyd Rural soils 0.2
(1989)recorded sediment PAH concentrations of 17 µg
TPAH/g dry sediment near a major combined sewage— Urban soils 4.2
stormwater outfall discharging into Vancouver Harbor. Forest soils 4.8
Sediment PAH concentrations in the central areas of the 'Sum of 17 individual PAH compounds from Bradley and
harbor were consistently in the range of 2 to 5 µg TPAH/g others(1994).
dry sediment. bSum of 10 individual PAH compounds from Wild
and Jones(1995).
35

Observed Concentrations of urbanized and industrialized areas as high as 791 µg/g in the
PAH in Aquatic Environments United Kingdom,and Cerniglia and Heitkamp(1989)meas-
ured sediment PAH levels up to 1.8 mg/g at an oil refinery
Because of the many natural sources,Polycyclic aromatic outfall in Southampton,England. Sediment PAH concentra-
hydrocarbons are ubiquitous in aquatic and terrestrial envi- tions in other industrialized areas ranged from 0.198 to
ronments.However,significantly increased levels have been 232 µg/g.These historic depositions are nearly all associated
recorded in all environments during the last two centuries. with industrial activities working with wood,coal,and petro-
Wakeham and others(1980)observed total PAH concentra- leum products.These point sources have declined since the
tions of 1.0 µg/g in deep core sediments representing histori- middle of the 20th century.However,as previously noted,
cal deposits beginning 3,000 years before present from Lake anthropogenic sources of PAH are currently dominated by
Washington in Washington State.Venkatesan(1988)re- transportation systems and are associated with internal com-
ported perylene concentrations as high as 4 µg/g in pristine, bustion engines,lubricants,tires,and asphalt and tars used in
but anoxic,marine sediments.Neff(1979)found low(<1 to road surfacing(Mikkelsen and others 1996). in addition to
2 µg/L)levels of PAH in the water column of pristine areas highway runoff,atmospheric deposition is a primary mode
and similarly low sediment contamination concentrations of of PAH transport to aquatic environments(Larsen and others
<0.050 µg/g.Eisler(1987)and Cemiglia and Heitkamp 1986,Bouloubassi and Saliot 1991).Table 26 summarizes
(1989)found similar distributions of sediment PAH levels. Eisler's(1987)assessment of PAH loading to aquatic envi-
Levels in pristine areas of Alaska,Africa,and the Amazon ronments from the most common sources.
Basin ranged from 0.005 to 0.544 µg/g.There are numerous There is a consistent thread running through research and
natural sources for this baseline PAH level including reviews by Bouloubassi and Saliot(1991),Neff(1979),
volcanoes,forest and prairie fires,natural oil seeps,and Eisler(1987),and others cited earlier.According to the
biosynthesis. sediment record,PAH have been ubiquitous on earth for at
The 1.0 µg PAH/g recorded in Lake Washington sediment least several thousand years with pre-industrial age concen-
cores dating from 3,000 years before present until the middle trations generally less than 1 to 5 µg TPAH/g. Worldwide,
of the 19th century by Wakeham and others(1980)increased urban areas,particularly those adjacent to roadways,have
to 7 to 8 µg/g after European settlement in the 1860s.There much higher baseline sediment PAH levels in the range of
are many potential point and nonpoint sources of PAH asso- 0.5 to 50 mg PAH/kg dry soil or sediment.Heavily industri-
ciated with urban and industrial areas.These include electri- alized areas may have TPAH concentrations of 10 to several
cal power generation,home heating,internal combustion hundred mg TPAH/kg.The major sources of PAH are at-
engine exhaust,lubricating oils,tires,asphalt paving,etc. mospheric deposition,wastewater,storm water,and surface
Christensen and others(1997)determined concentrations runoff associated with transportation systems.
and sources of eight PAH in sediments of the Kinnickinnic
River,in Wisconsin,as a function of time from 1895 until Fate of PAH in the Environment
1991. Sediments in the Kinnickinnic River are heavily con- Polycyclic aromatic hydrocarbons form a family of com-
taminated with PAH at concentrations of 80 to 1,000 µg pounds,-and the routes of degradation and fates are different
PAH/g dry sediment.Mean concentrations observed in dated for the major classes of PAH. In water,PAH evaporate,
cores declined from 423 µg/g in 1902 to 8 µg/g in 1991. disperse into the water column,become incorporated into
The dominant PAH shifted from LMW compounds(average bottom sediments,concentrate in aquatic biota,or experience
molecular weight= 179.3)in 1902 to higher molecular chemical and biological degradation.Borthwick and Patrick
weight compounds in 1991(average molecular (1982)estimated the chemical and biological half-life of the
weight=206.4). Earlier sources were dominated by coal dissolved components of marine grade creosote at less than
gasification and coking plants associated with the steel
industry.Polycyclic aromatic hydrocarbons in more recent
sediment deposits are mostly associated with highway run-
off.A recent decline in atmospheric PAH deposition was Table 26—Global sources of PAH to aquatic
also observed by Masclet and others(1995)who found that environments'
PAH concentrations in polar ice caps peaked during the
period 1910 to 1940 and have subsequently declined. Source PAH(Gg)
On a broader scale,Neff(1979)reported PAH concentra- Petroleum spillage 170.00
Atmospheric deposition 50.00
tions up to 15 µg/g associated with industrialized areas (from combustion)
and/or human population centers and Wild and Jones(1995) Wastewater 4.40
observed a mean freshwater sediment concentration of Surface land runoff 2.94
17.2 µg TPAH/g in the United Kingdom. Eisler(1987) Biosynthesis 2.70
reported sediment PAH concentrations associated with
'Eisler(1987).
36

one week in laboratory experiments.More recently,Bestari of B(a)P in the presence of complex hydrocarbon mixtures.
and others(1998a,b)observed an exponential decline in Crude oil,distillates of heating oil,jet fuel,and diesel fuel
creosote-derived PAH released to microcosms.The concen- supported up to 60%mineralization of 80 µg B(a)P/g soil in
tration of PAH in these microcosms reached baseline levels 40 days.Millette and others(1995)also demonstrated the
by the end of their 84-day study. interdependence and cometabolism of mixtures of creosote-
The most important degradative processes for PAH in derived PAH following an initial lag time of 5 to 7 days
aquatic environments are photo-oxidation,chemical oxida- during which the natural microbial community was selected
tion,and biological transformation by bacteria and animals for those phenotypes capable of more efficiently metaboliz-
ing PAH.In that study,60/o to 75/o of the phenanthrene was
of new creosote oil,may be rapidly lost from
mineralized within 30 days.This suggests that in the pres-
ated with particulate materials,and only about a third are
p ence of complex cometabolites,phenanthrene,which com-
resent in dissolved form.Dissolved PAH will probably Prises 19.4
degrade rapidly through photo-oxidation(EPA 1980).They /0
the matrix
degrade most rapidly at higher concentrations,at elevated
temperatures and oxygen levels,and at higher levels of solar into naturall PAH that move from creosote-treated wood
environments.e
irradiation.Different PAH vary significantly in their relative Bogan and Lamar(1995)showed that white rot basidiomy-
sensitivity to chemical and biological degradation. cetes are able to degrade a broad spectrum of intermediate
Because of their low aqueous solubility and hydrophobic (phenanthrene)and heavier creosote-derived PAH.Mueller
character,the higher molecular weight PAH readily adsorb and others(1989)provide an excellent review of bioreme-
to particulate materials and solid surfaces in water.The diation technologies designed to remove PAH,including the
ultimate fate of PAH that accumulate in sediments is be- HMW compounds,from creosote-contaminated sites.
lieved to be biotransformation and degradation by bacteria, Ingram and others(1982)observed that the concentration of
fungi,and algae(EPA 1980,Borthwick and Patrick 1982, creosote in leaching vats increased to greater than 700 µg/L
Cemiglia 1984,Boldrin and others 1993).Low molecular in the first 72 h and then decreased to less than 34 µg/L at
weight PAH,such as naphthalene,degrade rapidly,while the the end of 20 days.They attributed that decrease to bacterial
higher molecular weight PAH such as benz(a)anthracene and metabolism of the LMW PAH that was leached from the pile
B(a)P are more resistant to microbial attack.Herbes and sections in the study.
Schwall(1978)reported turnover times for naphthalene,
anthracene,and benz(a)anthracene of 13,62,and 300 h, Tagatz and others(1983)noted that creosote concentrations
respectively.Mueller and others(1991)found that natural decreased by 42%during an 8-week period in sediments
microbial communities mineralized 94%of the LMW PAH artificially contaminated as part of their mesocosm studies.
in 14 days but only 53%of the HMW PAH were degraded They attributed the decrease to microbial metabolism.
during the same period.They also noted that the most rapid Neff(1979)attempted to integrate the degradative processes
biodegradation of PAH occurred at the water—sediment associated with PAH removal from aquatic environments.
interface.This is because prokaryotes oxidize PAH as a first He concluded that the residence time of PAH in water is
step in metabolism.Deeper sediments usually contain little brief.The lower molecular weight aromatics(benzene to
oxygen,thus inhibiting microbial metabolism. phenanthrene)are removed primarily by evaporation and
Saylor and Sherrill(1981)and Cemiglia and Heitkamp microbial activity.Higher molecular weight PAH are re-
(1989)summarized the available literature describing the moved mainly by sedimentation and photo-oxidation.Deg-
half-life of PAH in aquatic environments.The results were radation of PAH by animals in the water column is of minor
highly variable and depended on PAH species as well as a importance. In nutrient rich,biologically active,aerobic
range of environmental and biological factors such as tem- sediments,the degradation of PAH is dramatically increased
perature,the presence of cometabolites,the nature of the by healthy bacterial and fungal communities.However,in
microbial community,and the availability of oxygen.A anaerobic sediments,the heavier molecular weight PAH
broad range of bacteria and fungi have been observed to (four through seven rings)may persist for years.
rapidly degrade numerous light and heavy molecular weight
PAH(Grifoll and others 1994;Stringfellow and Aitken PAH From Different Sources
1994;Cemiglia and Heitkamp 1989).Bacterial communities Khalili and others(1995),Sing and others(1993),O'Malley
in polluted areas metabolize PAH more quickly than com- and others(1996),Dickhut and Gustafson(1995),and
munities in unpolluted areas,and lighter weight PAH are Bender and others(1987)characterized the spectrum of PAH
metabolized more quickly than heavier PAH(Herbes and compounds associated with a variety of sources. In Figure
Schwall 1978).Naphthalene has a short turnover time(hours 24,their data are combined with results for weathered PAH
to days),whereas the five ringed B(a)P has a long turnover deposits in sediments adjacent to marine piling installed in a
time(years under unfavorable conditions).However,Kanaly pristine marine environment(Goyette and Brooks 1999)As
and Bartha(1999)demonstrated significant biodegradation seen in Figure 24,coal contains significant quantities of
37

35
384 BMP 0.5(marine sediment)
Bender of al.(1987)(coal dust)
® Sing et al.(1993)(highway dust)
30 O'Malley et al.(1996)(crankcase oil)
Dickhut and Gustafson(1995)(atmospheric deposition)
Khalili et al.(1995)(diesel exhaust)
25
a
m
20
0
c
0
r
0
0 15
a
a
0
a
Eo 10
U
5 lid
0 m m am d m a) m m a) c m o aci m
C c c c c C C C C C d
a) 0) C m d U t U y t 0. 20 M G a)
T
t $ 1 L E2 C a 12 Z C m a� m a a
t L n � r ns r t o 0 0 o o r
a a C C C p C U 7 Ncc N 01
co C 4) Q 7 f0 C C N O
Z Q ¢ a o m m m
(Dca
m
0
N
C
N
m
Figure 24—PAH profiles associated with a variety of sources.
intermediate and low molecular weight(LMW)PAH includ- The fingerprint of PAH from creosote-treated wood changes
ing naphthalene,fluorene,phenanthrene,fluoranthene,and with time and weathering.The degradation of creosote by
pyrene.The other sources involve PAH subjected to high photo-oxidation and microbial catabolism is well studied and
temperatures such as from crankcase oil,diesel exhaust,and verified.Brooks(1997a)reviewed the microbial degradation
atmospheric deposition. Sediment samples collected 384 of PAH and developed algorithms for estimating the degra-
days following construction of a creosote-treated dolphin are dation of sedimented PAH as a function of temperature and
presented in black columns in Figure 24.The creosote spec- ambient oxygen levels.Goyette and Brooks(1999)installed
trum is dominated by fluoranthene and other intermediate- three six-piling,creosote-treated dolphins in a pristine area
weight PAH(phenanthrene to benzo(b or k)fluoranthene). of Sooke Basin,British Columbia.The study periodically
Low molecular weight PAH represented less than 2%of the collected sediment samples for PAH,grain size,total organic
total PAH,and compounds heavier than benzo(b or carbon,and sulfide and biological analysis for 1,540 days.
k)fluoranthene contributed little to the overall spectrum. In The PAH composition of unused creosote oil,creosote
contrast,the PAH in crankcase oil are dominated by HMW pressed from the treated wood immediately following treat-
compounds.The relative proportions of phenanthrene and ment,and the sediments were determined in this study.The
fluoranthene are reversed in highway runoff compared with results are presented in Figure 25.The proportion of LMW
creosote.The suite of compounds associated with atmos- compounds decreased significantly during the treating proc-
pheric deposition is similar to creosote-derived PAH. ess.The PAH lost from freshly treated piling were rich in the
However,atmospheric deposition typically results in a spa- intermediate-weight compounds,particularly phenanthrene
tially uniform distribution at levels less than 1.0 µg PAH/g. and fluoranthene.As sedimented PAH weathered,
38

90
Raw oil 14BMP 0.5
80 ❑394 BMP 0.5 ❑1360BMP 0.5
iS 70
°OL 60
E
U
Q 50
0.
U
40
O
0 30
0
CL
a 20
CL
10
O '1 iL Ll MA .4 2-m_J_h _111ilil
w a�i 0) T m m L) y � m y m a
a
is a o w c [1 �° L CL 2
L
L Q L N L E0 L t 41 d a1 L
MC CCL CLL L Q LL M V 0 N N N F-
M d N Y c0 43
N O
m
.n
O
N
C
N
m
Figure 25---Changing composition of weathering creosote in marine sediments.
phenanthrene was reduced but remained at about 13%of the creosote-treated piling in Crab Bay,Alaska,were dominated
total. Fluoranthene was degraded but at a slower rate than by phenanthrene, fluoranthene,pyrene,and chrysene. All of
phenanthrene.At the end of 4 years,the creosote-derived these studies found very low proportions of PAH com-
PAH were dominated by fluoranthene. However,phenan- pounds heavier than benzo(b or k)fluoranthene.
threne,pyrene,benzo(a)anthracene,chrysene,and benzo(b
and k}fluoranthenes each represented approximately 10%of Wan(1991)examined sediments adjacent to operating rail-
the total.The PAH compounds lighter than phenanthrene way rights of way in British Columbia and adjacent to a
were weathered to very law concentrations,and those heav- creosoted wharf structure in Nova Scotia.The spectra are
ier than benzo(b and k)fluoranthene remained at low can- similar except that more naphthalene was found adjacent to
centrations similar to those found in the raw oil and the the railway rights of way than adjacent to the creosote-
newly treated wood. treated structures located in marine environments.That is
probably due to the presence of diesel fuel and coal dust,
Bestari and others(1998a,b)observed similar results in both of which contain higher proportions of the lower mo-
microcosm studies with either unused creosote oil or pros- lecular weight PAH and are associated with rail lines in the
sure-treated piling.In their studies,the PAH spectrum also lower mainland of British Columbia(Fig. 26).
shifted from low to heavier weight compounds.At the end of
The preceding discussion is important in that it clearly dem-
84 days,sediments contaminated with liquid creosote by
Bestari and others(1998a)were dominated by phenanthrene, onstrates that the suite of PAH associated with recent
fluoranthene,pyrene,and chrysene with very low concentra- (<4 Year old)losses from treated wood are dominated by
bons of other compounds. Bestari and others(1998b)ob- phenanthrene, fluoranthene,pyrene,and chrysene with lesser
served a similar PAH distribution at the end of 68 days in amounts of Benz(a)anthracene and benzo(b or k) fluoran-
microcosms containing piling freshly treated with creosote, these.Other compounds are found only at very law concen-
trations. It also demonstrates the complexity of attributing
While fingerprinting l8 possible sources of PAH associated environmental PAH to a single source,such as railroad ties.
with the Exxon Valdez oil spill in Alaska,Burns and others
(1997)also found that the suite of PAH in sediments next to
39

35
30 ■ 384 BMP 0.5
❑Wan(1991)
25 Ernst(1994)
0
20
Q
o_
0
15
10
5
� a
O N G � 0 Q) U L d U a) N 2 .0 N C C
L O L (� C a. fq + L_ (6 (U O N N
LL (D
CD ¢
CJ o
` ac `c pro o r
Z N N CD
rl a U W N N
Q O m O C
N )
o
N —
C
O
CA
Figure 26—Proportion of PAH compounds associated with creosote-treated piling (384 BMP 0.5)and railway
rights-of-way in the lower mainland of British Columbia(Wan 1991)with sedimented PAH adjacent to a
creosote wharf structure in Nova Scotia (Ernst,W., 1994, personal communication).
Weathering of Creosote-Derived PAH and others(1990)discussed the fate of hydrocarbons,includ-
Ingram and others(1982)observed increasing PAH concen- ing creosote,in Louisiana coastal environments.DeLaune
trations for approximately 72 h in their static leaching tests and others(1990)noted that microbial degradation deter-
of creosote-treated piling.The concentrations then declined mines the fate of sedimented creosote more than other fac-
exponentially.They hypothesized that the decreases were tors,and they discussed factors determining catabolic rates.
due to photodegradation and catabolism by microbes. In a partitioning of PAH Between Dissolved
more recent article,Bestari and others(1998a,b)observed
significant decreases in dissolved PAH concentrations in a and Particulate Phases in Water
series of static leaching tests that immersed between 0.5 and Polycyclic aromatic hydrocarbons are hydrophobic—that is
6 piling in 12,000-L microcosms. Initial concentrations as one reason they form sheens. Individual PAH solubility is
high as 97 µg TPAH/L in these static systems decreased to generally inversely correlated with molecular weight.The
less than 10 µg TPAH/L at the end of 85 days with no sig- LMW compounds have solubilities varying from 32 mg/L
nificant increases in sediment concentrations or uptake by for naphthalene to 0.044 mg/L for anthracene.The HMW
the polyethylene liners used in the microcosms. Bestari and compounds vary between 0.26 mg/L for fluoranthene and
others also attributed the exponential declines to photode- 0.00026 mg/L for benzo(ghi]perylene.
gradation and microbial catabolism. Colwell(1986) Goyette and Brooks(1999)determined the PAH composi-
identified the bacteria responsible for the degradation of tion in raw creosote oil, in piling, in surface sheens found
creosote-derived PAH in marine environments. Since then,a during construction,and in sediments during a period of
rich literature has evolved describing the microbial catabo- 535 days following construction. Naphthalene,the most
lism of PAH by bacteria and fungi.Much of that literature is soluble of the PAH,comprised 24%of the raw oil,but only
devoted to the growing field of biological remediation at 10%of the PAH in treated woad.The remaining 14%of the
PAH-contaminated sites.For instance,Godsey and others naphthalene was lost during the treating process,which
(1992)and Mueller and others(1991)described the biodeg- involves final steaming of the wood at high temperature
radation of creosote contaminants by methanogenic bacteria under vacuum. This process removes excess oil from the
in anaerobic environments, Lamar and others(1994)re- wood cells and preferentially removes the more volatile
ported on the degradation of creosote by fungi,and DeLaune LMW compounds. As shown in Figure 25,this resulted
40

in a PAH spectrum in treated wood that was dominated by would explain the extreme patchiness of PAH concentrations
intermediate-weight compounds(acenaphthene,phenan- found in association with PAH-contaminated sediments.It
threne,anthracene,fluoranthene,and pyrene).The heavier would also help explain why mixtures of PAH,like creosote,
compounds represented a very small fraction of both new oil are found to be less toxic than an additive toxicity assump-
and the preservative retained in the treated wood.The point tion would predict(Tagatz and others 1983,California EPA
is that the treated wood contains a PAH spectrum that is 1994).Lastly,this hypothesis would explain the presence of
dominated by intermediate-weight compounds with low square-centimeter-sized microsheens observed to depths of
water solubility(3.42 mg/L for acenaphthylene decreasing to 4 cm in creosote-contaminated sediments at Sooke Basin
0.13 mg/L for pyrene). when those sediments were exposed to air.
Water column concentrations of total PAH measured by Axehnan and others(1999)observed ten times more PAH in
Battelle within 15 cm of the six-piling dolphins in Sooke the colloidal phase and five times more PAH in the particu-
Basin using semipermeable membrane devices(SPMD)were late phase than in the dissolved phase.The concentration of
17.87,22.94,and 30.76 ng/L(parts per trillion).These PAH in the dissolved phase represented less than 10%of the
values were slightly higher than the 13.37 ng/L measured at PAH in the water column.Wade and others(1987)found
the Sooke Basin reference station.The values observed were creosote-associated PAH only in surface sheen samples
consistent with PAH concentrations measured in marine collected at the Charlestown,Virginia,Navy Yard.They
mussels(Mytilus edulis edulis)grown at the same distance of could find no creosote-associated polynuclear aromatic
15 cm from the piling and with known bioconcentration hydrocarbons in the water column immediately adjacent to
factors(BCF).The sum of toxic units(TU)(Swartz and the piers.In addition,no observable response was seen in
others 1995)in water immediately adjacent to this dense sea urchin(Arbacia punclulata)bioassays using water from
cluster of piling was 0.000745,which is well below the either Pier#2 or#4.All of this evidence indicates that creo-
recommended benchmark of 0.186 TU necessary to protect sote-derived PAH do not dissolve in open aquatic environ-
aquatic organisms. ments at concentrations that cause adverse biological effects.
Based on the results for water and sediment PAH analyses In contrast,the adverse biological effects associated with
presented in Goyette and Brooks(1999),the authors hy-
high concentrations of sedimented PAH are well known.
pothesized that PAH are transported to sediments in mi- Biological Effects Associated With PAH
croparticles or microliter-sized droplets.Preliminary labora-
tory studies(Brooks,unpublished data)have substantiated As seen in the previous section,PAH are ubiquitous in
this hypothesis.Microliter quantities of PAH released be- aquatic and terrestrial environments.They have been present
neath the air—water interface settled to the bottom of gradu- for eons at baseline levels ranging from less than 1 µg/g to
ated cylinders with speeds that appear consistent with those perhaps 4 or 5 µg/g.They are a natural part of our environ-
predicted by Stokes'equation.Furthermore,the particles ment,and organisms have evolved to coexist with them.
settled into either quartz sand or crushed oyster shell sub- Polycyclic aromatic hydrocarbons are all hydrophobic as
strates and remained intact for at least 2 years.Small quanti- expressed by the octanol—water partition coefficients(Log
ties of creosote oil injected above the air—water interface K,, ,),which increased from 3.33 for naphthalene to 6.22 for
formed sheens on the water's surface.These sheens re- benzo(ghi)perylene.The biological consequences of this
mained intact until the water was disturbed as it would be by hydrophobicity are that PAH tend to be found only at very
waves.The sheen then broke up into small,irregularly low dissolved concentrations and that they bind to dissolved
shaped particles that settled to the bottom and worked their and particulate organic matter(POM)in water and
way into the sediments.Milliliter quantities of creosote oil sediments.
injected under the air—water interface settled to the bottom of
glass vials where they retained their ellipsoidal shape for up Polycyclic aromatic hydrocarbons are bioconcentrated from
to 2 years.If the vials were vigorously shaken,the larger the dissolved fraction in water,and much higher levels are
droplets broke up into smaller particles,some of which found in plant and animal tissues than are found in the
adhered to the sides of the vials. dissolved state.Once PAH are taken up by living organisms,
several enzyme systems have evolved to excrete them or to
This hypothesis,if substantiated,will significantly change break them down and then to excrete the intermediate meta-
the approach to assessing toxicity of creosote-contaminated bolic products. Some of these intermediate metabolites are
sediments.Infauna,rather than being subjected to an envi- carcinogenic,and high environmental concentrations of
ronment that is uniformly contaminated by a diffuse pattern PAH can lead to chronic stress and/or increased risk for
of PAH,would be confronted with an environment that is cancer in organisms exposed to sediment PAH concentra-
predominantly uncontaminated with foci of high contamina- tions greater than 7 to 10 µg TPAH/g in sediments with
tion.In this scenario,exposure is best described stochasti- 1.0%organic carbon.The following sections of this report
cally with consideration for possible avoidance or attraction review some aspects of the biological response to PAH.
to the PAH foci by various organisms.This hypothesis
41

Bioconcentration, Bloaccuntulation, 402 µg/g in mussels growing on creosote-treated pilings.
and Biotnagnification of PAH Dobroski and Epifanio(1980)found that direct uptake of
Bioconcentration and bioaccumulation of contaminants is of B[a]P from seawater by diatoms was much greater than the
special importance because some aquatic species,most rate of trophic transfer from the diatoms to clam larvae.
notably bivalves,have demonstrated an ability to rapidly Eisler(1987)recorded elevated PAH concentrations,espe-
bioconcentrate some contaminants in water to high tissue cially benzo(a)anthracene,chrysene,fluorene,phenanthrene,
levels.The concern is that persistent contaminants may and pyrene,in oyster tissues and sediments from the vicinity
move up the food chain,biomagnifying to higher concentra- of marinas.These levels were notably higher in cooler
tions in each trophic level,until contaminants found at months when lipids and glycogen were being stored to
nontoxic levels in the ambient environment reach concentra- prepare for spawning(Marcus and Stokes 1985).
tions where they do cause stress and disease.For effective
biomagnification and movement of contaminants through the For mussels,the general trend towards lower levels of HMW
food chain,several conditions must be met.First,organisms PAH relative to the levels in associated sediment suggests an
must have the ability to bioconcentrate low levels of con- uptake mechanism that involves the solution of PAH in
taminants from the water column or to bioaccumulate PAH water.Supporting this hypothesis is the observed rapid
from sediments or their food.Second,these contaminants,or turnover and shorter half-life of the more soluble,LMW
their toxic metabolic intermediates,must be retained,unal- PAH(Dunn 1980).This suggests that the more soluble(and
tered,in the tissues of the organism until it falls prey to an more bioavailable)LMW PAH are effectively removed from
animal at a higher trophic level. sediments and metabolized by bivalves.The HMW PAH
(associated with chronic stress and genetic disorders)have
There are a number of factors that mitigate biomagnification. reduced bioavailability in sediments because of their lower
If contaminants are not absorbed,they cannot accumulate. solubility.However,once absorbed,HMW PAH are more
Numerous organisms,particularly arthropods and verte- slowly metabolized by bivalves.
brates,have the ability to rabidly metabolize and/or to ex-
crete organic contaminants.The gut,liver,kidney,and gall The PAH levels in fish are usually low because this group
bladder are common sites of PAR concentration,metabo- rapidly metabolizes all PAH(Lawrence and Weber 1984,
lism,and excretion in vertebrates.If the contaminants are West and others 1986a,b)or they excrete them.High con-
rapidly excreted or metabolized to nontoxic compounds, centrations of PAH are typically found in the gut,liver,and
then the chain is broken and biomagnification is not effec- bile.Raw fish from unpolluted or moderately polluted water
tive in passing contaminants upward through the food chain. seldom contains detectable amounts of PAH.However,
DDT is an excellent example of a persistent compound that smoking and cooking of fish can increase PAH content to
was bioconcentrated from low levels in the water to higher significant levels.
levels,first in plankton,then in fish,and finally in bird Neff(1982)reported BCF for several PAH in the clam
populations,with devastating consequences. Rangia cuneata.The BCF values,which ranged from 6.1 to
Neff(1982)reported that most aquatic organisms bioconcen- 32,are for PAH dissolved in water. Eisler(1987)has sum-
trate PAH from low concentrations in the ambient water to marized BCF values from the literature.The BCF values he
higher tissue levels.Bioconcentration factors are predicted reports contradict his assertion that bivalves accumulate
by the octanol-water partition coefficients(K,,,")associated PAH more rapidly than fish.For all of the values given in
with individual PAH compounds. his review,the average BCF values were
Bivalve mollusks,particularly the commercially important Bivalves 82(n=8)
mussel(Mytilus edulis)and oysters of the genera Ostrea and Fish 6,844(n=34)
Crassostrea have received far more attention than other
aquatic invertebrates,plants,or fish.They are excellent Eisler(1987)reported BCF values from 6 to 236 in the clam
subjects for monitoring pollutants because they filter sub- Rangia cuneata.Four of the five values were less than 33.
stantial quantities of water over large and highly permeable For fish,BCF values ranged from 44 to 82,916 with most
gills.For these reasons,mussels have been the subject of values in the hundred to thousand times range.
numerous studies such as the Global Mussel Watch Pro-
gram.Many of these studies have focused on the accumula- Biaccumulation of PAH From Sediments
tion of metals and the carcinogenic molecule B[a]P. The ultimate fate of most HMW PAH deposited in aquatic
environments is sedimentation.Working in Prudhoe Bay,
Benzo[a]pyrene levels recorded in Neff(1979)for uncon- Alaska,Roesijadi and others(1978)examined the accumula-
taminated areas fall in the undetectable to perhaps 50 µg/L tion of crude oil and specific PAH from oil-contaminated
range.Dunn and Stich(1975(in Dunn and Stich 1976)) sediments by three infaunal invertebrate species,the sipun-
recorded tissue levels averaging 59 µg/g in mussels from culid worm Phascolosoma agassizii and the clams Macoma
areas associated with marinas and higher levels averaging inquinata and Protothaca staminea. They found that the
42

efficiency of PAH uptake from sediments was much lower Haitzer and others(1999)observed decreasing PAH BCFs in
than from water.Bioaccumulation factors for uptake of the the nematode Caenorhabditis elegans in the presence of
four PAH from contaminated sediments were 0.2 or less, increased levels of humic substances in soils and sediments.
indicating no significant bioconcentration of PAH by this Bioconcentration factors for pyrene decreased from 12,000
route.However,BCF for uptake of these four PAH from in the absence of dissolved organic carbon(DOC)to 5,000
seawater were in the 10.3 to 1,349 range,indicating a low to to 7,000 at DOC values greater than 10 mg/L.The decreases
moderate potential for bioconcentration from water. for B(a)P were even more dramatic,decreasing from about
Similarly,Driscoll and others(1997)observed steady-state 35,000 to<5,000 at DOC levels exceeding 15 to 20 mg/L.
biota-sediment accumulation factors(BSAF)of 0.16 to 0.61 Similar results were obtained by Weinstein and Oris(1999)
for the freshwater amphipod Hyalella azteca and 0.34 to for fluoranthene.They found that the fluoranthene BCF
0.82 for another amphipod Diporeia spp. decreased from 9,054 in the absence of dissolved humic
Eisler(1987)suggested that bivalves readily take up PAH material to 2,810 when the water contained 5.0 mg carbon
per liter.The median lethal time for photoenhanced fluoran-
from sediments.This hypothesis is contradicted by numer-
ous thene at a concentration of 4.8 µg/L to fathead minnows
studies.O'Connor(1991)found that at 117 National Status and Trend Sites where there were both mollusks and (pimephales promelas)increased from about 55 h in the
absence of dissolved humic material to about 100 h in the
fine-grained sediments,the average ratio of mollusk tissue to presence of one or more milligram humic acid per liter.
sediment concentration was only 1.2 for total PAH.He also These authors also reported strong attenuation of ultraviolet
noted that mollusks accumulate the LMW(and more highly (UV)-A and moderate attenuation of UV-B as a function of
soluble)PAH to a greater extent than the HMW PAH(ratio increasing humic substances in water.
of mollusk tissue to sediment PAH concentration 2.0 and
0.64,respectively).Eaton and Zitko(1978)noted that PAH Accumulation of PAH from sediment may be attributed in
levels in clams and mussels were two orders of magnitude large part to uptake of PAH desorbed from sediment parti-
below those detected in sediments.Neff(1979)cites Per- cles into interstitial water.Numerous studies cited above and
driau's(1964)finding that in no case did benthic animals in Neff(1982)and Meador and others(1995)led to the
contain elevated levels of B[a]P compared with sediment general conclusion that sediment-adsorbed PAH are not
concentrations.Tissue concentrations in the animals were, readily assimilated by benthic animals.This hypothesis is
on average,36%of the sediment concentrations. further supported by Swartz and others(1989)who con-
The bioavailability of PAH is affected by sediment physico- cluded that the concentration of chemicals in interstitial
chemistry including the proportion of organic carbon,which "Water is the primary determinant of sediment toxicity,not the
binds PAH making them unavailable,and the sediment bulk concentration in the sediment.Both the historical litera-
texture,which affects uptake by sediment ingesting detri- ture and more recent research support the importance of
tivores(Meador and others 1995).Maruya and others(1997) organic carbon in binding aromatic hydrocarbons and reduc-
estimated the uptake of sediment contaminants by determin- ing their bioavailability.
ing the ratio of contaminant concentration in organism lipid Depuration of PAH
to the concentration in sediment on an organic carbon basis. Southworth and others(1978)found a half-life of less than
This work is important in that most modern sediment bench- 1 h for all PAH metabolized by Daphnia puler.Jackim and
marks evoked for purposes of protecting biota from excess Lake(1978)reported that the half-life of PAH in most bi-
PAH contamination are based on sediment organic carbon. valves is on the order of 2 to 16 days.These studies suggest
Maruya and others(1997)observed BSAF varying between that PAH are either rapidly metabolized or excreted,at least
0.0069 and 5.4,confirming the low potential for uptake of by these species.
PAH from sediments.
Biomagnigcation of PAH in the Food Chain
Johnsen(1987)observed that numerous PAH,including Neff(1979)reported that the annelid,Neanthes arena-
form strong bonds with natural aquatic humic substances.
anthracene,fluoranthene,pyrene,and benzo(a)anthracene, ceodentata,had little,if any,ability to accumulate 2-methyl-
naphthalene from its food.However,the situation is quite
The strength of these bonds increased with time and with the
octanol-water partition coefficient.In other words,the different in marine crustaceans and fish where uptake from
HMW compounds were more tightly bound than the LMW food was much more efficient than uptake from water.Ar-
compounds.White and others(1999)and Tang and Alexan- thropods(crabs,amphipods,shrimp,etc.)rapidly accumulate
der(1999)observed that phenanthrene,anthracene,fluoran- LMW PAH and very rapidly excrete or metabolize these
thene,and pyrene became more tightly bound to sediments compounds.The half-life of B[a]P in Callinectes sapidus
and soil humin as time passed.Their hypothesis was was 6 days.Neft's(1979)conclusion was that all results
confirmed using both mild extractive techniques designed to dramatically demonstrated the importance of metabolism in
release only the bioavailable fraction of the PAH and by eliminating PAH from contaminated crustaceans.Broman
measured uptake kinetics in plants and animals.Similarly, and others(1990)examined the trophic transfer of PAH in a
study involving seston,the blue mussel(Mytilus edulis),and
43

the eider duck(Somateria mollissima).Contrary to biomag- Table 27—Acute toxicity of various PAH to marine
nification,they observed decreasing PAH concentrations organisms as measured by 96-h LC50 values.
with increasing trophic levels. All values are in µg/L
Bioaccumulation Summary Species 96-h LC50
Aquatic organisms are able to efficiently bioconcentrate Mysids(Mysidopsis bahia)a 18 to 21
PAH from the water column. It appears that direct transfer Oysters(Crassostrea virginica)a 700
from sediments to organisms living within and on those Pink shrimp 240
sediments is minimal.Benthic organisms rarely contain (Penaeus duorarum)a
higher concentrations of PAH than are found in the sedi- Sheepshead minnows 3,500
ments in which they live. PAH are rapidly metabolized and (Cyprinodon variegatus)a
excreted by vertebrates and arthropods.In bivalves,which Mosquito fish(Gambusia afnis)a 150,000 naphthalene
do not metabolize PAH as efficiently as arthropods and Mosquito fish(Gambusia affrnis)b 1,180,000 toluene
vertebrates,the half-life of most PAH examined was in the
range of 2 to 16 days.These data suggest that PAH are not Dungeness crab larvae 8 naphthalene
persistent in the tissues of aquatic species and that movement (Cancer magister)
of PAH through food chains to higher trophic levels is Dungeness crab larvae 170 naphthalene
minimal,if it occurs at all. (Cancer magister)
Neff(1979)concluded the following:"From the limited data bNerthwick and Patrick(1982)
Neff(1979)
available,it would appear that there are large interspecific
differences in ability to absorb and assimilate PAH from
food.Polychaete worms have a very limited ability to absorb enzymes into the cytoplasm or blood serum with pathologi-
and assimilate PAH,whereas fish absorption of PAH from cal consequences including autophagy. Eisler(1987)noted
the gut is limited and variable depending on species of fish, that the LMW,unsubstituted PAH compounds,containing
the PAH,and possibly the food matrix in which PAH is two or three rings,such as naphthalene,fluorene,phenan-
administered.Crustaceans,on the other hand,apparently threne,and anthracene,have significant acute toxicity to
readily assimilate PAH from contaminated food.In all cases some organisms,whereas the HMW,four-to seven-ring
where assimilation of ingested PAH was demonstrated, aromatics do not.However,these heavier molecules contain
metabolism and excretion of PAH were rapid.Thus,the numerous potentially carcinogenic and mutagenic intermedi-
potential for food chain biomagnification of PAH seems to ates.
be limited. For such biomagnification to occur,the material
must be readily absorbed from food,and once assimilated,it Dissolved PAH Toxicity in Marine Environments
must be relatively resistant to metabolism or excretion." A common measure of acute toxicity is the concentration of
Creosote and PAH Toxicity a toxicant that causes 50%mortality in a test population
within some specified period of time(often 96 h).This
in Aquatic Environments measurement is referred to as the 96-h LC50. Borthwick and
Aquatic organisms have been exposed to baseline levels of Patrick(1982)and Neff(1979)reported 96-h LC50 values
PAH for eons.The diversity of life in aquatic environments for several marine animals.These are summarized in
attests to aquatic species ability to tolerate baseline PAH Table 27.Interestingly,in Neff s(1979)discussion of the
levels of 1 to 2 µg/L in water and 0.010 to 4.0 µg/g in effects of PAH on aquatic animals,he cites Caldwell and
sediments.Thus,it is important to determine the level where others'(1977) finding that continuous exposure to dissolved
PAH cause significant stress and/or pathological responses naphthalene concentrations of 19 to 170 µg/L had no effect
at the organismal and population levels.In answering that on the survival of Dungeness crab larvae.No explanation
question,we will consider two types of toxicity: acute was given for the very low(8 ppb)value reported in Neff s
and chronic. (1979)paper or for the differences in the values reported.
Acute toxicity causes observable physiological lesions and is One might expect that exogenous factors contributed to the
usually measured by mortality.PAH can interact with cells differences.The LC50 values reported in the literature for
most organisms and PAH compounds are in the 500 to
in several ways to cause toxic responses.As an example, 5,000 ppb range.Neff(1979)found that in all but a few
they may bind reversibly to lipophilic sites in the cell and cases,the concentrations of aromatic hydrocarbons that are
thereby interfere with cellular processes.Potentially im- acutely toxic to aquatic animals are several orders of magni-
tude higher than concentrations found even in the most
lysosomes,which contain strong enzymes important in heavily polluted marine and fresh waters.However,
intracellular digestion of complex organic molecules and in the immune response.Increased lysosomal membrane sediments from polluted regions may contain aromatic hy-
permeability can result in the unregulated flow of these drocarbons at concentrations similar to or higher than those
44

that are acutely toxic.The limited bioavailability of sedi- Table 28—Summary of consensus LCS0 values for
ment-adsorbed PAH undoubtedly renders them substantially sediment PAH compounds from Swartz(1999)and
less acutely toxic than dissolved PAH.He also noted that lowest daphnid dissolved PAH chronic values
PAH-induced stress is cumulative and exacerbated by reported by Suter and Tsao(1996).
exogenous stress factors such as abnormal thermal and Suter&Tsao
osmotic conditions. Swartz (1996)
(1999) lowest daphnid
PAH Toxicity in Freshwater LCso chronic value
Because PAH heavier than naphthalene are so hydrophobic, Compound (µg/g) (µg/L)
they are generally found at extremely low concentrations in Naphthalene 71 1,163
freshwater and have little potential to create acute or chronic Acenaphthylene 15 Not given
stress in aquatic communities.As will be seen,this statement
is not necessarily true for sedimented PAH.Suter and Tsao Acenaphthene 23 6,646
(1996)and Swartz(1999)summarized conventional bench- Fluorene 90 Not given
marks for priority contaminants in freshwater.These values Phenanthrene 155 200
are summarized in micrograms per liter in Table 28.Because Anthracene 114 <2.1
daphnids and dragonflies(Odonata)are both arthropods,the Fluoranthene 371 15
lowest daphnid chronic values are presented from Suter and Pyrene 481 Not given
Tsao(1996).Additional freshwater acute toxicity data pro- Benz(a)anthracene ill 0.65
vided in EPA(1993)are summarized in Table 29.
Chrysene 169 Not given
The data presented in Table 29 suggest that at least some Benzo(b)fluoranthene 180 Not given
odonates are not particularly susceptible to PAH intoxica- Benzo(k)fluoranthene 155 Not given
tion.As an example,Ophiogompus spp.has a UV-photo- Benzo(a)pyrene 179 0.30
enhanced fluoranthene LC50 of 109.7 µg/L.This UV- Low molecular weight PAH 468
exposed acute value is much higher than the values of 1.0
to 3.0 µg UV-enhanced anthracene or fluoranthene per liter High molecular weight 1,646
PAH
observed to cause mortality in other organisms.The point is
that the available evidence suggests that this order may be Total PAH 2,114
more robust to PAH contamination than are other,more
sensitive,species.
Toxicity associated with mixtures of compounds can be Table 29—U.S. Environmental Protection Agency
(EPA 1993)LC50 values describing fluoranthene
additive,antagonistic,or synergistic.This is true of mixtures toxicity to freshwater arthropods
of PAH,which appear to have slightly less than additive
toxicity.For instance,the LC50 for rainbow trout(Oncorhyn- Sediment LC50
thus mykiss)associated with fluoranthene is>90.5 ppb.The (µg/g organic Water LCso
LC50 for rainbow trout subjected to whole creosote oil is Species carbon) (µg/L)
almost 10 times higher at 880 µg/L(Polisini 1994).Padma Daphnia magna 3.5
and others(1998)examined the toxicity of the water soluble Hyalela azteca 500 44.9
fraction of creosote to the mysid(Mysidopsis bahia)and Chironomus tetans 1,587 30.4
found median lethal concentrations(expressed as total Ophiogompus spp. >178.5
identified aromatic hydrocarbons)of 180 µg/L.
Ophiogompus spp. >109.7
Photoenhanced PAH Toxicity (UV exposed)
The interaction of UV light with anthracene and fluoran-
thene resulted in modified compounds with increased toxic-
ity to aquatic organisms,at least in laboratory experiments.
Landrum and others(1987)reported photoenhanced anthra- Lake Michigan sediments.These authors reported that expo-
cene LC50 of 12 µg/L in bluegill sunfish and 1.2 µg/L for sure of the sediment elutriates to UV did not result in in-
Daphnia pulex.The authors were unsure whether the UV creased toxicity in subsequent bioassays.Increased toxicity
light sensitized the target tissues or if it modified the anthra- was observed only when the daphnids were cultured in the
cene to a more toxic compound.The observed toxicity was presence of PAH-contaminated elutriate and UV light.
reported to be 400 times greater in the presence of UV than Concentrations of PAH in these tests were not reported.
in its absence.Davenport and Spacie(1991)extended these Krylov and others(1997)reported on a quantitative
results by demonstrating increased toxicity to Daphnia structure—activity relationship model predicting the photoen-
magna associated with a suite of PAH extracted from hanced toxicity of 16 PAH.Their model assumed that
45

biological stress is associated with PAH that are UV- approximately 29 µg fluoranthene per liter in low UV envi-
modified outside the organism,with uptake of these modi- ronments.Acute toxicity thresholds were lower under me-
fied PAH and with damage to a group of endogenous bio- dium light intensity(8 µg/L)and lowest under high intensity
molecules necessary for photosynthesis in duckweed(Lemna UV(75.2 mW/cmZ UV-A)radiation(4 µg/L).These authors
gibba).Their model suggested that photoenhanced PAH noted that L. variegatus purifies fluoranthene and that the
toxicity is a function of several factors including the length annelid's physiology includes repair mechanisms that de-
of exposure to PAH and UV,the relative absorbance of crease short-term toxicity during periods of darkness.Under
simulated solar radiation by each PAH,the resulting quan- medium light intensity(33.5 mW/cmZ UV-A),mortality did
tum yield for formation of triplet-state PAH,and the rate of not occur until after 26 h at a fluoranthene concentration of
PAH photomodification.They found that toxicity associated 60 µg/L.This is important because sunlight is intermittent,
with nine PAH compounds was dominated by the PAH lasting for only about 16 h at temperate latitudes.Therefore,
modification constant and that the photosensitization con- these values probably overestimate the photoenhanced toxic-
stant was more important in describing toxicity for the re- ity of fluoranthene to this species.Monson and others(1999)
maining seven PAH.This work suggested that photoen- observed similar responses in larval frogs(Rana pipiens)
hanced PAH toxicity is a function of the particular PAH where increasing mortality was observed in exposures to
compound's propensity for modification to a more toxic 3.5 µg/L following exposure to intense light for periods
photoenhanced form and of the target organism's(or tis- greater than 30 h.However,Hatch and Burton(1998)
sues')susceptibility to photosensitization.The photosensiti- reported photoenhanced fluoranthene toxicity only at much
zation constant is probably particular to different taxa and to higher levels in the same species.These authors reported
various life stages within taxa.This model provides relative EC50 concentrations of 276 µg fluoranthene per liter in Rana
toxicity data and not absolute data upon which to determine pipiens, 247 µg/L in Ambystoma maculatrrnr,and 52 µg/L in
numerical estimates of toxicity.The authors concluded that Xenopus laevis.
photosensitization of target organism tissues and photomodi-
fication contribute additively(not synergistically)to pho- This review indicates that UV light decreases the concentra-
toenhanced PAH toxicity. tions at which PAH contamination can result in acute toxic-
ity.Photoenhanced PAH toxicity appears to be associated
Gala and Giesy(1992)reported UV-enhanced anthracene with acute responses and not long-term chronic stress.The
toxicity in green alga(Selenastrrrm capricornutum).The increased toxicity is associated with photomodification of
22-h EC50(the concentration of material in water to which PAH compounds and with photosensitization of target
test organisms are exposed that is estimated to be effective in tissues.These factors appear to act in an additive manner.
producing some sublethal response in 50%of the test organ- It appears that photomodified anthracene is more toxic than
isms)for specific growth rate ranged from 37.4 to 3.9 µg other PAH,including fluoranthene and phenanthrene.
anthracene per liter depending on the intensity of UV-A
radiation.Huang and others(1993)observed similar results In the absence of ameliorative constituents,the threshold for
for the higher plant Lemmna gibba exposed to anthracene, photoenhanced anthracene toxicity appears to be in the range
phenanthrene,or B(a)P in the presence of UV or simulated of 1.2 to 4 µg/L.However,the presence of humic substances
sunlight.These authors reported the relative toxicity of appears to significantly ameliorate photoenhanced PAH
anthracene to be greater than phenanthrene,and both were toxicity in addition to absorbing UV in the water column.
more toxic than photomodified B(a)P.Growth inhibition was Humic substances are typically abundant in high organic
reported at values exceeding thresholds of approximately carbon wetland sediments such as those found in the
200 µg anthracene per liter,500 µg phenanthrene per liter, Des Plaines River wetlands.
and 3,000 µg B(a)P/L.The lower toxicity of phenanthrene PAH Toxicity to Aquatic Plants
(compared with anthracene)was substantiated by McConkey
and others(1997)who hypothesized that the photoenhanced The effects of various PAH on aquatic plant growth are
toxicity of phenanthrene is associated with the intermediate highly variable.At low concentrations(10 to 20 ppb),sev-
product phenanthrenequinone.These authors reported an eral PAH act as a stimulant to plant growth.At 300 ppb,
EC50 of 3,500 µg phenanthrene per liter in Lemna gibba in chrysene was observed by Boney(1974(in Neff 1979))to
simulated solar radiation and 10,800 µg phenanthrene per induce a 58%increase in the growth of the red alga,An-
liter in visible light(no UV).In contrast,the EC50 for the tithamnion plumula.Other PAH(anthracene and
photomodified compound phenanthrenequinone was 2-methylanthracene)caused declines of—20%and—12% in
independent of the presence of UV at 530 to 570 µg/L. the same alga at 300 ppb.In general,PAH concentrations
greater than 1,000 ppb inhibit algal growth.
Ankley and others(1995)demonstrated that increased Chronic Toxicity Associated With Dissolved PAH
UV-enhanced fluoranthene toxicity to Lumbriculus variega-
tus was a function of both dissolved PAH concentration and Neff(1979)addressed chronic stress associated with PAH
UV intensity.Oligochaete mortality increased above contamination.He cited Ott and others(1978)and noted that
the copepod,Eurytemora ajfinis, suffered statistically
46

significant reductions in the length of life,total number of development occurred in the cohort grown immediately
nauplii produced,and brood size when exposed to 10 µg/L adjacent to the weathered piling dolphin.
naphthalene,2-methylnaphthalene,2,6-dimethylnaphthalene,
or 2,3,5-trimethylnaphthalene for the duration of their lives. From the preceding discussion on the uptake of PAH from
water,food,and sediments,it appears that PAH concentra-
Documented instances of chronic stress will be discussed,by
effect,in the following paragraphs. lion in the water column(including interstitial water in
sediments)is the parameter of greatest significance in defin-
Nearly all PAH are hydrophobic and lipophilic.Thus,there ing chronic stress.Furthermore,it appears that sustained
is a potential for these compounds to become associated with water column concentrations of 30 to 50 µg TPAH/L can
stable lipid pools in aquatic organisms.Energy is generally have subtle but important chronic impacts on populations of
stored as glycogen in bivalves until gametogenesis when the marine organisms.However,it appears that dissolved PAH
glycogen and lipid stores are converted into eggs and sperm. concentrations do not normally reach those levels,except in
The eggs contain significant lipid reserves and could become the case of oil spills or other accidental PAH losses.
a repository for lipophilic PAH.Moore and others(1989)
cited Lowe and Pipe's(1985)observation that long-term Biologics!Response to Sedimented PAN
exposure to diesel oil at 30 and 130 ppm caused a decrease The adverse biological response to dissolved PAH is gener-
in the mass of gametes produced by Mytikrs eduhs and ally inconsequential because these compounds are so hydro-
Macoma balthica. phobic and do not readily dissolve in water.This same hy-
drophobicity causes PAH to bind with dissolved and
Mollusks elicit reduced ventilation(feeding)rates at PAH particulate organic substances,thereby reducing their
levels as low as 30 to 40 µg/L in seawater(Moore and others bioavailability in the water and in sediment.High concentra-
1989).The feeding inhibition probably resulted from the tions of sedimented PAH,with significant biological conse-
narcotic effect of hydrocarbons,particularly aromatic hydro- quences,are well documented in literature.
carbons.These compounds have a direct effect on cilia,
muscles,and/or the nervous system.Reduced feeding rates Acute and Chronic Toxicity Associated
result in a reduction in scope for growth,a commonly meas- With Sedimented PAH
ured parameter that quantitatively describes the energy It has long been recognized that it is the concentration of
available for tissue growth,reproduction,and activity.In PAH in sediment interstitial or pore water that correlates
bivalves,the major problem caused by reduced scope for with toxicity,not the bulk sediment concentration of PAH.
growth is poor reproductive capacity.While this does not For instance,Tagatz and others(1983)found that the lowest
have immediate consequences at the organismal level,the creosote concentration at contaminated sites affecting the
long-term consequences of reduced recruitment could be abundance or number of taxa was 844 µg creosote per gram
significant for the population. dry sediment for mollusks and 177 µg/g for echinoderms,
Neff(1979)concluded his discussion of PAH-induced annelids,and arthropods. Similarly,Padma and others
chronic toxicity by suggesting that while environmentally (1998)reported that the median lethal concentration for
realistic dissolved PAH concentrations of 1 to 50 µg/L can Mysidopsis bahia in the water soluble fraction of creosote
cause potentially detrimental,sublethal responses in aquatic extracted from sediments was 700 µg/L compared with the
organisms,in most cases,the PAH concentrations required significantly lower level of 180 µg/L obtained when the
to elicit significant sublethal responses are higher than those water soluble fraction was added to water without the medi-
encountered in all but the most heavily polluted aquatic ating influence of sediment.
environments.This statement was strongly supported by the Pastorok and others(1994)reported sediment TPAH con-
low levels of creosote-derived TPAH(<30 ng/L)observed centrations as high as 1,800 µg/g associated with a creosote
by Goyette and Brooks(1999)in the immediate vicinity treating plant at an industrial site in Oregon.They observed
(15 cm)of a major creosote structure in Sooke Basin.The significant mortality in Hyallela azteca and Microtox(Stra-
concentration of PAH in the whole tissues of mussels grown tegic Diagnostics,Inc.,Newark,Delaware)bioassays within
within 15 cm of these structures(21.9 ng TPAH/g wet tis- 91 in of the plant's pier and shoreline.However,significant
sue)was not significantly different from that found in mus- increases in neoplastic lesions were not observed in the
sel tissues from the open control(reference)site(21.7 ng livers of large-scale suckers(Catastomus macrocheilus)and
TPAH/g).However,approximately twice as much PAH was no adverse effects on other demersal species were observed
sequestered in the gonads of ripe mussels at both sites outside the highly contaminated nearshore area.Sediments
(44.3 ng/g compared with 21.9 ng/g in whole tissue).Repro- associated with historical industrial activity and spills in
ductive bioassays on all mussel cohorts grown at varying Eagle Harbor(Malin and others 1985),the Elizabeth River
distances from new and aged creosote-treated piling and (Huggett and others 1992),the Willamette River(Pastorok
untreated Douglas-fir piling did not reveal significant differ- and others 1994),and Bayou Bonfouca(Catallo and
ences.Of all larvae,65%to 89%developed normally to the Gambrell 1987)have been contaminated with greater than
"D"hinge stage.The highest percentage of normal larval 49,000 µg/g of creosote-derived PAH.Significant acute
47

toxicity and changes in microbial,meiofaunal,and macro- consumed by humans,although,the hepato-pancreas is
faunal communities have been associated with these indus- sometimes eaten as"crab butter."
trial sites,which have received significant study.The results
of some of this research are reviewed in the following para- Melanomacrophage centers are an integral part of the teleost
graphs.Studies describing the biological response to very immune system.Payne and Fancey(1489}observed that the
high levels of sedimented PAH associated with historical numbers of melanomacrophage centers were increased in the
industrial activity should not be used to infer environmental livers offish exposed to TPAH concentrations in the range
of 25 to 50
response to the use of creosote-treated wood products. µg/g.These concentrations are found only in
heavily polluted harbors,industrially polluted sites,or oil
Acute toxicity has not been documented in low to moderate spills.Payne and others(1988)observed changes in MFO
concentrations of sedimented TPAH in open environments enzyme levels and liver fat content in fish exposed to low
(Baekken 1994,Carman and others 1995,Wendt and others dissolved hydrocarbon levels of 1,000 µg/L(perhaps even as
1994,Brooks 2000).However,there is evidence of chronic low as 200 to 300 µg TPAH/L).
effects associated with sedimented TPAH at concentrations
above perhaps 7 to 10 µg TPAH/g dry sediment.The litera- The increased levels of P-450,MFO,and AHH enzymes in
ture describing these effects is reviewed in the following fish and crustaceans exposed to high levels of PAH suggest
paragraphs, active catabolism of these molecules.Enzyme induction is
not a sign of stress,per se.However,there is concern be-
Neoplasia Associated With Polycyclic cause some of the intermediate products of HMW PAH
Aromatic Hydrocarbons catabolism are carcinogenic,mutagenic,and teratogenic.
Hyperplastic,preneoplastic,and neoplastic lesions have been Bioindicator Studies
reported in fish for a number of years.These same types
of lesions are far less common in bivalves and other There is growing interest in enzyme induction and genotox-
invertebrates. icity tests as indicators of environmental risk.However,it is
important to understand what these tests actually tell us.
In vertebrates,enzymes produced by the cytochrome P-450, Effects at the organismal level,associated with external
the mixed-function oxidase(MFO)system,and the aryl factors,are mediated by numerous levels of protection.
hydrocarbon hydroxylase(AHH)system are responsible for Detrimental factors(abnormal temperature,xenobiotics,
initiating catabolism of lipophilic compounds(including desiccation,disease organisms,low dissolved oxygen,high
PAH).These systems render hydrophobic molecules more levels of pollution,UV radiation,etc.)are often avoided by
water soluble and therefore increase their potential for excre- mobile animals.Sessile animals(including many bivalves)
tion and detoxification.In the case of certain HMW PAH, isolate themselves within tightly closed valves in an attempt
the intermediate metabolic products of these enzyme systems to avoid harmful conditions.
can be highly toxic,mutagenic,or carcinogenic.Oxidative
metabolism of some PAH(like B[a]P)results in the produc- At the next level of protection,an animal's integument iso-
tion of arene oxides,some of which bind covalently to de- lates internal organs and structures from harmful conditions.
oxyribonucleic acid(DNA)and ribonucleic acid(RNA) The skin and gut epithelia are capable of selective absorption
(particularly with guanine).The resulting chromosomal of material.For instance,HMW PAH,adsorbed to sedi-
lesions can result in unregulated cell growth and division menu,apparently pass through the digestive tract of many
(cancer). annelids without being absorbed through the gut epithelia.
The ability to metabolize HMW PAH varies significantly Once foreign materials are absorbed into the blood serum
between phyla.Among invertebrates,mollusks have low through the skin,gills,or gut,organisms respond by seques-
AHH activity and a limited ability to metabolize HMW tering them in vacuoles,metabolizing them in the liver,or
PAH.Arthropods and annelids show increased activity,and cleansing them from the serum as it passes through the kid-
ney.Whether or not a molecule is metabolized or excreted
cytochrome P-450,MFO,and AHH activity. depends,in great part,on its ability to penetrate cell mem-
branes.The plasmalemma is highly permeable to essential
Vertebrates,including fish,demonstrate high MFO,AHH, molecules such as glucose,amino acids,and lipids.These
and cytochrome P-450 capabilities(Varanasi 1989).The phospholipid bilayers are not very permeable to ions or to
liver is the primary site of MFO activity in fish,and the large charged polar molecules.The four-to seven-ring
liver,gut,and gall bladder are primary sites of PAH concen- HMW PAH are generally not charged,and therefore,they
tration,metabolism,and excretion.Humans do not normally pass across the cell membrane and are actively metabolized
consume these organs.In Crustaceans,the hepato-pancreas, by vertebrates.
green gland(excretory organ),pyloric stomach,gills,testes, It is well documented that some metabolic intermediates of
and eyestalks are major sites of PAR accumulation and AHH HMW PAH,particularly arene oxides,can bind covalently
enzyme activity.Again,these tissues are not normally
to guanine,producing DNA lesions,which may result in
48

unregulated cell growth(cancer).These metabolic interme- solvent for both polar and nonpolar compounds.DMSO is
diates are frequently found in the digestive gland(liver or often used as a reaction medium for bimolecular nucleo-
hepatopancreas)where metabolism is most active.The litera- philic reactions in which the attacking nucleophile(arene
ture contains many citations regarding hepatic lesions(in- oxide)bears a negative charge.Its use in these genotoxicity
cluding hepatic carcinomas)in demersal fish associated with studies greatly facilitates transfer of PAH across the plas-
PAH-contaminated sediments.However,at Eagle Harbor, malemma and of arene oxides into the nucleus.As discussed
the Duwamish River,Elizabeth River,etc.,the levels of in Table 30,there are a range of conditions in the genotoxic-
contamination at which hepatic carcinomas significantly ity testing environment that may lead to an overestimation of
increased were generally greater than 25 to 50 mg/kg.In toxicity relative to the natural environment.
some areas,Eagle Harbor sediments contained TPAH con-
centrations as high as 6,000 mg/kg. Payne and others(1988)reported a study supporting the
hypothesis that many point sources of hydrocarbon contami-
Mixed function oxidases,Cytochrome P-450,ethoxy reso- nation could be harmful to fish health.They found that MFO
furin-O-deethylase,and AHH are important enzyme systems enzyme levels were altered at hydrocarbon levels as low as
for the metabolism of HMW PAH.There are numerous 1.0 mg TPAH/kg.The authors noted that PAH levels in this
reports in the literature suggesting that PAH metabolizing range are encountered in a broad range of aquatic environ-
enzyme systems are activated at sediment PAH levels as low ments,many of which are not associated with pollution.
as 1.0 ppm(Johnson and others 1994). They suggested that hydrocarbons often occur in sufficient
concentrations to affect biological responses in fish.They
As previously stated,intermediate PAH metabolites,such concluded that meaningful bioindicators must distinguish
as arene oxides can covalently bind to DNA resulting in between effects per se and between chronic or acute effects.
lesions.However,DNA contains numerous mechanisms that
repair miscoded or damaged sequences.This repair is Vogelbein and others(1990)described hepatic neoplasms in
achieved by a suite of enzymes capable of recognizing dam- Mummichogs(Fundulus heteroclitus)from a site with high
aged or mismatched base pairs and excising them.Environ- PAH levels(22 mg TPAH/kg)in sediments.Ninety-three
mental and/or random damage to DNA is not unusual,and percent of the Mummichogs collected at this site had gross
the presence of nicks or double-stranded breaks in nuclear hepatic lesions,and 33%of these had hepatocellular carci-
(or ribosomal)DNA does not often lead to unregulated cell nomas. Fish from a site of lower contamination(0.063 mg
growth.Increased DNA damage obviously increases the risk TPAH/kg)did not show signs of hepatic lesions or carcino-
for failure of these repair mechanisms resulting in a number mas. Similar cellular lesions have been described in fish
of diseases. from a highly urbanized area(the Duwamish River estuary)
The point is that there are numerous levels of protection in Puget Sound(Pierce and others 1977).
involved in maintaining the biological integrity of an organ- Colwell(1986)examined mussels and seawater associated
ism.In evaluating environmental risks,we must recognize with creosoted marine pilings at the Roosevelt Roads Naval
the importance of these cellular safeguards.The questions Station Complex in Puerto Rico.She employed Salmonella
we ask must recognize that different levels of biological typhimurium in the familiar Ames test(Ames and others
organization will respond differently to the same level of 1975)for mutagenicity and found no detectable mutagenic
insult.Therefore,our questions must be posed carefully and activity in bacteria from either the water or mollusks associ-
caution should be exercised when extrapolating biological ated with the creosote.She concluded that the creosote did
responses at one level of organization to responses at not exhibit any appreciable leaching into the surrounding
another level. water.
Ernst(1994,personal communication)reported the results of Effects of PAH Contamination on Populations of
genotoxicity tests using subtidal sediments collected at Aquatic Organisms
varying distances from a wharf constructed of creosote-
treated wood.The PAH were extracted from the sediments, Mesocosm studies by Stekoll and others(1980)and Wid-
dried,and redissolved in dimethylsulfoxide(DMSO).Trout doves and others(1982, 1985)reported similar community
hepatocytes were exposed to varying concentrations of the responses to petroleum and PAH contamination.Significant,
PAH preparation,and genotoxicity was assayed using the long-term reductions in the abundance and diversity of
nick translation assay of Gagne and Blaise(1993)and a invertebrate fauna were reported when ambient water levels
modified version of the alkaline precipitation assay de- contained as little as 130 µg/L dissolved diesel oil for pro-
scribed by Olive(1988).The results were quantified by longed periods of time.Less significant population effects
defining a toxicity threshold as the geometric mean of the were observed on a rocky shore community exposed to
lowest observed effect concentration and the no observed 30 µg/L diesel oil for 2 months.
effects concentration.This test measured the response of Tagatz and others(1983)examined the impacts of creosote-
DNA in naked digestive gland cells to isolated PAH contaminated sand on macrofaunal communities.They found
suspended in a material,which is an exceptionally powerful
49

Table 30—Comparison of exposure conditions in the genotoxicity testing environment and the natural environment
and the potential effects of these environments on toxicity
Genotoxicity test environment Organismal environment in open aquatic systems
1.PAH are desorbed and extracted from sediments. 1.PAH are bound to sediments.They are not readily available
They are made very available to the test cells, in a dissolved and therefore bioavailable phase.
2.No organismal epithelium present 2.After desorption from sediments, PAH must cross an external
epithelium(skin,gills,gut)before entering the blood stream for
delivery to the digestive gland.
3.No kidney present to clear PAH. 3.Kidney present. It functions to clear some xenobiotics. Fish
rapidly excrete most PAH.
4.Plasmalemma compromised by DMSO 4.Cell membrane selectively restricts movement of PAH into the
cell.This increases the probability of excretion and decreases
the probability of metabolism.
5.Lysosomal membranes compromised by DMSO. 5.Lysosomal membranes help contain intermediate metabolites
during metabolism.
6.Nuclear membrane compromised by DMSO 6.Nuclear membrane provides another level of protection for DNA.
7.DNA lesions assumed to result in unregulated 7.DNA repair mechanisms reduce the probability of unregulated
cell growth, cell growth.
that the lowest creosote(in sediment)concentration that scape.Ten-day Hyalella azteca laboratory bioassays did not
affected the number of individuals or species was 844 mg reveal toxicity associated with any of the treatment stations
TPAH/kg for mollusks and 177 mg TPAH/kg for echino- compared with survival in either laboratory control sedi-
derms,annelids,and arthropods. ments or the upstream reference station.No observed ad-
verse effects were documented in the invertebrate communi-
The adaptation of microbial communities in the gut of Lim- ties associated with either bridge or with the small amount of
noria tripunctata and in sediment are well documented and PAH lost from them.
discussed in Neff(1979). Similar adaptations were described
by Wade and others(1989)in Gulf of Mexico hydrocarbon PAH Toxicity Summary
seep communities including numerous species of annelids, The LMW PAH such as naphthalene and acenaphthene
crustaceans,bivalves,and fish.Tissue PAH concentrations
indicated that these organisms were chronically exposed to produce acute toxic effects in marine animals because they
high levels of PAH.The seep organisms were able to survive are more soluble than the HMW compounds.Acute intoxica-
and thrive in an environment of high PAH exposure. tion in the sensitive larval stages of marine invertebrates may
The apparent ability to cope with these elevated levels of occur at water column concentrations as low as 8 to 10 µg/L.
PAH may involve specially adapted enzyme systems. However,for most species,the literature suggests that water
column concentrations of greater that 20 µg/L are required
Brooks(2000)examined the loss of PAH and the biological for significant responses.The LMW PAH are more soluble
response to creosote-treated bridges crossing Pipe Creek in than the HMW compounds,and bacteria and other aquatic
Indiana.Total organic carbon was low at both bridges stud- organisms more rapidly metabolize them.The potential for
ied(0.48%at one bridge(B 146)and 0.89%at the other their accumulation to toxic levels is small except when
(B 148)). Higher sediment concentrations of PAH(0.114 to introduced in large quantities such as occurs in petroleum
5.3 µg TPAH/g dry sediment)were observed under and spills.However,laboratory(including mesocosm)studies
downstream from 2-year-old B 146 than at 17-year-old B 148 have demonstrated photoenhanced toxicity associated with
(0.209 to 2.256 µg TPAH/g). Sediment concentrations of fluoranthene and anthracene at levels as low as 3 µg/L in the
individual or total PAH did not exceed the threshold effects water column.
level(TEL; Smith and others 1996)at B148.However,
concentrations of naphthalene,acenaphthene,fluorene, Because of their decreased biological availability,sedi-
phenanthrene,and fluoranthene exceeded the TEL but not mented PAH have a low potential to cause acute pathologi-
the probable effects level(PEL;Smith and others 1996)at cal responses at either the organismal or population levels in
the newer B 148.Adverse effects were not observed in the aquatic species. However,sediment levels of creosote
robust aquatic community observed in this slow moving,silt- exceeding 177 mg/kg have been shown to cause significant
and sand-laden stream flowing through an agricultural land- impacts on populations of the most sensitive taxa(Tagatz
50

and others 1983).Furthermore,bacteria and eukaryotes have (Y—TUi=0.186,P124=0.05)is the toxic-unit concentration
demonstrated a remarkable ability to adapt to relatively high below which mixtures of PAH are unlikely to contribute to
levels of baseline PAH. sediment toxicity and above which PAH mixtures increase
Chronic toxicity is more difficult to measure than acute P124 over baseline conditions."Swartz and others(1995)did
ty not distinguish between chronic and acute toxicity in stating
toxicity.This appendix suggests that chronic stress can occur that ETU=0.186 is an appropriately protective benchmark.
in organisms,including bivalves,at concentrations as low as The Swartz and others(1995)model was developed based
30 to 40 µg TPAH/L.Chronic stress causes reduced scope on equilibrium partitioning to estimate sediment toxicity for
for growth and reduced reproductive capacity,which infauna. More importantly,Swartz and others(1995)com-
can have long-term consequences for populations of pared the TPAH model with other PAH benchmarks and
aquatic species. found that ETU=0.186 was equivalent to both the screen-
In addition to direct physiological stress there is a potential ing level concentration(SLC)and the National Oceanic and
for the HMW PAH(particularly B[a]P)to form carcino- Atmospheric Administration's(NOAA)effects range-low
genic,mutagenic,and teratogenic compounds during me- (ER-L).Both the SLC and ER-L are sediment benchmarks
tabolism by crustaceans and vertebrates.Neff(1979)sum- below which adverse effects(including chronic effects)are
marized his section on neoplasia by noting that while rarely observed(lower 10th percentile of the effects data-
carcinogenic PAH can produce cancer-like growths and base).The SLC and ER-L are frequently used as benchmarks
cause teratogenesis and mutagenesis in some aquatic inver- to determine if sediments require further investigation.Con-
tebrates and vertebrates,there are no reports of cancer being taminant levels at or below the ER-L or SLC are not consid-
induced by exposing aquatic animals to environmentally ered biologically stressful and generally require no further
realistic levels of carcinogenic PAH in the water,food,or evaluation.
sediments. However,recent studies describe increases in the Swartz and others(1995)assumed toxicity was additive for
number of hepatic lesions and carcinomas with sediment the suite of PAH in creosote. However,there is evidence
TPAH burdens as low as 7 to 10 mg/kg. indicating that the PAH in creosote are less than additive in
their cumulative toxicity.The California EPA(1994)deter-
Recommended Numerical Benchmarks mined 96-h LC50 of 990 µg/L for bluegill(Lepomis macro-
for Evaluating Environmental Risks chirus)and 880 µg/L for rainbow trout(Oncorhynchus
Associated with PAH mykiss)exposed to whole creosote oil.Assuming that the
creosote components were present in the bioassay in propor-
Numerous jurisdictions have established benchmarks for tion to that found in whole creosote oil,these LC50 values
evaluating environmental risks associated with PAH in represent approximately 112 TU.Munoz and Tarazona
aquatic environments.Washington State(regulation WAC (1993)noted that"when the sum of individual compounds
173-204)published sediment quality standards(SQS)for have to be used,the differences in acute toxicities between
individual PAH and for the sum of LMW and HMW com- individual chemicals(and their cumulative action)could be
pounds.In addition,the U.S.EPA has proposed,but not higher than an order of magnitude."
adopted,freshwater criteria for acenaphthene,phenanthrene,
and fluoranthene.This appendix does not reveal freshwater Application of a 0.1 factor to convert the 96-h LC50 of
sediment quality criteria for individual PAH compounds or 880 µg creosote/L for rainbow trout to a chronic value sug-
their mixtures.There are numerous proposals for maximum gests that I t.2 TU would be a defensible benchmark for
allowable levels based on the lowest levels at which adverse creosote.However,the 0.186 TU benchmark suggested by
effects are observed in a broad spectrum of environments. Swartz and others(1995)is very conservative for evaluating
The broad application of criteria based on the observance of the risks associated with dissolved PAH.The TU approach
effects in worst-case environments results in very conserva- was adopted in the preceding report on railway ties because
tive assessments that are not representative of the worst case. the combined stresses of multiple contaminants may cause
In addition,the following discussion assumes that the toxic- environmental effects that would not be expected if the risk
ity of mixtures of PAH is additive.As previously discussed, of each contaminant were evaluated separately.However,
it appears that toxicity associated with the mixture of PAH assuming additive toxicity for creosote may be unnecessarily
called creosote is significantly less than additive,thereby conservative.
adding to the conservativeness of proposed benchmarks.
Sediment Quality Benchmarks for PAHs
Benchmarks for Assessing Risk of Dissolved PAH in Aquatic Environments
The TPAH model in Swartz and others(1995)assigns a Freshwater and estuarine sediment quality benchmarks are
<5%probability of mortality greater than 24%for all summarized in Table 23.Numerous other screening bench-
samples with ZTUi<0.186. Swartz and others(1995) marks are available,but these are representative. Swartz
stated that,"The TPAH Threshold of Acute Toxicity (1999)provided a concise summary of the types of existing
51

guidelines and attempted to consolidate various benchmarks positive responses),and the PEL resulted in 21 false positive
into three tiers for which he claimed consensus support. responses.The mean of the TEL and PEL((TEL+PEL)/2)
These levels were the TEL(290 µg TPAH/g organic car- resulted in 30 false predictions of adverse effects where none
bon),median effects concentration(MEC)(1,800 µg were observed.These results suggested that either the mean
TPAH/g organic carbon),and the extreme effects concentra- of the TEL and PEL or the Washington State apparent ef-
tion(EEC)(10,000 µg TPAH/g organic carbon). Swartz fects threshold based SQS were both protective and efficient.
(1999)noted that the TEC(290 µg/g organic carbon)is the In contrast,the TEL and the ER-L(Long and others 1998)
easiest benchmark to interpret because adverse effects can- were not very efficient and were considered overprotective
not be anticipated at values less than this.He notes that in the Sooke Basin environment.
values exceeding the EEC are always associated with obvi-
ous adverse effects. Swartz(1999)councils that conclusions Several recent studies have suggested that these levels may
not be sufficiently protective in marine environments.John-
which the ecological effects of sediment contamination,
which probably occur somewhere between the TEC and the son and others(1994)and Horness and others(1998)rely on
MEC,should be based on site-specific analysis and weight the precept that observance of an enzyme induction response
of evidence derived from the three elements of the sediment to PAH implies physiological impairment.However,enzyme
quality triad. induction per se does not imply physiological impairment
(Brooks 1997a;Payne and others 1988).Payne and others
None of the benchmarks given in Table 23 are enforceable (1988)supported the hypothesis that many point sources of
SQS.They are simply guideposts for evaluating the effects hydrocarbon contamination could be harmful to fish health.
of contaminants in sediments.Washington State(regulation They found that MFO enzyme levels were altered at hydro-
WAC 173-204)developed enforceable SQS. Draft rule carbon levels as low as 1.0 ppm.However,the authors noted
amendments to these standards were distributed in June of that PAH levels in this range are encountered across a broad
1999.The new standards include an increase in the LMW range of aquatic environments,many of which are not asso-
PAH standard from 370 mg/kg organic content(OC)to 593 ciated with pollution.They suggested that hydrocarbons
mg/kg OC and a decrease in the HMW PAH standard from often occur in sufficient concentrations to affect biological
960 mg/kg OC to 900 mg/kg OC.The sum of these two responses in fish and concluded that meaningful bioindica-
classes of PAH is proposed to increase from 1,330 mg tors must distinguish between effects per se and between
TPAH/kg OC to 1,493 mg TPAH/kg OC. chronic or acute effects.It is important to recall that Johnson
and others(1994,p. 304-329)did not find any adverse
Goyette and Brooks(1999)examined the effects of creosote- effects at the population level.
treated piling in Sooke Basin,British Columbia.The exten-
sive physicochemical and biological database included in- Johnson and others(1994)and Horness and others(1998)
faunal community analysis and in situ and laboratory bioas- also underestimated sediment PAH exposure,at least in
says using the amphipods Rhepoxynius abronius and Elliott Bay(10 mg TPAH/kg),the Duwamish Waterway
Eohaustorius estuarius,liquid and solid phase Microtox (6 mg TPAH/kg),and Eagle Harbor(90 mg TPAH/kg).
(Strategic Diagnostics,Newark,DE),echinoderm fertiliza- Eagle Harbor sediments contained PAH concentrations as
tion and Mytilus edulis edulis growth,survival,and high as 6,461 mg TPAH/kg(Swartz and others 1989).
reproductive tests.Physicochemical analyses included a Washington Department of Ecology(1995)contains
detailed description of sediment and water column concen- sediment concentrations of PAH for a large number of sta-
trations of alkylated and parental PAH.This database al- tions in Elliott Bay. Significant areas contain PAH concen-
lowed for an examination of the efficacy of existing and trations in the top 4 cm of the sediment column at 111.3 to
proposed SQS in predicting adverse biological response.The 593 mg TPAH/kg dry sediment.The Puget Sound Water
U.S.EPA draft sediment quality criteria for acenaphthene Quality Authority(PSWQA 1996)indicates sediment TPAH
(130 µg/g OC),phenanthrene(180 µg/g OC),and fluoran- levels at numerous locations in the Duwamish Waterway at
thene(620 µg/g OC)were found to be underprotective in greater than 21 mg TPAH/kg.In general,higher contaminant
that they failed to predict observed adverse biological effects concentrations are found in shallow nearshore areas associ-
in three database samples. False negative responses(adverse ated with Seattle's intensely urbanized upland and with
effects observed but not predicted by the benchmark)were numerous waterfront docks and industrial facilities.Concen-
not observed for any of the other benchmarks.Goyette and trations of TPAH decline in the middle and outer reaches of
Brooks(1999)found that 60 individual PAH compounds Elliott Bay(PSWQA 1996). Sediments in these Puget Sound
exceeded the TEL in seven separate sediment samples where industrial areas also contain high levels of polychlorinated
no toxicity was observed(TEL described by Jones and biphenyls(PCBs)and metals. Misitano and others(1994)
others 1997).These false positive indications associated with reported much higher concentrations of both HMW and
the TEL were observed for every PAH compound except LMW PAH in these areas than reported by Johnson and
naphthalene.The Washington State SQS (WAC 173-204) others(1994)and Homess and others(1998).
were most efficient in predicting adverse effects(12 false
52

Both papers are based on the false assumption that the Eng- deep enough to attenuate incident sunlight and where sedi-
lish sole subjected to histopathological examination was ments are infrequently disturbed to the degree implicit in
exposed to a single sediment concentration of TPAH.Juve- swirling them in 800 mL of water.It is not appropriate to
nile English sole(Pleuronectes vetulus)are found in shallow infer that the same response is likely in the real world.The
water in the intertidal zone where sediment concentrations of literature suggests that there is a reasonable correlation
all contaminants are highest.As they grow,English sole between concentrations exceeding 700 to 1,000 µg TPAH/g
move into deeper water but tend to seasonally migrate from OC and preneoplastic lesions or neoplasia but not at
deep water in the winter to shallow water in the spring.In concentrations less than this.
British Columbia,English sole are known to make extensive
migrations of at least I,100 km(Hart 1973).The point is that Swartz(1999)examined existing and proposed SQS and
proposed consensus guidelines that appear to resolve some
English sole in Elliott Bay and the Duwamish Waterway are
exposed to a variety of sediment conditions including TPAH of the current inconsistencies.He described a TPAH toxicity
concentrations that greatly exceed those reported by Johnson threshold that is consistent with the ER-L of Long and others
and others(1994)and Horness and others(1998). (1995)and a TPAH mixture LCso that is similar to the effects
range median described by the same authors.Table 31
Misitano and others(1994)worked in highly contaminated summarizes these benchmarks.
sediments found in Eagle Harbor,Commencement Bay,and
Elliott Bay associated with depositional environments.The
sediments are fine grained,and except when disturbed by the
thrust of large vessels,they remain undisturbed.These char- Table 31--Summary of the TPAH toxicity threshold,
acteristics are commonly associated with most,but not all, TPAH mixture lethal concentration(LC50),and the
contaminated sediments.The bioassay protocol used by mean of these two values for 17 parental PAH.
Misitano and others(1994)contains two elements that make TPAH
it difficult to compare the results with real world toxicity TPAH
environments. thresh- mixture
n
Mea
First,the authors swirled 20 g of sediment and 800 mL of olds(µg/g LC50a LC508 ea
seawater in 1-L glass beakers to begin the bioassays.This organic organic organic-
probably resuspended the sedimented PAH particles and PAH compound carbon) carbon) carbon)
PAH adsorbed to clay and/or POM,greatly increasing its
bioavailability in the water column.The PAH particles and Naphthalene 13 71 42.0
fine-grained particulate inorganic matter(PIM)and POM to Acenaphthylene 3 15 9.0
which the PAH were probably adsorbed would be the last to Acenaphthene 4 23 13.5
settle and would have accumulated on the surface of the Fluorene 17 90 48.5
well-sorted sediment at the end of 4 h,again unrealistically Phenanthrene 29 155 92.0
increasing the exposure of surf smelt larvae to the Anthracene 21 114 67.5
contaminants. Fluoranthene 69 371 220.0
Second,the authors then placed the beakers under contanu- Pyrene 90 481 285.5
ous fluorescent light at 3,240 lux.The photoenhanced Benz(a)anthracene 21 ill 66.0
(W spectrum)toxicity of anthracene,phenanthrene, Chrysene 31 169 100.0
fluoranthene,and B[a]P is well known to occur at thresholds Benzo(b) 33 180 106.5
of 3 to 12 µg/L(Gala and Giesy 1992,Landrum and others fluoranthene
1992,Ankley and others 1995).Photoenhanced PAH toxic- Benzo(k) 29 155 92.0
ity occurs at a lower PAH concentration than occurs in the fluoranthene
dark or at low light levels.Photoenhanced PAH toxicity has Benzo(a)pyrene 33 179 106.0
been well documented in laboratory bioassays and in micro-
cosm studies but not well documented in natural aquatic Low molecular 87 468 277.5
systems. weight PAH
High molecular 306 1,646 976.0
The results of this study are interesting and demonstrate that weight PAH
the observed effects can be associated with larval exposure Total PAH 393 2,114 1,253.5
to a mixture of contaminants in industrial sediments under OFrom Swartz(1999)
the conditions imposed(resuspension of contaminated,fine-
grained sediments in a small volume of water and photoacti-
vation).Those conditions are not characteristic of very many
depositional areas,which more frequently occur in water
53