WI0700035_Report_20011010

MEMORANDUM
To:
From:
DIVISION OF WATER QUALITY
GROUNDWATER SECTION
October 10, 2001
Willie Hardison, Regional Groundwater Supervisor
Groundwater Section
Washington Regional Office
Mark Pritzl MarkPritzl@ncmaiLnet
Hydrogeological Technician II
UIC Group
Groundwater Section
Raleigh Central Office
Re: Issuance of injection well permit type 5I (in -situ Groundwater Remediation Well)
Permit Number WI0700035 is for a Pilot Study to inject a slurry containing zero valent iron
(ZVI), molasses, water and a thixotropic polymer to enhance reductive dehalogenation of the
dissolved chlorinated solvent contamination at this site. These injection points will be located at
234 Springs Road, in Washington, North Carolina. Please retain the application paper work
and permit copy for the WARO-UIC files. If you have any questions regarding this permit or
the UIC program, please contact me at [phone].
cc: CO-UIC Files
Enclosures

Memorandum
To: Mark Pritzl
UIC Program
From: Betty Wilcox
Environmental Chemist II
Subject: Permit Revie 70003%-5
I have reviewed the information supplied for Permit
me September 26-27, 2001.
Groundwater Section
September 27, 2001
nd submitted to
After reviewing the application package, including information submitted to Dr.
Luanne Williams on June 14, 2001, I have concerns about the constituent acrylamide,
which is highly soluble in water. Data provided by Radian Engineering indicate that the
Anionic Polyacrylamide (PAM) used at the site may contain up to 0.05% residual
acrylamide. Radian further states that 480 ppm and 217 ppm of PAM are expected in
groundwater at test locations after the pilot test. Based on that information, up to 240
ug/L and 108 ug/L respectiwly, of acrylamide may-be-expected±rthe-groundwater as
well. The groundwater standard for acrylamide is 0.01 ug/L.
Due to the potential for additional contamination of groundwater, if a permit is
issued, I strongly recommend that acrylamide should be included in the list of
groundwater monitoring parameters.
cc: Debra Watts
Files

GROUNDWATER SECTION
September 25, 2001
MEMORANDUM
To: Debra Watts, Groundwater Supervisor, Permits and Compliance Unit
From: Mark Pritzl, Hydrogeological Technician II, UIC Group
Re: Hamilton Beach Proctor Silex Facility (HBPS), addressing issues and concerns you have at this
site to conduct a pilot study using Zero Valent Injection (ZVI) Technology. Your questions are in
Italic followed by the UIC's comments.
1. Did not see this permit in your log...?
Please open "Permit Log" excel file and click on the 1999 tab, on bottom left of spread-
sheet.
2. VOCs, ferrous iron and chloride will be tested for. Does Betty or EPI have other recomd.
considering what's being injected?
It is true VOCs, ferrous iron and chloride will be tested, but so will dissolved oxygen, pH,
conductivity, temperature and oxidation-reduction (ORP) to determine the effectiveness
of ZVI Technology at this site.
Since Betty did not review this application it is impossible for her to have comments.
Betty did not review the last application proposing ZVI technology nor did you
recommend her review.
Epidemiology, Luanne Williams, reviewed ZVI Technology and had not expressed a
concern to monitor specific parameters in Groundwater. Her review was included in this
application package for your convenience.
3. See my comments on your summary and permit.
• summary: Same contaminant?
Yes, a chlorinated solvent.
• summary: Same soils?
Since 99% of the pilot study injection will take place below the soil profile this
may not be a relevant question. This is a pilot study application and pilot studies
determine environmental impacts on a remediation design.
4. Has the region seen i1? Do they feel it was satisfactorly?
The UIC Program contacted Willie Hardison of the WARO and asked if they had any
concerns with this technology at the Hamilton Beach Proctor Silex site. They only had
concerns with the oxidation technology and not with the ZVI technology.
Since your review, I have asked Mr. Hardison to please email me with their comments
which will be incorporated into the permit application..
He also had concerns about oxygen build up?
Oxygen build up was a concern dealing with the oxidation pilot study, which has already
taken place, and not with ZVI technology.

5. You circled version type and permit #
You circled the Shell Doc's version conception date which has appeared on the last
several permits you have signed. You also approved the UIC's GW/UIC-6 Shell Doc on
Drive I back in March/2001.
Permit # is appropriate.
6. You have requested using a different language concerning Epidimiology's review comments under
Part X-Special Conditions. "Because of potential presence of acrylamide in the injectant
proposed, high water solubility and toxicity of acrylamide (injectant) extreme caution should be
taken to prevent contamination of groundwater as specified in...)
You did not require this language in the first permit you signed in July 16, 2001, which a
copy is enclosed, concerning the exact ZVI technology and Epidemiology's review.
The concerns you wish to add is addressed several times in the actual permit under; the
first page 2nd paragraph and Part IV -Performance Standards, 1-3.

GROUNDWATER SECTION
September 21, 2001
MEMORANDUM
To: Debra Watts, Groundwater Supervisor, Permits and Compliance Unit
From: Mark Pritzl, Hydrogeological Technician 1T, UIC Group
Re: Hamilton Beach Proctor Silex Facility (HBPS) pertinent information regarding their injection
well permit application
1. Application received to conduct a pilot study for the injection of a slurry containing zero valent
iron (ZVI), molasses, water and a thixotropic polymer to enhance reductive dehalogenation of the
dissolved chlorinated solvent contamination.
2. The water -table aquifer movement varies with time and the dominate direction is toward the
south-east. This water -table aquifer has been designated as unit A by the applicant. The first
confining aquifer moves in a north-west direction and has been designated as unit B by the
applicant. It is interesting to note that at times these two aquifers move in opposite directions.
This dynamic movement has caused the dissolved plume to look unconventional due to different
directions at different times and depths.
3. HBPS originally submitted two pilot study injection well applications on August/1999 with one
application proposing to inject Hydrogen Peroxide, Oxidation technology, and the other to inject
Zero Valent Iron (ZVI), Reduction technology, at HBPS in Washington, NC. Since both
applications deal with contrasting types of technologies, it was agreed upon all parties to conduct
the hydrogen peroxide injection pilot study first, then proceed with the ZVI injection pilot study.
On July/2001 the applicant contacted the UIC Program and requested a permit for ZVI injection at
this site and that the injection of Hydrogen Peroxide pilot study was complete. Z
• The consultant, r .: PS, is the same onsultant that is currently conducting a pilot
study using t e exact ZVI injection technolo t the Abbott Lab facility in Laurinburg NC
and that permit, permitMO-WO 10, was issued on July 16, 2001. I have added this permit
file for your convenience with this review.
4. The Washington Regional Office reviewed this permit application in conjunction with the
Hydrogen Peroxide permit application. The reviewer, Keith Starner, mainly had issues
concerning the Hydrogen Peroxide application and didn't really have a problem with this
application or the ZVI technology. The only issues Keith Starner had with ZVI technology was
iron fouling and the `.lack of details" ernin this permit application. Potential iron fouling is
a concern and will be monitore during e pi of test. Since Washington's review the applicant
has submitted much more information, therefore "lack of details" is not a concern this time. In
fact, I wish all our UIC applications had this much detai ed in ormation in them.
6. At this time I recommend that an injection well permit be given to HBPS for a pilot study using
ZVI technology at this site. � c
5. The thixotropic polymer helps keep the slurry mixture homogeneous.
0116_4)'` ,k- ?ilk-3

Radian Engineering Inc.
June 14, 2001
Dr. Luanne Williams
NC Department of Health and Human Services
Occupational and Environmental Epidemiology Branch
1912 Mail Service Center
Raleigh, NC 27699-1912
(Shipping) 1600 Perimeter Park Drive
Morrisville, NC 27560
(Mailing) P.O. Box 13000
Research Triangle Park, NC 27709
[phone]
FAX # [phone]
RE: Request for Approval: Use of Product Applied to Groundwater
Dear Dr. Williams:
Enclosed for your review is information to describe a zero-valent iron and molasses slurry,
which we propose to use during an in -situ pilot -scale test at the Abbott Laboratories facility in
Laurinburg, NC. The pilot -scale test is being conducted to evaluate the effectiveness of zero
valent iron (ZVI) and molasses for the dehalogenation of chlorinated organic compounds in the
• groundwater. The "iron slurry" proposed for injection will consist of ZVI, molasses, water, and
a thixotropic agent to control slurry viscosity.
An Underground Injection Control (UIC) permit application was submitted to Mark Pritzl of the
NCDENR UIC program on 2 March 2001. Mark awaits your decision on the use of this slurry.
If you have any questions or comments, please contact me at 919-461-1290 or Perry•Gayle at
919-461-1295. We greatly appreciate your expedited review of this Request for Approval.
Thank you for your consideration.
Sincerely,
RADIAN ENGINEERING
Brett Berra
Enclosure
cc Curt Michols, Abbott
Perry Gayle, Radian Engineering
Mark Pritzl, NCDENR-UIC

INFORMATION NEEDED TO DO RISK ASSESSMENTS FOR
PRODUCTS APPLIED TO GROUNDWATER OR SOIL
CONTAINING NO MICROORGANISMS
SEND TO: DR. LUANNE WILLIAMS
NC DEPARTMENT OF HEALTH AND HUMAN SERVICES
OCCUPATIONAL AND ENVIRONMENTAL EPIDEMIOLOGY BRANCH
1912 MAIL SERVICE CENTER
RALEIGH NC 27699-1912
Phone: [phone]
Required General Information
1. Department of Environment and Natural Resources Groundwater Section contact person
and phone number.
2. Current or future use of site with site contact person, address, and phone number.
3. Contractor applying product, contact person, address, and phone number.
4. Distance and likelihood of impact to public or private wells used for drinking, industrial
processes, cooling, -agriculture, -etc and-is-area-servedhy-public_watecsupply9
Verification must be provided by the regional Groundwater and Public Water Supply
Sections. Send their responses to me.
5. General description of the contaminants present in the soil and/or groundwater at the site.
6. Approximate distance and likelihood of impact to nearest body of surface water to the
site (please provide name).
7. Approximate distance to nearest resident(s) and workplace.
Required Product/Process-Specific Information
1,. Product manufacturer name, address, phone number, and contact person.
2. Identity of specific ingredients (including CAS#) and concentrations of ingredients
contained in the product and purpose of each.
3. Approximate concentration of each ingredient following release into groundwater or soil.

INFORMATION NEEDED TO DO RISK ASSESSMENTS FOR
PRODUCTS APPLIED TO GROUNDWATER OR SOIL
CONTAINING NO MICROORGANISMS
Page 2
4. Approximate distance and direction of travel for product in groundwater, the groundwater
concentration of each ingredient at this distance, and distance from this point to the
nearest drinking water source (that is currently used for drinking purposes). These should
be reasonably accurate estimates based on the best available information and calculations
(modeling, if necessary) regarding aquifer characteristics and flowpaths at the site; where
uncertainty exists in critical aquifer parameters (e.g. effective porosity), conservative
assumptions should be made in estimating these values so that worst -case predictions of
travel distances are made. •
5. Approximate groundwater concentration of each ingredient after pumping or recovery (if
applicable).
6. If the product is expected to discharge to a nearby surface water, approximate
concentrations of product in the water.
7. Documentation from authoritative technical references of specific degradation products
expected.
8. Documentation-fromauthoritative_technicaLreferences_oLexpected_migratoryPotential of
specific ingredients and degradation products in soil and groundwater.
9. Complete description of the use of the product at the site.
•
The risk assessment will be forwarded to the designated contact person for the site, consultant
applying the product, and Groundwater Section contact person.

INFORMATION NEEDED TO DO RISK ASSESSMENTS FOR
PRODUCTS APPLIED TO GROUNDWATER OR SOIL
CONTAINING NO MICROORGANISMS
Required General Information
1. Mark Pritzl
Underground Injection Control Program
919.715.6166
2. Abbott Laboratories
Kim Kashmer
Junction of Hwys. 15/501 & 401
Laurinburg, NC 28352
910.276.4274
The facility produces medical devices including sets for intravenous administration of
drugs and health maintenance solutions. Products are manufactured using polyvinyl
chloride and other plastics.
3. NESCO Inc., Remediation Technologies Group
Scott Noland
6870 North Broadway, Unit H
Denver, CO 80221
303.487.1001 (Ext 13)
4. Based upon previous injection experience in similar hydrogeologic conditions, this
product is expected to travel a maximum of 50 feet (conservative) from the point of
injection. The nearest property line is another 250 beyond the anticipated travel
distance of the product. The Abbott Labs facility and surrounding businesses and
industries are connected to the Laurinburg municipal water system. The only wells
on the property are monitoring wells and remedial extraction wells that will be turned
off during this application. The City of Laurinburg obtains water from nine wells
located southwest of the city. In addition, six more wells have recently been
constructed to utilize as water supply wells in the near future. The Abbott Labs
facility is located north of the City of Laurinburg and is farther than 1.5 miles from
the nearest existing or recently constructed city water supply well. Based upon the
information presented above, no public or private wells will be impacted by this
injection.
5. The operation of a former solvent disposal pit between 1970 and 1976 resulted in
groundwater contamination at this site. A contaminant plume, consisting primarily of
volatile organic compounds (VOCs), in groundwater underlies the site. The primary
contaminants of concern include tetrachloroethene (PCE), trichloroethene (TCE),
chloroform, vinyl chloride, benzene, toluene, 4-Methyl-2-Pentanone, 1,1-

dichloroethene (1,1-DCE), 1,2-dichloroethene (1,2-DCE), and 1,2-dichloroethane
(1,2-DCA).
6. The nearest surface water body to the Abbott facility is an unnamed tributary to Leith
Creek west of the site. This tributary is located approximately 150 feet west of the
Abbott property and over 400 feet from the maximum anticipated travel distance of
the injected product . Based upon previous injection experience and the distance to
the nearest surface water body, it is not anticipated that the product will discharge to
any surface water in the area.
7. The nearest workplace is the Abbott Labs manufacturing facility located on -site.
Proposed pilot test injection locations are on the Abbott Labs property adjacent to this
facility. No injection locations are located off -site. The nearest residents are located
in a neighborhood approximately 1,500 feet east and southeast of the site.
Required Product/Process-Specific Information
1. For information on the zero-valent iron and molasses contact:
NESCO Inc., Remediation Technologies Group
Scott Noland
6870 North Broadway, Unit H
Denver, CO 80221
303.487.1001 (Ext 13)
For information on the thixotropic agent (SUPERFLOC+ A-130 HMW Flocculant)
contact:
CYTEC Industries, Inc.
Randy Deskin (Toxicology)
Five Garret Mountain Plaza
West Patterson, NJ 07424
800.527.9313 (Ext 3372)
2. The technology chosen to remediate chlorinated solvent contamination in the
groundwater relies on reductive dechlorination and utilizes activated iron powder
(Zero Valent Iron, ZVI) as an electron donor. ZVI facilitates a chemical reduction
process that sequentially dehalogenates chlorinated hydrocarbons. Organic substrate
augmentation using agricultural grade molasses, facilitates both biological and
chemical processes that results in reductive dehalogenation of chlorinated organic
compounds. The iron powder is mixed with water, molasses, and a thixotropic agent,
which is needed to control slurry viscosity. In general, slurry properties and
composition will remain fairly constant, containing:

•
1. Water
2. Thixotropic Agent
3. Iron Powder
4. Molasses
69%to 91.8%
0.1%to 0.15%
3 % to 20 %
5% to 10%
The above composition is expressed as weight percent. MSDS's (Attachment 1) are
included for the iron powder and the thixotropic agent.
Note: Fluid viscosity is expected to range from 1500 cp to approximately 5000 cp.
The thixotropic agent employed will be a high molecular weight water-soluble
acrylamide polymer. The product, SUPERFLOC+ A-130 HMW Flocculant, is a
polymer from the Anionic Polyacrylamide (PAM) Chemical Family. The material
consists of long chains of repeating Acrylamide units and exhibit molecular weights
of from 10 to 20 million. Although the polymer exhibits very little toxicity and does
not degrade to release Acrylamide (AMD), commercial material may contain up to
0.05% residual AMD from the manufacturing process.
No CAS Number has been assigned to this material as the manufacturer has
established that this product does not contain any hazardous or regulated components
(see the MSDS in Attachment 1). NESCO, Inc and Radian Engineering intend to use
the material to control the viscosity of a slurry of iron powder in molasses and water.
The material is used in a variety of other commercial processes including:
1. Approved by NSF for use as a potable water flocculant.
2. Approved-by-USFDA as-aclarifier-for-sugar-juice-used-in-distilled-beverages.
3. Used by cities and industrial plants for clarification of sewage and wastewater.
4. Used by Paper manufacturers for food wrappers and containers.
This materials is a non -toxic biodegradable product that is widely used throughout
industry from foods to mining and waste water treatment.
3. Two general conditions are expected to be encountered at the pilot test locations at
the site . The first area, where native soils were mixed and compacted, exhibits a low
porosity of approximately 10 % and elsewhere the undisturbed native soils have a
porosity of about 25%. The injection scheme is designed to result in a "radius of
influence" of about 15 feet and to affect an approximate thickness of 5 feet. Based on
these parameters, the following concentrations are expected in groundwater, 10 feet
from the injection point, once hydrogeologic equilibrium has been re-established
(several days):
Mectooled Area (low porosity area)
Molasses:
PAM:
Iron:
1.5 % (vol.)
480 ppm
0.27 lbs/ft

•
Native Soils (25 % porosity)
Molasses: 0.72 % (vol.)
PAM: 217 ppm
Iron: 0.27 lbs/ft
The iron concentration is an average loading within the formation and does not
depend on soil porosity. Molasses is rapidly consumed due to anaerobic bioactivity,
so it is not expected to persist in groundwater for more than a month or two. Due to
its high molecular weight and anionic character, PAM does not readily move with
groundwater and it is expected that concentrations of this material will rapidly
decrease with distance from the injection point. Given site conditions, no detectable
levels of PAM are expected to occur beyond 20 to 50 feet from perimeter injection
points over the project lifetime.
4. Slurry injection into groundwater creates an artificial, transient gradient due to
localized mounding around the injection point. As a consequence, virtually every
direction from the injection point is "downgradient" and the localized groundwater
flow patterns are disturbed. This disturbance is temporary in nature and normal
behavior is quickly re-established. Injected materials will tend to emanate from the
injection point and the distance traveled is a function of the volume of material
injected. Injections will be designed to push material approximately 15 feet from the
injection point.
As the -solution is adsorbed, -iron-powder-is-leftbehind-in-the-formation for -reaction
with contaminants of concern. No movement of iron is expected to occur after
injections are completed. Naturally occurring bacteria will experience rapid localized
growth, stimulated by the injected molasses.
The thixotropic agent (PAM), as supplied, is an off-white granular solid and must be
mixed with water for a period of time to develop the desired properties. As this
occurs, the long molecular strands tend to unfurl and a homogeneous solution results.
It appears that prepared solutions are readily adsorbed onto soils and that the viscous
solution tends to rapidly disperse, once installed. Due to its high molecular weight
and anionic character, PAM does not readily move with groundwater and it is
expected that concentrations of this material will rapidly decrease with distance from
the injection point. Given site conditions, no detectable levels of PAM are expected
to occur beyond 20 to 50 feet from perimeter injection points over the project
lifetime.
5. No pumping for the purpose of recovery is planned for this application.
6. Based upon previous injection experience and the distance to the nearest surface
water body, it is not anticipated that the product will discharge to any surface water in
the area.

7. Principal site contaminants include chlorinated alkenes (PCE, TCE, DCE, and VC)
and chlorinated alkanes such as TCA. Results from a bench study performed to
evaluate reductive dechlorination for treatment of contaminants showed that toxic
daughters such as vinyl chloride were not formed at such a rate as to cause an
increase in concentration and that concentrations began to decrease within 60 to 90
days. Ultimate degradation byproducts include methane, ethane, and ethene. In
addition to these gases, carbon dioxide, ferrous iron, and chloride will be produced.
Biodegradation of PAM occurs slowly, producing intermediates that appear to be low
molecular weight polyacrylates. Eventually, these polyacrylates are completely
mineralized.
The following references discuss the byproducts of degradation expected as a
consequence of the biologic and chemical processes at work.
• Fate of Acrylamide Monomer Following Application to Cropland (F.W. Barvenik,
R.E. Sojka, R.D. Lentz, F.F. Andrawes and L.S. Messner— Cytec Industries,
Stamford, CT and USDA-ARS, Kimberly, ID — Presented at the Conference on
MANAGING IRRIGATION -INDUCED EROSION and INFILTRATION WITH
POLYACRYLAMIDE Twin Falls, Idaho, U.S.A., May 6-8, 1996). (See Attachment
2)
• Natural Attenuation of Fuels and Chlorinated Solvents in the Subsurface:
Wiedemeier, Todd, Rifai, Hanadi S., Newell, Charles J., and Wilson, John T.
John Wiley -and- Sous Inc., 199t(Chapters 3, 5 and 6).
8. See documentation for question # 7.
9. The objective is to inject iron powder and molasses into the affected formation in
close contact with chlorinated solvent contamination so that reductive dechlorination
can occur through abiotic mechanisms and by biodegradation pathways. A bulk
mixing tank is used to prepare the iron slurry in water and molasses. The purpose of
the thixotropic agent is to increase viscosity to a point where iron particles can be
temporarily held in suspension until injection into the subsurface is completed.
Injections are planned at various depths throughout the affected formation with
horizontal spacing as shown in Figure 1 in Attachment 3. On average, a fifteen -foot
radius of influence can be assumed. The volume of slurry injected at each location is
expected to vary from 50 gallons up to a high of 300 gallons.

Page 1 of 2
Potential pollution source Distance from well
North Carolina Department of Environment and Natural Resources
Division of Water Quality
Groundwater Section
PRECONSTRUCTION INJECTION FACILITY INSPECTION
REPORT -FORM A
INJECTION WELL PERMIT NO. WI
DATE 41/VI
NAME OF OWNER F/AMILTU J /PRL TM -SILL *rTN MAX -VD Kt4-mg_
ADDRESS OF OWNER *L2/ IdkrackONT D2.
4rLC/1 4LLt , VA Z30(,0
(Street/ road or lot and suddivision, county, town)
LOCATION OF PROPOSED INJECTION WELL (and source well(s), if applicable)
HAM A
20 1 EAsr zoo ST
wASHiNiTiON, MC 2.7 54111
(Street/ road or lot and suddivision , county, town, if different than owner's address, plus description of location on site)
Potential pollution source TCE Distance from well ,fct '
Potential pollution source pe; NY020CAe. Distance from we 1 Epp
wotal it_ so PP' -
Minimum distance of proposed well from property boundary 5D
Quality of drainage at site Po pQ Flooding potential of site /K 0D cR 7F - LO w
(good, adequate,poor) (high,moderate, low)
DRAW SKETCH OF SITE
(Show property boundaries, buildings, wells, potential pollution sources, roads, approximate scale, and north arrow.)
SEE" 51TE MAP OF MY UCA-11 4 0.1 50AM.crr
w t
March 98

Page 2 of 2
PRECONSTRUCTION INJECTION FACILITY
INSPECTION REPORT - FORM A (cont.)
COMMENTS
SCF ArrAC.c (.t itc-Att,er tR
Ofler/
INSPECTOR V -
es Office W, f2,0
WITNESS
Address
WITNESS
Address
March 98

i
WASHINGTON REGIONAL OFFICE
DIVISION OF WATER QUALITY
GROUNDWATER SECTION
September 27, 1999
MEMORANDUM
TO: Mark Pritz1,SJIC Group, Groundwater Section Central Office
THROUGH: Willie Hardison, Grounwater Supervisor, Washington Regional Office w
o cIrri
FROM: Keith Starner, Groundwater Section KS
SUBJECT: Hamilton Beach Proctor Silex Facility, Injection Well Permit Review -o;C7
� :ter
< n
r :)
I received and reviewed the injection well permit applications for the proposed oxygen rele4g
compound and the "zero valent" iron cleanup processes at the above site. These permit
applications contain extracts of large portions of the comprehensive site assessment and the
preliminary corrective action plan previously submitted for this site. Attached is my response to
the preliminary CAP, which addresses my two main concerns for the proposed injection wells,
which are:
1. The pilot tests lacked adequate detail.
2. The rationale for choosing an oxygen re ease compound was not supported by the
CAP. N A 11,5 rz D,cja1LW\-k (C..?OflkI)
Other concerns include potential iron -fouling of well screens when using the iron/guar
technology, and the potential for the concentration of oxygen along preferential pathways
because of the large areas covered by asphault and concrete at the site which can lead to an
explosive situation. Also attached are Forms A as requested in the review packages.

GROUP
RADIAN INTERNATIONAL
A DAMES & MOORE GROUP COMPANy
September 2, 1999
Department of Environment and Natural Resources
Division of Water Quality
Groundwater Section
Attn: Mr. Mark Pritzl
1636 Mail Service Center
Raleigh, North Carolina 27699-1636
RE: UIC Permit Application
Zero-Valent Iron Pilot Test
Hamilton BeachOProctor-Silex, Inc.
Washington, North Carolina
Dear Mr. Pritzl:
Mailing Address:
Post Office Box 13000
Research Triangle Park,
North Carolina 27709
Physical/Shipping Address:
1600 Perimeter Park Drive
Morrisville, North Carolina 27560
919 461 1100 Tel
919 461 1415 Fax
I, James Narkunas, a Licensed Geologist in the State of North Carolina, certify that this
permit application and its contents have been prepared under my direct control and
personal supervision.
•; % sIa1a,,,,,
•
gH CARP `e
m�oE�,,��oII
i i0, " SEAL 1 41 Lo ci
es Narkunas
NC 399
= 399a Date
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Engineering Services in North Carolina are performed through Radian International's wholly owned subsidiary, Radian Engineering, Inc
Offices Worldwide

MEMORANDUM
To:
From:
GROUNDWATER SECTION
August 23, 1999
Willie Hardison
Groundwater Section
Washington Regional Office
Mark Pritzl; [e-mail]
Hydrogeological Technician II
UIC Group
Groundwater Section
Central Office
Re: Request for inspection and review of a new injection well permit application to use zero-
valent iron at Hamilton Beach/Proctor-Silex, Inc., 234 Springs Road in Washington, North
Carolina.
The application was submitted by Hamilton Beach/Proctor-Silex, Inc. for a new permit to operate
injection well(s) was received by the CO—UIC group. A copy of this application is attached for
your review.
1. Please review the application and submit any comments to CO-UIC. Retain the
application -copies -for -your UT UU C filesfiles
2. Please inspect the proposed injection well site to verify that the location and construction
plans submitted in the application are accurate and that the NCAC T15A:02C.0200
standards are being complied with, using the enclosed Preconstruction Injection Facility
Inspection Report (form 4).
Return any application review comments and the completed Preconstruction Injection Facility
Inspection Report (form A) to the CO-UIC by September 30, 1999. If the application review
comments and inspection cannot be accomplished by this date, please inform CO-UIC.
After the permit has been issued and when operation is about to commence, the CO-UIC will notify
the WARO, which may, at your discretion, inspect the facility in operation.
cc: UIC files
WARO files
enclosures

:DENR
JAMES B. HUNTJR'
. GOVERNOR
.i,
NORTI-,-AROLINA DEPARTMENT OF
ENVIRONMENT AND NATURAL RESOURCES
DIVISIONOF WATER QUALITY
WAYNE MCDEVITI' Mario Kuhar
SECRETARY s'I. -a 1 ,Hamilton Beach/Proctor-Silex, Incorporated.
4421 Waterfront Drive
;Glen Allen, VA 23060
August 23, 1999
Dear Mr. Kuhar:
Your application for a permit to construct and/or use a well(s) for a pilot -scale
test that will consist of injecting an iron slurry through three injection points and
placing a permeable zero-valent iron wall perpendicular to the plume flow direction
has been received and is under review. A member of the Groundwater Section's
Washington Regional Office staff may be contacting you to arrange an inspection of
the injection site as part of the review.
If you have any questions regarding the permit or injection well rules please
contact me at [phone] or Amy Axon at [phone].
Mark Pritzl
Hydrogeological Technician II
Underground Injection Control Program
cc: UIC Files
WARO Files
GROUNDWATER SECTION
1636 MAIL SERVICE CENTER, RALEIGH, NC 27899-1636 - 2728 CAPITAL, BLVD., RALEIGH, NC 27604
PHONE[phone] FAX [phone]
AN EQUAL OPPORTUNITY / AFFIRMATIVE ACTION EMPLOYER - SO% RECYCLED/10% POST -CONSUMER PAPER

I�l1IILIc�\ BE VA-I0PROCfl)R-SILEI\.I\( .
August 19, 1999
Ms. Amy Axon
North Carolina DENR-DWQ
Groundwater Section, Room #1C143
2728 Capitol Blvd.
Raleigh, NC 27604
-- via DHL Express No. 7814552804 --
Reference: Hamilton Beach/Proctor-Silex, Inc.
Washington, North Carolina
Ms. Axon:
Enclosed for your review are the Applications for Permit to Construct and/or Use
A Well(s) for Injection for the pilot -scale testing of two proposed remedial
technologies for the above referenced site. As required, there are two originals
along with two copies.
If you have any questions, please call me at 804/527-7222.
Sincerely,
Mario Kuhar
Sr. Environmental Engineer
cc: G. P. Manson, Jr. —w/o enclosures
C. Zachwieja — w/o enclosures
B. A. DeVore
J. Narkunas
0
rAn
CD
371
co=
rfs.�
n
Corporate 11eadquartcrs •n .

North Carolina Department of Health and Human Services
Division of Public Health • Section of Human Ecology and Epidemiology
1912 Mail Service Center • Raleigh, North Carolina 27699-1912
Tel [phone] • Fax [phone]
Michael F. Easley, Governor Carmen Hooker Buell, Secretary
June 20, 2001
MEMORANDUM
TO: Mark Pritzl
Groundwater Section
FROM: Luanne K. Williams, Pharm.D., Toxicologist
Medical Evaluation and Risk Assessment Unit
Occupational and Environmental Epidemiology Branch
North Carolina Department of Health and Human Services
SUBJECT: Use of zero-valent Iron and Molasses Slurry for In -Situ Pilot -Scale Test at the
Abbott Laboratories Facility in Laurinburg, North Carolina to Determine
Effectiveness of Dehalogenation of Chlorinated Organic Compounds in
Groundwater
I am writing -in response-to--a-request-from Radian.Engineeringlnc.foLahealth_risk
evaluation regarding the use of zero-valent iron and molasses slurry for in -situ pilot -scale tests at
the Abbott Laboratories facility in Laurinburg, North Carolina to determine effectiveness of
dehalogenation of chlorinated organic compounds in groundwater. Based upon my review of
the information submitted by Radian Engineering Inc., I offer the following health risk
evaluation:
WORKER PRECAUTIONS DURING APPLICATION
1. Some effects reported to be associated with the products are as follows:
molasses — There are no major health hazards (OHM/TADS ® — Oil and Hazardous
Materials/Technical Assistance Data System Micromedex, Inc. ChemKnowledge TM
System Plus Ariel GlobalView TM, Volume 49 CD-ROM , 2001).
iron — Direct contact with this material may cause eye irritation and bronchitis (Peerless
Metal Powders 7 Abrasives material Safety Data Sheet, January 28, 2000). There are
many potential physical hazards or interactions with other substances. As a precaution,
the contractor applying this product should be made aware of these potential interactions.
See enclosed reference Meditext ® - Medical Management Micromedex, Inc.
ChemKnowledge TM System Plus Ariel GlobalView TM, Volume 49 CD-ROM , 2001.
r•
Location: 2728 Capital Boulevard • Parker Lincoln Building • Raleigh, N.C. 27604 An Equal Opportunity Employer

SuperFloc®A-130 HMW Flocculant - The SuperFloc®A-130 HMW Flocculant consists
of long chains of repeating acrylamide units. Direct contact with the polymer may cause
eye and skin irritation (CYTEC Material Safety Data 12/21/99). The polymerized
acrylamide is relatively nontoxic as it is used as a food additive in gelatin capsules and in
potable water treatment (Hazardous Substances Data Bank® Micromedex, Inc.
ChemKnowledge TM System Plus Ariel GlobalView TM, Volume 49 CD-ROM , 2001).
According to Radian, the commercial material may contain up to 0.05% residual
acrylamide from the manufacturing process. The acrylamide monomer can cause nerve
damage and is a probable human carcinogen. Significantly increased incidences of
benign and/or malignant tumors at multiple sites in both sexes of rats, and carcinogenic
effects in a series of one-year limited bioassays in mice by several routes of exposures
have been reported. The recommended daily lifetime groundwater concentration for
acrylamide based on the carcinogenic endpoint is 0.008 ug/L .
2. If the products are released into the environment in a way that could result in a
suspension of fine solid or liquid particles (e.g., grinding, blending, vigorous shaking or
mixing), then it is imperative that proper personal protective equipment be used. The
application process should be reviewed by an industrial hygienist to ensure that the most
appropriate personal protective equipment is used.
3. Persons working with these products should at least wear goggles or a face shield, gloves,
and protective clothing. Face and body protection should be used for anticipated splashes
or sprays. Again, consult with an industrial hygienist to ensure proper protection.
4. Eating, drinking, smoking, handling contact lenses, and applying cosmetics should never
be permitted in the application area during or immediately following application. Safety
controls should be in place to ensure that the check valve and the pressure delivery
systems are working properly if used.
5. The Material Safety Data Sheets should be followed to prevent adverse reactions and
injuries.
OTHER PRECAUTIONS
Access to the area of application should be limited to the workers applying the products.
In order to minimize exposure to unprotected individuals, measures should be taken to
prevent access to the area of application.
2. According to the information submitted (see enclosure), these products are expected to
travel a maximum of 50 feet from the point of injection. The nearest property line is
another 250 feet beyond the anticipated travel distance of the products. The nearest
residents are located 1,500 feet east and southeast of the site. According to Radian, the
Abbott Labs facility and surrounding businesses and industries are connected to the
Laurinburg municipal water system. The City of Laurinburg obtains water from nine
wells located southwest of the city. The Abbott Labs facility is located north of the city

of Laurinburg and is farther than 1.5 miles from the nearest existing or recently
constructed city water supply well.
Because of the potential presence of acrylamide in this product, the high water solubility
and toxicity of acrylamide; caution should be taken to prevent contamination of
groundwater that could be used as a drinking water source in the near future. The
recommended daily lifetime groundwater concentration for acrylamide based on the
carcinogenic endpoint is 0.008 ug/L.
According to the literature, acrylamide can undergo biodegradation (Hazardtext ® -
Hazard Management Micromedex, Inc. ChemKnowledge TM System Plus Ariel
GlobalView TM, Volume 49 CD-ROM , 2001). According to Radian, the injection of
these products is not expected to impact public or private wells.
3. According to the Radian, these products are not expected to impact nearby waters
including an unnamed tributary to Leith Creek west of the site. According to Radian, this
tributary is located approximately 150 feet west of the Abbott property and over 400 feet
from the maximum anticipated travel distance of the injected products.
Please do not hesitate to call me if you have any questions at [phone].
Enclosures
cc: Abbott Laboratories
Kim Kashmer
Junction of Hwys. 15/501 & 401
Laurinburg, North Carolina 28352
NESCO Inc., Remediation Technologies Group
Scott Noland
6870 North Broadway, Unit H
Denver, Colorado 80221
Radian International
Brett Berra
P.O. Box 13000
Research Triangle Park, North Carolina 27709

INFORMATION NEEDED TO DO RISK ASSESSMENTS FOR
PRODUCTS APPLIED TO GROUNDWATER OR SOIL
CONTAINING NO MICROORGANISMS
Required General Information
1. Mark Pritzl
Underground Injection Control Program
919.715.6166
2. Abbott Laboratories
Kim Kashmer
Junction of Hwys. 15/501 & 401
Laurinburg, NC 28352
910.276.4274
The facility produces medical devices including sets for intravenous administration of
drugs and health maintenance solutions. Products are manufactured using polyvinyl
chloride and other plastics.
3. NESCO Inc., Remediation Technologies Group
Scott Noland
6870 North Broadway, Unit H
Denver, CO 80221
303.487.1001 (Ext 13)
4. Based upon previous injection experience in similar hydrogeologic conditions, this
product is expected to travel a maximum of 50 feet (conservative) from the point of
injection. The nearest property line is another 250 beyond the anticipated travel
distance of the product. The Abbott Labs facility and surrounding businesses and
industries are connected to the Laurinburg municipal water system. The only wells
on the property are monitoring wells and remedial extraction wells that will be turned
off during this application. The City of Laurinburg obtains water from nine wells
located southwest of the city. In addition, six more wells have recently been
constructed to utilize as water supply wells in the near future. The Abbott Labs
facility is located north of the City of Laurinburg and is farther than 1.5 miles from
the nearest existing or recently constructed city water supply well. Based upon the
information presented above, no public or private wells will be impacted by this
injection.
5. The operation of a former solvent disposal pit between 1970 and 1976 resulted in
groundwater contamination at this site. A contaminant plume, consisting primarily of
volatile organic compounds (VOCs), in groundwater underlies the site. The primary
contaminants of concern include tetrachloroethene (PCE), trichloroethene (TCE),
chloroform, vinyl chloride, benzene, toluene, 4-Methyl-2-Pentanone, 1,1-

dichloroethene (1,1-DCE), 1,2-dichloroethene (1,2-DCE), and 1,2-dichloroethane
(1,2-DCA).
6. The nearest surface water body to the Abbott facility is an unnamed tributary to Leith
Creek west of the site. This tributary is located approximately 150 feet west of the
Abbott property and over 400 feet from the maximum anticipated travel distance of
the injected product . Based upon previous injection experience and the distance to
the nearest surface water body, it is not anticipated that the product will discharge to
any surface water in the area.
7. The nearest workplace is the Abbott Labs manufacturing facility located on -site.
Proposed pilot test injection locations are on the Abbott Labs property adjacent to this
facility. No injection locations are located off -site. The nearest residents are located
in a neighborhood approximately 1,500 feet east and southeast of the site.
Required Product/Process-Specific Information
1. For information on the zero-valent iron and molasses contact:
NESCO Inc., Remediation Technologies Group
Scott Noland
6870 North Broadway, Unit H
DenverCO 80221
303.487.1001 (Ext 13)
For information on the thixotropic agent (SUPERFLOC+ A-130 HMW Flocculant)
contact:
CYTEC Industries, Inc.
Randy Deskin (Toxicology)
Five Garret Mountain Plaza
West Patterson, NJ 07424
800.527.9313 (Ext 3372)
2. The technology chosen to remediate chlorinated solvent contamination in the
groundwater relies on reductive dechlorination and utilizes activated iron powder
(Zero Valent Iron, ZVI) as an electron donor. ZVI facilitates a chemical reduction
process that sequentially dehalogenates chlorinated hydrocarbons. Organic substrate
augmentation using agricultural grade molasses, facilitates both biological and
chemical processes that results in reductive dehalogenation of chlorinated organic
compounds. The iron powder is mixed with water, molasses, and a thixotropic agent,
which is needed to control slurry viscosity. In general, slurry properties and
composition will remain fairly constant, containing:

1. Water
2. Thixotropic Agent
3. Iron Powder
4. Molasses -
69%to 91.8%0
0.1%to0.15%
3%to20%
5% to 10%
fr-
The above composition is expressed as weight percent. MSDS's (Attachment 1) are
included for the iron powder and the thixotropic agent.
Note: Fluid viscosity is expected to range from 1500 cp to approximately 5000 cp.
The thixotropic agent employed will be a high molecular weight water-soluble
acrylamide polymer. The product, SUPERFLOC+ A-130 HMW Flocculant, is a
polymer from the Anionic Polyacrylamide (PAM) Chemical Family. The material
consists of long chains of repeating Acrylamide units and exhibit molecular weights
of from 10 to 20 million. Although the polymer exhibits very little toxicity and does
not degrade to release Acrylamide (AMD), commercial material may contain up to
0.05% residual AMD from the manufacturing process.
No CAS Number has been assigned to this material as the manufacturer has
established that this product does not contain any hazardous or regulated components
(see the MSDS in Attachment 1). NESCO, Inc and Radian Engineering intend to use
the material to control the viscosity of a slurry of iron powder in molasses and water.
The material is used in a variety of other commercial processes including:
1. Approved by NSF for use as a potable water flocculant.
pprovo arifrerfor sugar juice -used in distilled beverages.
3. Used by cities and industrial plants for clarification of sewage and wastewater.
4. Used by Paper manufacturers for food wrappers and containers.
This materials is a non -toxic biodegradable product that is widely used throughout
industry from foods to mining and waste water treatment.
3. Two general conditions are expected to be encountered at the pilot test locations at
the site . The first area, where native soils were mixed and compacted, exhibits a low
porosity of approximately 10 % and elsewhere the undisturbed native soils have a
porosity of about 25%. The injection scheme is designed to result in a "radius of
influence" of about 15 feet and to affect an approximate thickness of 5 feet. Based on
these parameters, the following concentrations are expected in groundwater, 10 feet
from the injection point, once hydrogeologic equilibrium has been re-established
(several days):
Mectooled Area (low porosity area)
Molasses:
PAM:
Iron:
i
1.5 % (vol.)
480 ppm
0.27 lbs/ff3

Native Soils (25 % porosity)
Molasses: 0.72 % (vol.)
PAM: 217 ppm
Iron: 0.27 lbs/ft
The iron concentration is an average loading within the formation and does not
depend on soil porosity. Molasses is rapidly consumed due to anaerobic bioactivity,
so it is not expected to persist in groundwater for more than a month or two. Due to
its high molecular weight and anionic character, PAM does not readily move with
groundwater and it is expected that concentrations of this material will rapidly
decrease with distance from the injection point. Given site conditions, no detectable
levels of PAM are expected to occur beyond 20 to 50 feet from perimeter injection
points over the project lifetime.
4. Slurry injection into groundwater creates an artificial, transient gradient due to
localized mounding around the injection point. As a consequence, virtually every
direction from the injection point is "downgradient" and the localized groundwater
flow patterns are disturbed. This disturbance is temporary in nature and normal
behavior is quickly re-established. Injected materials will tend to emanate from the
injection point and the distance traveled is a function of the volume of material
injected. Injections will be designed to push material approximately 15 feet from the
injection point.
thesolution-is adsorbed; im ormation-for-reaction
with contaminants of concern. No movement of iron is expected to occur after
injections are completed. Naturally occurring bacteria will experience rapid localized
growth, stimulated by the injected molasses.
The thixotropic agent (PAM), as supplied, is an off-white granular solid and must be
mixed with water for a period of time to develop the desired properties. As this
occurs, the long molecular strands tend to unfurl and a homogeneous solution results.
It appears that prepared solutions are readily adsorbed onto soils and that the viscous
solution tends to rapidly disperse, once installed. Due to its high molecular weight
and anionic character, PAM does not readily move with groundwater and it is
expected that concentrations of this material willrapidly decrease with distance from
the injection point. Given site conditions, no detectable levels of PAM are expected
to occur beyond 20 to 50 feet from perimeter injection points over the project
lifetime.
5. No pumping for the purpose of recovery is planned for this application.
6. Based upon previous injection experience and the distance to the nearest surface
water body, it is not anticipated that the product will discharge to any surface water in
the area.

7. Principal site contaminants include chlorinated alkenes (PCE, TCE, DCE, and VC)
and chlorinated alkenes such as TCA. Results from a bench study performed to
evaluate reductive dechlorination for treatment of contaminants showed that toxic
daughters such as vinyl chloride were not formed at such a rate as to cause an
increase in concentration and that concentrations began to decrease within 60 to 90
days. Ultimate degradation byproducts include methane, ethane, and ethene. In
addition to these gases, carbon dioxide, ferrous iron, and chloride will be produced.
Biodegradation of PAM occurs slowly, producing intermediates that appear to be low
molecular weight polyacrylates. Eventually, these polyacrylates are completely
mineralized.
The following references discuss the byproducts of degradation expected as a
consequence of the biologic and chemical processes at work.
• Fate of Acrylamide Monomer Following Application to Cropland (F.W. Barvenik,
R.E. Sojka, R.D. Lentz, F.F. Andrawes and L.S. Messner — Cytec Industries,
Stamford, CT and USDA-ARS, Kimberly, ID — Presented at the Conference on
MANAGING IRRIGATION -INDUCED EROSION and INFIL11tATION WITH
POLYACRYLAMIDE Twin Falls, Idaho, U.S.A., May 6-8, 1996). (See Attachment
2)
• Natural Attenuation of Fuels and Chlorinated Solvents in the Subsurface:
Wiedemeier, Todd, Rifai, Hanadi S., Newell, Charles J., and Wilson, John T.
John-Wiley-and-SSons-Inc ;-1999 Chapters 3, 5-and-6).
8. See documentation for question # 7.
9. The objective is to inject iron powder and molasses into the affected formation in
close contact with chlorinated solvent contamination so that reductive dechlorination
can occur through abiotic mechanisms and by biodegradation pathways. A bulk
mixing tank is used to prepare the iron slurry in water and molasses. The purpose of
the thixotropic agent is to increase viscosity to a point where iron particles can be
temporarily held in suspension until injection into the subsurface is completed.
Injections are planned at various depths throughout the affected formation with
horizontal spacing as shown in Figure 1 in Attachment 3. On average, a fifteen -foot
radius of influence can be assumed.. The volume of slurry injected at each location is
expected to vary from 50 gallons up to a high of 300 gallons.

Fate of Acrylamide Monomer
Following Application of
Polyacrylamide to Cropland
F.W. Barvenik', R.E. Sojka2, R.D. Lentz2,
F.F. Andrawes' and L.S. Messner'
'Cytec Industries, Stamford, CT
and
2USDA-ARS, Kimberly, ID
Presented EROSION And
INFILTRATION WITH POLYACRYLAMIDE Twin 'Fells, �ho, U.S.,AMay 6-8, 1996.
AR.SIBACI
Although palyacrylamides (PAMs) exhibit little toxicity and do
not degrade to release acrylamide (AMD) monomer, commercial PAMs
may contain up to 0.05% residual AMD from manufacturing. PAMs
are used in treatment of potable water, wastewater discharging to
surface streams, and FDA sanctioned food contact applications.
The environmental tate of AMD monomer will be reviewed in this
paper. AMD is not adsorbed significantly by soil, and is
chemically and biologically labile in natural environments,
especially under aerobic conditions. There is no literature
evidence of AMD uptake by plants, except for rice grown
hydroponically In the presence of extremely high AMO levels. In
addition, recent work with field crops showed no uptake.
Potatoes, beans, corn and sugar beets, were grown in the presence
of very high dosages of was PAM, and ot detected In the analyzed
(detection
gas
chromatography.m0ppb
limit <t00 ppb). Reactivity of AMO was demonstrated by spiking
studies, in which freshly added AMD rapidly dropped to
undetectable levels.
MAR 22 2000 14:23
203 321 2982 PAGE.02

ACRYLAMIDE (AMD)
MW = 71.08
CH=CH2
I
C=0
NH2
ANIONIC POLYACRYLAMIDE (PAM)
«cH-CH2
b-
�
Na' Ofm
MW = 10-20 million
m + n = 140,000 - 280,000
[Cci.7:0C1-4-r-mysiv
I
42
MAR 22 2000 14:23
203 321 2982 PAGE.03

DEGRADATION
of PAM
• HYDROLYSIS
(Removal of N'to yield polyacrylate, under acidic & basic
conditions)
• MOLECULAR WEIGHT DEGRADATION
— MEht PAM
CHANICAL
can yield fragear of mentsgh witholecular molecular weight of
10,000 to 100,000)
— UV LIGHT
— STRONG OXIDIZERS
• BIODEGRADATION VERY SLOW '
(Removal of N & biodegradation of very low molecular weight
polyacrylatas)
• NO REGENERATION of AMD MONOMER
(Thermodynamics
bond; no evidence of AMD regeneration ltionrInliteraturdoubleon of
e.)
PAM---/---> AMD
PAM DOES NOT DEGRADE TO
YIELD ACRYLAMIDE MONOMER
(However commercial PAMs contain residual AMD;
typically 0.05% or Tess).
MAR 22 2000 14:23
203 321 2982 PAGE.04

AMD is Mobile
However, at 10 ppm l FAMMO in he irrigation
m AMD conen ration
with 0.05% residual AMD,
In the furrow would be 5 ppb.
• High water solubility (215.5 g/100 ml @ 30°C)
• Octanol/Water partition Indicates tow lipid
-0.67)
solubility & bioaccumulation (log
Kow• Low adsorption by activated carbon, silica, clay
minerals, peats, sediments and sludges
•
• Soil TLC: mobileostlmobileinoils tlowed (organ c soils
2.8-16%
organic matter);;
Lande, et a1.1979.
• Brown, et a1:1980a.
o Health& Envlron.Internat.1990.
Anon.1991.
Aquatic Toxicity of
AMD Monomer (Lc5o)
• Goldfish: 460, 140 ppm
• Fathead Minnow: 56,120 ppm
• Rainbow Trout: 110 ppm
• Bluegill Sunfish: 100 ppm
• Daphnia magna: 160 ppm
• Midges 410 ppm
° Health&Environ.Internat.1990.
Anon.1991.
Nag: Above values are'10,000 fold higherthace
would result from current recommended p a
cti
MAR 22 2000 14:24
203 321 2982
PAGE .05

AMD Volatility
— • Low Vapor Pressure at temperatures < 40° C,
therefore unlikely to transport from soil/water into
atmosphere
• In Atmosphere, would mostly adsorb to
particulates, therefore likely to precipitate
• In Atmosphere would react rapidly ith• radicals
photochemically produced hydroxyl
(half lice - 6.6 hr)
• Health& Envlron. Internat. 1990.
• Anon.1991.
• Heberman.1991.
• Smith&Oehme.1991.
AMD is CHEMICALLY
REACTIVE at DOUBLE BOND
and AMIDE GROUP
• HYDROLYSIS with acid or base to ACRYLIC ACID
(taster under basic conditions)
• POLYMERIZATION with itself or other vinyl monomers
(presence of free radicals, absence of oxygen)
• Reacts with NH,, amines, alcohols,
h, B de hydOes, ccel ul sunder
starch, mercaptans, S032, ,o, C12, 2 4
certain pH and temperature conditions
• HOWEVER: relatively stable (time frame = weeks to
months) at neutral pH, under environmental conditions in
absence of microorganisms or enzymes.
MacWilliams. 1973. Anon.1991.
Brown, et al.1982. Haberman.1991.
Thomas & Wang. 1985. Smith & Oehme.1991.
MAR 22 2000 14:24
203 321 2902 PAGE.06

INHIBITION of PLANTS
(ALL SHIGHERCTAMD LEVELS HAN CURRENT PRACTICE) FOLD
• Tumips
— Inhibition of growth by >220 ppm AMC
Kubol and Fu)11.1984.
• Rice
— no apparent Inhibition by 50 ppm AMD
NIshlkawa, et al. 1983
• Chinese Cabbage
— inhibition of growth by >5 ppm AMD
. Nlshlkawa, at al. 1983
UPTAKE by PLANTS
(ALL S HIGH RCTHAMD LEVELS AN CURRENT PRACTICE) 000 FOLD
• Tomatoes
— no AMD detected In tomato frult (LD r 1 ppb)
. Castle, et al. 1991.
• Mushrooms
— no AMD detected In mushrooms (ID = 0.5 ppb)
Castle.1993.
Rice
— evidence of uptake by roots (1.7 ppb) and stalks (41 ppb)
(vs. SO ppm In hydroponics medium)
— rapid decay (10-100 fold Inc. 5 days) within rice tissues
Nlshlkawa, et 31.1983.
MAR 22 2000 14:24
203 321 29B2 PRGE.07

AMD Uptake Studies
at Kimberly, ID; 1994-95
• by plants under r eaned to investigate whether AMD is taken up
realistic Held condlt ons
• 1994: irrigation water for two crops treated with
10 ppm PAM.
• 1995: PAM broadcast on land at a high rate
(1000 kg/ha), then tilled into soil Used to groW four
crops. Irrigation water treated with 20 ppm PAM.
• Crops harvested, then analyzed for AMD by gas
chromatography.
PAM APPLICATIONS
NUMBER d
YEAR L111. TRFATMFNT$
1994 potatoes
1994 beans
1995 potatoes
1995 beans
1995 sugar beets
1995 corn
15
5
10+
broadcast
10+
broadcast
10 +
broadcast
10+
broadcast
TOTS PI Q. 2d11e AM TAXAMUln
OP Iatoot
19.9 5
7.4 2
1140 312
1140 312
1140 312
1140 312
MAR 22 2000 14:25
203 321 2992 PAGE.08

Analytical Method
• Extract Into Water by
homogenization with blender
• Derivatlze with Bromine to
2,3-dibromopropionamide
• Extract with ethyl acetate
• Convert to 2-bromopropenamide
with triethylamine
• AnalElwith Gas Chromatography and
econ Capture Detector
t t
• Hashimoto. 1976. Analyst 101:932-938.
• Andrawes, et al. 1987.J.Chromatogr. 399:269-275.
Summary of Results
• Standard curve linear in range of 25-100 ppb
(R2 = 0.967 - 0.993).
• Limit of detection 10 ppb or less.
• AMD, IF PRESENT AT ALL, WAS BELOW
10 PPB IN ALL SAMPLES.
• AMD added to aqueous extracts of the crops was
labile, the concentration decreasing In the
timespan of minutes to hours. This suggests that
AMD Is likely to convert to some other chemical
species in the plant tissue itself.
MAR 22 2020 14:25
203 321 2982 PRGE.09

Decay of Spiked AMD in Aqueous
Extract of Beans
(SPIKED @ 100 ppb at Time Zero)
Siendino time % RecoverY
10 sec 75
1 min 56
2 min 48
5 min 29
10 min 22
(SPIKED @ 500 ppb at Time Zero)
overnight
Decay of Spiked AMD in Aqueous
Extract of Potatoes
(SPIKED @ 100 ppb at Time Zero)
% Recovery
Blending time P 25G. Bkin
5 min 90
10 min 81 85
20 min 90 88
MAR 22 2000 14:25
203 321 2982 PAGE.10

maim
Decay of Spiked AMD in
Aqueous Extracts
rt:
(SPIKED @ 50 ppb at Time Zero)
e� aP�ovent
BlPndina time �---
10 sec
1 min
5 min
112
103
29
seats. (SPIKED @ 100 ppb at Time Zero)
•�_ o,,,,�v�
�ndina time
1 min
5 min
93
n
AMD BIODEGRADATION
IN WATER
• Studied in rivers, lakes, seawater, sewage effluents &
aquatic sediments
• Lag period (hours to weeks)
• Enrichment for AMD decomposing microorganisms
• Half -Life = hours to weeks in acclimated water
• Slow in oligotrophic water, more rapid in eutrophic
waters and sewage effluent
• Slower at low temperature
• More Rapid in Aerobic than Anaerobic Waters'
• Inhibited by Autoclaving
Croll, et al. 1974. Brown, et a1.1980b.
Davis, et a1.1976. Health& Envlron.Internat.1990.
MAR 22 2000 14:25
203 321 2982 PRGE.11

AMD BIODEGRADATION
IN SOIL
• 1°C-AMD half-life" 18-45 hr @ 22°C in four soils
• 2.5X slower In early spring soil than same soil In June
• significant temperature effect (10X difference 37°C
vs. 10°C)
• very slow rate in autoclaved soil
• half-life much shorter@ 25 ppm AMDthan @ 500ppm
• much lower rates under anaerobic conditions
° Lando, etal.1979:
AMD BIODEGRADATION
IN SOIL
• AMD concentration reduced from 500 ppm to
undetectable in 5 days in tropical soil @30°C
• Acrylic Acid = intemediate product of AMD
biodegradation
• NH4• and NO; production from AMD
demonstrated
• Pseudomonas AMD oxidizing bacterium isolated
'AMD = sole C and N source
•Amidase enzyme isolated
. Shenker, et al. 1990.
MAR 22 2000 14:26
203 321 2982 PAGE.12

AMD BIODEGRADATION
IN SOIL- (NITROGEN)
• AMD @ 197 ppm
• Five Different Moist and Air•dried Sails
• Aerobic conditions:
AMD.N- ,NH,•—>Na2`'Na3
Anaerobic conditions:
AMD-N—>NH;
• Mineralization rate higher at 30°C vs. 20°C vs.10°C
Abdelmagld and Tabataba1.19132.
POSTULATED AMD
BIODEGRADATION19 ATHWAY
(Shenker, et al.0)
Acrylemide
V
Acrylic Acid • NH3
V
♦ Hp
1
V
V
Acetyl Coenzyme A • CO2
Cot • H,0
.... ..................................................
........ ......
MAR 22 2000 14:26
203 321 2982
PAGE.13

SUMMARY
• Residual AMD in PAM products < 0.05%
• PAM does NOT Degrade to AMD monomer
• AMD is transportable by water
• AMD concentration from current recommended
practice < 5 ppb in water
• AMD not likely to volatilize from soil or water but
does degrade rapidly in atmosphere •
• AMD slowly chemically labile in sterile soil & water
• AMD is rapidly biologically labile in soil & water
• AMD Is not inhibitory to plants or aquatic animals at
usage concentrations
• AMD is not taken up by plants at usage
concentrations
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•
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