DEQ-CFW_00000228

C - 3 A c: ,& d'� nti.'l,,,
Brower, Connie
From: Belnick, Tom
Sent: Friday, June 05, 2015 10:45 AM
To: Brower, Connie; Ventaloro, Christopher; Risgaard, Jon; Henson, Belinda
Subject: FW: strynar contact
Attachments: C3_acid dimer.pdf; DuPont.pdf
Here's the material I received from EPA Mark Strynar on their Cape Fear River study. I looked at his presentation to
AWWA but didn't understand most of it (very heavy on analytical methodology).
Sidebar Note: he also included a link to NSF video interview with Detlef Knappe regarding 1,4-dioxane, which might be
of interest.
Tom Belnick
Supervisor, NPDES Complex Permitting Unit
NCDWR/Water Quality Programs
919-807-6390
E-mail correspondence to and from this address may be subject to the
North Carolina Public Records Law and may be disclosed to third parties
From: Strynar, Mark [mailto:[e-mail]]
Sent: Thursday, June 04, 2015 4:16 PM
To: Belnick, Tom
Subject: strynar contact
Tom,
Nice to chat with you. Here is the info I said I would send you.
1. The WV DEP NPPES permit documents for a new polyfluorinated compound
2. The NSF piece on 1,4-dioxane in NC waters with Detlef Knappe.
http://www.nsf.gov/news/soecial reports/science nation/capefearwatershed.isp
3. My presentation from the AWWA meeting in April in Wilmington,
NC http•//cymcdn com/sites/www ncsafewater orrgZresource/collection/F6F34F34-COBC-479A-9F40-
lE8F09B65B43/WTR Mon AM 1025 Strynar.pdf
Let me know if you need more.
Mark
Dr. Mark J. Strynar
US EPA
Physical Scientist
919-541-3706
[e-mail]
1
DEQ-CFW 00000228

west virginia department of environmental protection
Division of Water and Waste Management
601 57`n Street SE
Charleston, WV 25304-2345
Telephone Number: [phone]
Fax Number: (304) 926-0,163
January 31, 2012
Jim and Della. Tennant
15 Mansion € lvd.
Parkersburg, VN 26101
Earl Ray Tomblin, Governor
Randy C. Huffnian, Cabinet Secretary
www.dep,wv,gov
CERTIFIED MAIL RETURN RECEIPT REQUESTED
Re: WV/NPDES Permit No. WV0001279
Consent Order No. 7418 Comments
Dear Mr. and Mrs. Tennant:
This correspondence is in response to your comment letter dated December 13, 2011.
regarding draft Consent Order No. 7418 for WV/NPDES Permit No. WV0001279 issued to the
Dupont - Washington Works facility. Comments are summarized first in bold italics followed by
the agency's responses.
1. Comment: The order should not allow Dupont to discharge the new compound until all
of the treatment upgrades are completed.
The existing treatment employed at the facility will provide treatment of the new
compound. The additional treatment proposed by the perrnittee will enhance treatment
and allow for less frequent change -outs of activated carbon from the existing; carbon bed
system. Regardless of the treatment enhancements to be made by the permittee, the
effluent limitations for the new compound are effective immediately upon issuance of the
consent order and will be protective of the water quality standards and designated uses of
the Ohio River.
2. Comment. The order shouldn't be issued without explaining the new compound, its
effects on people and the environment, its toxicity, and host/ the DEP arrived at the
safety levels and monitoring requirements fair the new compound,
The new compound (C3 Dimer Acid/Salt) is a new fluoropolyrner compound that Dupont
is representing; as an ultimate replacement for the existing fluoropolyrner known as C8
(or PFOA, perifuorooctanoic acid). Dupont entered into a Toxic Substances Control Act
Consent (TSCA) Consent Order with the U.S. EPA in January 2009 which granted
Dupont approval, under conditions set forth in the TSCA Consent Order, to manufacture,
process, and distribute the new compound. The U.S. EPA TSCA Consent Order
Promoting a healthy environment,
DEQ-CFW 00000229

WVNPDES Permit No. VVVOOO 1279
Consent Order No. 7418
Response to Comments
Page 2 of 2
prescribed certain requirements and toxicological studies regarding the now compound.
In 2011, Dupont provided toxicological data to the WV DEP as well as plans to begin
production of the new compound. As noted, the U.S. EPA TSCA Consent Order
prescribes certain requirements on Dupont regarding the new compound and those
requirements are required to be achieved independent of Consent Order Pilo. 7418 that is
proposed by the WV DEP. The WV DEP reviewed the toxicological information
provided by Dupont regarding the new compound. Chronic studies which provide data
regarding long-term impacts are still being conducted by Dupont on the new compound
and are not yet complete. Although such long-term studies are preferable, toxicological
data from shorter -term (e.g. subehronic) studies may be used to determine a suitable
toxicity criterion, provided an additional safety factor is applied. Thus the agency
utilized subehronic (90 day) data developed by DuPont in support of its PMN submission
(subsequent to the 2009 TSCA Consent Order), incorporatmig appropriate
,safety/uncertainty factors, in order to calculate a risk -based Drinking Water Equivalent
Level (DWEL) for the new compound. As a courtesy, the agency has attached a memo
prepared by a WV DEP toxicologist which summarizes how the agency arrived at the
risk -based DWEL. As the requisite chronic studies are completed in the future, the
agency will revisit and revise, as necessary, the value indicated in the WV DEP Consent
Order. However, based on the information provided and all other information available
at this time, the WV DEP has determined that the requirements imposed will be
protective of West Virginia's narrative water quality standards found in 47 CSR 2,
Section 3 of the West Virginia Legislative Rules.
3. Comment: A public hearing is requested.
The agency received three (3) requests for a public hearing regarding the consent order.
Based on the limited comments received by the agency and resultant limited requests for
a public hearing, the agency has deten-nined that a public hearing is not warranted.
The agency would like to thank you for taking the time to submit comments.
The Division of Water and Waste Management issued Consent Order No. 7418 on January
31, 2012. Thank you for your interest in this order.
Sincerely,
Scott G. Mandirola
Director
Encolsure
cc w/enclosure: U.S. EPA Region 3
Env. Inspector Supervisor
Env. Inspector
DEQ-CFW-00000230

west viTglnia department of environmental protection
Office of Environmental Remediation
131 A Peninsula Street
Wheeling, WV 26003
Phone: [phone]/F-ax: 304-238-1006
To: Yogesh Patel
Matthew Sweeney
From: Lawrence P. Sirinek, Ph.D.
Date: January 31, 2012
Subject: DuPont GenX Toxicity
Pat Campbell
Scott Mandirola
Ken Ellison
Don Mat -tin
Earl Ray Tomblin, Governor
Randy C. Huffman, Cabinet Secretary
WWW'dep.wv.gov
I have completed my review of the documentation provided by DuPont regarding the toxicity of
GenX Compound A and Compound B. As I requested redacted documents, the identities and
chemical differences between the substances were not provided; however, most of the
toxicological studies appear to involve compound B. For this reason I have focused my
discussion on this compound. The relevance of the different compounds as they relate to
permitted discharges should be clarified with DuPont.
With regard to ecological endpoints, I concur with the points provided in the documents
provided by DuPont. Thus, 4.2 mg/L, reported as the 21 day NOEL (no observed effect
concentration) for Daphnia magna seems to be an appropriate endpoint for use in determining
discharge levels that would protect aquatic receptors.
With regard to human health effects, there were no data from chronic studies performed in either
rats or primates contained in the material provided by DuPont. Chronic studies in both rats and
mice are apparently ongoing, however data was not provided. While these data -would be
preferable, derivation of an appropriate toxicity criterion for human heflth cmi be based on a
subehronic (90 day) study performed in rats. In this particular study, DuPont indicates a
NOAEL (no observed adverse effect level) at 10 mg/kg/day, based on evidence of regenerative
anemia in mates at 100 mg/kg/d and females at 1000 mg/kg/d. Other effects were reported, but
are likely attributable to mechanisms that are often considered irrelevant to potential human
toxicity (e.g. PPARcx agonists).
With regard to the NOAEL, it must be noted that male rats exposed at this concentration (10
mg/kg/day) did exhibit significant decreases in erythrocyte (red blood cell) counts, hernatocrit,
and hemoglobin levels that are also indicative of anemia. DuPont considers the anemia
Promoting a healthy environment.
DEQ-CFW-00000231

DLIP0;It GenX Review
Janumy 31, 2012
Page 2
described by these parameters as non -adverse in this group, since the animals lacked evidence of
compensatory erythrocyte production (e.g. elevated reticulocyte counts). On the other hand,
while the reticulocyte counts were not sip ;ifnl icantly elevated in this group, there was a clear,
dose -dependent trend in the mean reticulocyte count at week 13. Unfortunately it cannot be
determined whether continued dosing beyond this time point would have resulted in more
dramatic indications of a compensatory response, or whether the impact was sufficiently limited
at the 10 mg/kg/day dose, such that no compensatory response was needed. Absent more
definitive data, the depressed red cell counts, hematocrit and hemoglobin levels should be
sufficient to constitute a health -protective endpoint for purposes of assessing the potential
impacts from chronic exposure to the test compound. Additional consideration should be made
when results of the chronic study are provided.
On the basis of a revised NOAEL of 0.1 mg/kg/day, and applying relevant uncertainty factors for
chronic to subchronic extrapolation (10) and rat to human extrapolation (10), the oral reference
dose (R.fDo) = 0.001 mg/kg/day. Based upon this value, a reasonable risk -based drinking water
equivalent level (DWEL) assuming total intake of the substance from a contaminated source
would be 35}ig/L. As discussed in subsequent communications, a source adjustment of 50%
could reasonably be applied to this value to allow for potential intake from other sources. Use of
this adjustment would result in a final DWEL of 18 µg/L. Based upon the information provided
by DuPont, I believe this value would protect both human health and the environment.
I hope this discussion is helpful. Please contact me should you require further discussion or
clarification.
DEQ-CFW-00000232

west virginia department of environmental protection
Division of Water and Waste Management
601 57°i Street SE
Charleston, WV 25304-2345
Telephone Number: [phone]
Fax Number: [phone]
Earl Ray Tomblin, Governor
Randy C. Huffman, Cabinet Secretary
www.dep.wv.gov
CONSENT ORDER
ISSUED UNDER THE
WATER POLLUTION CONTROL ACT
WEST VIRGINIA CODE, CHAPTER 22, ARTICLE 11
TO: E. I. du Pont de Nemours and Company DATE: 11/18/2011
Washington Works
c/o Karl J. Boelter, Plant Manager
P. O. Box 1217 ORDER NO.: 7418
Washington, WV 26181-1217
INTRODUCTION
This Consent Order is issued by the Director of the Division of Water and Waste
Management, Department of Environmental Protection, (hereinafter, the "Director") under the
authority of Chapter 22, Article 11, Section 1, et. seq. of the Code of West Virginia to E. I. du
Pont de Nemours and Company (hereinafter "DuPont").
FINDINGS OF FACT
In support of this Order, the Director hereby finds the following:
1. DuPont operates a multiple product line manufacturing facility and associated industrial
wastewater treatment plant located in Washington, Wood County, West Virginia. This
facility is known as the Washington Works Plant ("Facility" or the "Plant").
2. This Facility is permitted under WV/NPDES Permit No. WV0001279 (the "Permit"),
issued August 4, 2003 to authorize die Plant's point source dischargcs into the Ohio
River or tributaries thereof.
3. In accordance with 47 CSR 10-4.3, DuPont timely applied for renewal of the Permit on
December 20, 2007, over 180 days prior to the Permit's scheduled expiration date of June
30, 2008.
Promoting a healthy environment.
DEQ-CFW 00000233

DuPont Washington Works
Consent Order 7418
Page 2 of 6
4. Since DuPont's submittal of its renewal application, WVDEP has administratively
extended the Permit. As of the date of this Consent Order, the Permit remains
administratively extended until December 31, 2011.
DuPont has developed patented technology for a new -generation processing aid for the
production of high-performance fluoropolymers using a new compound C3 Dimer
Acid/Salt (CAS # 13252-13-6 and CAS # 62037-80-3) (hereafter the "New Compound").
DuPont represents that this technology is a sustainable solution that includes a new
processing aid with a favorable toxicological profile and rapid bioelimination. DuPont
further represents that it will utilize environmental control technologies that reduce
environmental release and exposure. The U.S. EPA, through a Toxic Substances Control
Act Section 5(e) Consent Order ("TSCA Order") executed by DuPont on January 28,
2009, granted DuPont approval, under conditions set forth in the TSCA Order, to
commercially manufacture, process, and distributes the processing aid. The TSCA Order
requires that DuPont shall recover and capture (destroy) or recycle the New Compound
"at an overall efficiency of 99% from all the effluent streams and the air emissions (point
source and fugitive)." This requirement is interpreted by DuPont to be applied in the
aggregate on an annual basis, for all U.S. sites where the New Compound is used. The
wastewater treatment system for the Facility's fluoropolymers processes will be modified
to achieve the TSCA Order requirements at present and future production capacity.
6. At this time, based on the results of its ongoing research and development activities,
DuPont is planning to undertake construction of related upgrades to the Facility's
wastewater treatment system for fluoropolymers processes currently discharging through
internal Outlets 102 and 305, in conjunction with the use of the New Compound, and to
commence the initial phase of commercial -scale production using the New Compound.
7. The planned upgrades to the fluoropolymers wastewater treatment system include new
higher efficiency processing aid recovery, addition of a new reverse osmosis ("RO")
system, and expansion of the existing carbon bed systems.
8. The Director cannot modify a WV/NPDES permit that has been administratively
extended beyond its original expiration date. Accordingly, WVDEP cannot currently
modify the Permit to authorize DuPont to scale up the use of the New Compound, to
discharge the New Compound, and to undertake the related wastewater treatment plant
upgrades described in Paragraphs 6-7, above.
9. DuPont provided toxicity data to WVDEP in March of 2011. Since that time, ongoing
dialogue has occurred and additional information shared between the parties regarding
the planned upgrades and the New Compound. On August 3, 2011, DuPont provided
additional toxicological information as well as plans to begin production using the New
Compound to the WVDEP.
10. The parties have entered into this Consent Order as the most expedient mechanism to
allow DuPont to begin construction activities in connection with necessary upgrades to
the wastewater treatment system and to commence commercial scale production using
DEQ-CFW 00000234

DuPont Washington Works
Consent Order 7418
Page 3 of 6
the New Compound, as described in Paragraphs 5 and 6 above, pending the Director's
renewal of the Permit. This Consent Order does not constitute and shall not be construed
as a finding by the Director that DuPont has committed any violation(s) of the terms and
conditions of the Permit.
ORDER FOR COMPLIANCE
Now, therefore, in accordance with Chapter 22, Article 11, Section 1 et seq. of the West
Virginia Code, it is hereby ORDERED by the Director as follows:
1. DuPont shall undertake construction activities associated with the above -described
wastewater treatment plant upgrades in accordance with the following schedule:
a. Modifications to the Granular Mother Liquor ("GML")/Lamella system to
achieve enhanced solids removal shall be initiated no later than six months after
the effective date of this Consent Order.
b. Construction of a new stage 1 RO unit with new membrane technology for
enhanced processing aid recovery shall be initiated no later than 12 months after
the effective date of this Consent Order.
c. Sub -micron filtration and additional RO units for recovery of processing aid from
previously non -recoverable process streams, and carbon beds for capture of
processing aid shall be installed no later than 24 months after the effective date of
this Consent Order.
d. Additional carbon beds in W9 Line 1 for enhanced abatement capability when
carbon change -outs occur shall be installed no later than 24 months after the
effective date of this Consent Order.
e. Connection of production areas to new recovery/abatement system as reflected in
the permit application shall occur no later than 24 months after the effective date
of this Consent Order.
2. During the period of transition to the new processing aid and treatment system upgrades,
wastewaters from fluoropolymers processes covered by these changes shall continue to
be treated by existing treatment facilities such that all wastestreams that are currently
receiving treatment via activated carbon will continue to receive such treatment. DuPont
has indicated that the New Compound will require more frequent change -outs of carbon
in the carbon beds in order to maintain treatment removal efficiencies. DuPont shall
replace the lead bed of granulated activated carbon within seven (7) days of detecting
break -through of the New Compound from the lead bed while maintaining an effective
polish bed in the system or cease discharge from the affected carbon bed systual, Should
monitoring detect breakthrough from the final polish bed, DuPont shall cease discharge
from the affected carbon bed system within 24 hours of detecting such break -through
until unspent carbon is in place to treat that wastestream. For purposes of this Consent
Order, "break -through" will be deemed to have occurred when concentrations of the New
Compound are detected at 1 mg/l or greater using the analytical method specified in
Paragraph 5, below. This requirement shall apply to internal Outlets 102, 305 and a new
internal monitoring location being designated as internal Outlet 605. Further, DuPont
DEQ-CFW 00000235

DuPont Washington Works
Consent Order 7418
Page 4 of 6
shall operate and maintain the granulated activated carbon beds at internal Outlets 102,
305 and 605 in a manner to prevent the inhibition of treatment of other pollutants.
3. Based on the toxicological information provided and all other information available at
this time, WVDEP has determined that a concentration of no more than 17.5 ug/1 of the
New Compound in the receiving stream outside of an applicable mixing zone will be
protective of West Virginia's narrative water quality standards found in 47 CSR 2,
Section 3 of the West Virginia Legislative Rules. To this end, WVDEP has established
the discharge limitations for the New Compound as set out in Paragraph 4, below.
4. DuPont shall adhere to the following limitations and perform the following self -
monitoring for the New Compound during the term of this Order in accordance with the
following:
Outlet
Monthly
Average
Maximum
Daily
Units
Monitoring
Frequency
Sample
Type
102A
Monitor
Monitor
u /1
1/day°
Grab
102E
Monitor
Monitor
u /l
1/week°
Grab
305A
Monitor
Monitor
u /1
1/dayD
Grab
305B
Monitor
Monitor
u /l
1/week°
Grab
605A,C
Monitor
Monitor
u /1
I/dayD
Grab
605B,C
Monitor
Monitor
u /l
1/week°
Grab
002
77E
112E
ug/1
1/week
24-hour
Composite
005
191E
278E
ug/l
1/week
Composite
A Monitoring location after exiting lead activated carbon bed and prior to entering polish
activated carbon bed.
s Monitoring location after exiting the polish activated carbon bed.
c Discharge from carbon treatment system located in building 127.
D When discharging.
s As discussed in Paragraph 3, above, these limits have been calculated to ensure a
concentration of no more than 17.5 ug/1 in the receiving stream outside of the applicable
mixing zone, as determined by application of the mixing zone dilution factor for the
respective outlet specified in the current Fact Sheet for the Permit.
5. Samples taken at Outlets 002 and 005 pursuant to Paragraph 4 above shall be analyzed by
Liquid Chromatography/Mass Spectrometry/Mass Spectrometry ("LC/MS/MS") with a
method detection limit ("MDL") of 1 ug/1 or less. Samples taken at internal Outlets 102,
305 and 605 pursuant to Paragraph 4 above shall be analyzed by liquid Chromatography
("LC") or Gas Chromatography ("GC") per internal plant method with an MDL of 1 mg/1
or less.
DEQ-CFW 00000236

DuPont Washington Works
Consent Order 7418
Page 5 of 6
6. Outlet results for sampling performed pursuant to Paragraph 4 above shall be reported
monthly to the WVDEP on the attached Discharge Monitoring Reports ("DMRs"). In
addition, DuPont shall maintain a log of the results of the daily monitoring required by
Paragraph 4 at internal Outlets 102, 305 and 605, and shall submit this log to WVDEP on
a monthly basis as an attachment to its DMR.
7. Commercial production using the New Compound and generating wastewaters for on -site
treatment may commence upon the execution of this Order, subject to compliance with
the provisions of this Order.
S. This Consent Order may be reopened and revised by agreement of the parties to prescribe
additional and/or different requirements, including different monitoring requirements
and/or increased or decreased discharge limitations, pursuant to any new information or
data regarding the New Compound.
9. This Order shall terminate upon notification by DuPont that the actions required by the
Order of Compliance have been completed and the Director's written concurrence
therewith or upon the issuance by WVDEP of a renewed permit for the Facility that
authorizes the activities covered by this Order that have not been completed as of that
time, whichever occurs earlier.
OTHER PROVISIONS
1. DuPont hereby waives its right to appeal this Order under the provisions of Chapter 22,
Article 11, Section 21 of the Code of West Virginia. Under this Order, DuPont agrees to
take all actions required by the terms and conditions of this Order and consents to and
will not contest the Director's jurisdiction regarding this Order. However, DuPont does
not admit to any factual and legal determinations made by the Director and reserves all
rights and defenses available regarding liability or responsibility in any proceedings
regarding DuPont other than proceedings, administrative or civil, to enforce this Order.
If any event occurs which causes delay in the achievement of the requirements of this
Order, DuPont shall have the burden of proving that the delay was caused by
circumstances beyond its reasonable control which could not have been overcome by due
diligence (i.e., force majeure). Force majeure shall not include delays caused or
contributed to by the lack of sufficient funding. Within three (3) working days after
DuPont becomes aware of such a delay, DuPont shall provide written nutificatiuii to the
Director. Within ten (10) working days of initial notification, DuPont shall submit a
detailed written explanation of the anticipated length and cause of the delay, the measures
taken and/or to be taken to prevent or minimize the delay, and a timetable by which
DuPont intends to implement these measures. If the Director agrees that the delay has
been or will be caused by circumstances beyond the reasonable control of DuPont (i.e.,
force majeure), the time for performance hereunder shall be extended for a period of time
equal to the delay resulting from such circumstances. A force majeure amendment
DEQ-CFW 00000237

DuPont Washington Works
Consent Order 7418
Page 6 of 6
granted by the Director shall be considered a binding extension of this Order and of the
requirements herein. The determination of the Director shall be final and not subject to
appeal.
3. Compliance with the terms and conditions of this Order shall not in any way be construed
as relieving DuPont of the obligation to comply with any applicable law, permit, other
order, or any other requirement otherwise applicable. Violations of the terms and
conditions of this Order may subject DuPont to additional penalties and injunctive relief
in accordance with the applicable law.
4. The provisions of this Order are severable and should a court or board of competent
jurisdiction declare any provisions to be invalid or unenforceable, all other provisions
shall remain in full force and effect.
5. This Order is binding on DuPont, its successors and assigns.
This Order shall become effective upon the date on which a true and correct copy of this fully
executed Order is received by DuPont.
E. I. du Pont de Nernours and Company
Public Notice begin:
Public Notice end:
Date
Date
Scott G. Mandirola, Director
Division of Water and Waste Management
West Virginia Department of Environmental Protection
SGM:rt/mis
Enclosure(s)
cc: Environmental Inspector
Environmental Inspector Supervisor
EPA Region III
i1 1-9 11
ate
Date
DEQ-CFW 00000238