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`Telomer Resetech Program Update, Apel 3, 2003
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TRP Telomer Research Program
AGC passcoum
s Clariant
Presentation For
US Environmental Protection Agency
y
3
TRP Presentation Outline
e Introductions and Agenda eo TRP US EPA Letter of Intent (LOI)
e March LOI Submissions April LOI Submissions
e Product & Article Analysis Rationale e Preliminary Biodegradation Study Overview
e Conclusions, Discussion & Questions
#
e Investigate the potential formation and/or release of
perfluorooctanoic acid (PFOA) from Fluorotelomer-based
polymeric products and consumer articles treated with such products and from manufacturing operations making or using these products
e Better understand telomer-based polymeric product
environmental fate and disposal
Ss
er
Fr Product and
Analysis
ra ER Analysis of
ER NY (oS)
Potential PFOA
Potential PFOA
+
Release from (8 3 EEO
Product Manufacture
Manufacture
and
Bio`dAengalryasdiastoifon
ae Te]
| EEE'] LT
*Analyses on Polymeric Products for Carpet, Textile, and Paper Segments Most of these analyses will be done in parallel, not sequential
Product Stewardship:
Added Programs & Handbook
Continuation of
ZA LEYEI e] Research Activities
7
Information
Exchange & Document Submissions
Product and Article Analysis
= Scope and rationale for analyzing for PFOA in telomer-based products
and telomer-treated articles by 31 March 2003 (done)
= Analysis for PFOA in representative telomer-based polymeric products
and telomer-treated articles
= Covers primary polymeric product end-use applications: carpet, textiles,
paper
= Information on products to be tested to be provided by TRP companies (under CBI) -- by March 2003 (done); other products and applications -- by May 2003 [CAS #/ name/ structure, 2002 use and volume |
= Method development and validation to begin in March 2003 followed by
sample analysis; results expected by June / July 2003
8
Analysis of "Aged" Products and "In Use" Articles*
= Develop plan for conducting PFOA "aging" and "in use" analytical studies in initial end use segments of Carpet, Textiles, and Paper by April 2003.
= Define relevant "aging" and "in use" conditions for carpet, textiles, paper
including light exposure, "walk off', degradation, volatilization, and
leaching
= Develop appropriate analytical methods and study protocols -- in Qtr 2 /
2003
= Conduct and complete studies by Qtr 3/2003
*For this analysis, "aged" means the storage and distribution of products and
"in-use" means the distribution and use of the treated articles
7
Characterizing Potential PFOA Release from Product
Manufacture
= Provide general outline of process chemistry employed in telomer
manufacturing and processing operations -- by March 2003 (done)
= Describe specific telomer manufacturing process chemistry by
member companies and submit information about potential release of
PFOA or exposure points from telomer manufacturing and processing (US operations; likely under CBI) - by April 2003 = Develop action plans to investigate the potential for PFOA release and exposure (TRP member companies) - by end of May 2003
Io
ere
CF,CF,
Tetrafluoroethylene
FCF. (CF.CF.),!
SEE F(CF,CF,) CH,CH,l
Telomer Intermediate.
"Building Blocks"
ood Sow F(CF,CF;),CH=CH,
F(TCeFl,oCmFe;r)8,CAHl.cCoHho,lOH
rit Honorsiha motomen owatl a rian F(CF,CF),CH,CH,0C(O)CH=CH,
u
L [SaT]E
Amcatnuuaflacptruorciensgs and
company practices vary by
+ PFOA is not used or
processes added in these
+ Generally, these processes are closed and PFOA creation
aenxdp/eocrteedmitsosbieonast are
very low levels
Characterizing Potential PFOA Release from Article
Manufacture
= Develop article manufacture release estimations of PFOA (carpet, textiles, paper); completion by June / July 2003
= Develop and demonstrate sampling and analytical methods for PFOA determination in mill simulations -- during Qtr 3/2003
= Conduct mill simulations of potential releases of PFOA from telomertreated article manufacture -- begin in Qtr 3/2003
=
Telomer Research Program
_
Biodegradation Analysis of Polymeric Products
= Develop study approach, protocols and rationale for conducting
biodegradation analyses of telomer-based polymeric products -- by
April 2003 to EPA for review and comment
= Conduct biodegradation studies for potential generation of PFOA from
polymeric products used in Product & Article Analysis -- results
expected beginning in July 2003
3
Analysis of Incineration
= Compile information on polymeric products and uses to understand ultimate fate and disposal routes (landfill versus incineration) for
telomer-treated articles in US -- provide to EPA by July 2003
= Review applicable incineration tests and provide summary of information to EPA by end of Qtr 2/2003
I
Product Stewardship for Customers
= TRP member companies will have additional product stewardship
programs for customers / users of telomer-based products and telomer-treated articles in place by July 2003
= Programs will be designed with reference to the Responsible Care guidelines outlined in SOCMA Management Practices / Product
Stewardship Code
= Develop TRP Safe Handling and Use Handbook for customer review --
by August 2003
I
is
Continuation of 8-2 Telomer Alcohol Research Activities
= Toxicology and Pharmacokinetics (pilot studies) = Physical-Chemical Properties = Submit 8-2 Telomer alcohol preliminary biodegradation screening
study reports to EPA by 24 March 2003 (done)
= Environmental Fate & Effects
Hydrolysis, atmospheric degradation, ecotoxicity, biodegradation
16
o Information Exchange
= Final reports from TRP-sponsored studies as they become available (ongoing); report schedule for 2003 provided to EPA
= Provide list and copies of documents and materials in TRP database
-- March / April 2003; new documents as they become available
= Information from TRP companies on their own studies on telomer products sold in US market -- as they become available
= Periodic briefings, expected to be monthly, to summarize current
results from telomer studies
EN
--
= Develop site specific plans on its US operations to assess levels of PFOA in air and water from manufacturing operations around each site; development of plans
will begin not later than 30 days after the date of this letter.
= Conduct site-specific air dispersion modeling for applicable manufacturing operations, using the EPA approved Industrial Source Complex Short Term 3 (ISCSTS) model, as described in EPA's Guideline on Air Quality Models (40 C.F.R. Part 51, Appendix W), and assess the results using the air screening levels
established in West Virginia.
= Conduct ground and surface water analyses at each site, and assess the results using the water screening levels established in West Virginia.
= Use the West Virginia screening levels to determine what additional actions, if any,
may need to be taken, after reviewing the information with EPA.
18
= Six months after this Letter is submitted, reports will be submitted for each site on progress made with respect to environmental assessments.
= In addition, by April 1, 2003: provide EPA with applicable existing industrial
hygiene air monitoring data for PFOA from DuPont operations at Chambers Works; and the DuPont telomers business will provide EPA with summary data on existing employee blood monitoring results from telomer manufacturing operations and PFOA recycle operations at Chambers Works. (item completed)
9
are
TRP March LOI Submissions
TRP Submissions to EPA - Planned for March 2003
[
e/Descripon
[TRP Database List
|Company-specific information on products --- submitted as CBI
General Description of Telomer Process
Biodegradation Research - Scope & Rationale
Product & Article Analysis - Scope & Rationale
Air monitoring data for PFOA from DuPont operations at Chambers Works
Employee blood monitoring data from telomer manufacturing + PFOA recycle
operations
3Apil 2008
[Contracto|r
[asp|
[arp|
m [aer] e|
|oom |
(DuPont)
I
20
arr TRP April LOI Submissions
TRP Submissions to EPA - Planned for April 2003
3 April 2003
Title / Description
|Contractor|
[Submit plan for review and comment on conducting PFOA "aging" and "in-use" analytical
studies in carpe, textile, and paper end-use segments
Description of specific telomer manufacturing process chemistry by member companies
and information about potential releases of PFOA and exposure routes from US
operations
(TRP Companies)
Develop study approach, protocols, and rationale for biodegradalion analysis of polymeric
[products used in the Product and Article Analysis and share with EPA for review and
comment
(RP)
Provide copies of documents and other materials from the TRP database
I
&
re
i}
Product & Article Analysis Summary
Purpose
= To investigate the potential formation and/or release of PFOA from
telomer-based products and consumer articles treated with such
products
= To determine whether articles treated with representative telomer-based products contribute to significant human or environmental exposure to
PFOA
22
Overview
= Screening Study -- being conducted by independent research lab - Treated Articles
+ 3 major end-use applications -- carpets, textiles and paper = Samples of telomer-treated articles under representative or actual mill
conditions
Primary Products
+ Polymers -- represent approximately 85% of telomer-based products manufactured and sold by TRP member companies
= Primary product classes in commerce - 12 product formulations to be
tested
I
Product& Article Analysis Summary
Appr &Mo ethaodc olohgy
Method Development and Validation
Develop sampling, shipment and analysis procedures (TRP experts) Prepare primary and [1,2-13C] PFOA analytical standards
Identify and solicit bids from potential contract labs; select lab Develop method for quantitative determination of PFOA in various article matrices and
telomer-based products (contract lab) Validate methodology for determining PFOA in treated articles
Atticle Analysis
Collect and provide samples of 12 telomer-treated articles (TRP companies)
- samples from pilot plant facilities or commercial manufacturing facilities
Types of samples: representative textile, carpet and paper articles (12 total) Analyze samples for PFOA using developed / validated analytical method
er
Product & Artile Analysis Summary
Approach & Methodol
Atticle Analysis (cont)
LC/MS/MS method with [1,2-'3C] PFOA internal standard Lower limitof quantitation for PFOA: 1 ppb
Relative standard deviation: less than 20%
Extraction efficiencies goal: 70-110% for 3 matrices - carpet (nylon), textile (polyester) and paper
- PFOA fortification levels: 1 ppb, 10 ppb, 100 ppb
Samples: 162 untreated carpet (shaved), textile and paper samples
Method validation under GLP - 36 samples for each article: 6 samples each at 1 ppb, 10 ppb, 100 ppb
on 2 separate days (108 total)
EE
a5
Product & Article Analysis Summary
:
Approach & Methodology
Article Analysis (cont) Test Samples: 12 articles treated with single telomer-based polymeric product
(4 unique carpet/product paris, 6 textile/product pairs, 2 paper/product pairs)
- 6 sub-samples to be analyzed for each article / product pair (72 total) - samples selected by block design approach - 4 untreated samples for control and extraction efficiency verification
| cosoiospoceze
26
|]
Product &Article Analysis Summary
=
Approach & Methodolo:
Product Analysis
Product types: acrylate and urethane polymers (12 product formulations) LC/MS/MS method with [1,2-1C] PFOA internal standard Lower limit of quantitation for PFOA: 1 ppm Relative standard deviation: 20% Extraction efficiencies to be evaluated (prior to product analysis) on 2-3
product groups Product analysis to be conducted under GLP
I
27
Telomer Research Program
Product & Article Analysis Summary
poi
Schedule
January - February 2003
Develop sampling, shipment and analysis procedures (TRP experts)
Prepare primary and [1,2-'3C] PFOA analytical standards
Identify and solicit bids from potential contract labs; select lab
Prepare internal standard for use by contract lab (TRP company)
March -- April 2003
Develop and validate analytical and sample methods (contract lab)
Prepare and deliver samples to contract lab for analysis (TRP companies)
May - June 2003
Analyze telomer-treated articles and telomer-based polymeric products Prepare final report (expected June/July 2003)
28
Preliminary Biodegradation Screening Overview:
EY
29
|
CATABOEBiodegradation Prediction IRs eve URIS ls
se 4
0.0%
C4F,CH,CH,OH
0
i
\
13.7%
C,FsCF=CH,
75%
6.8%
C4F,,CH,COOH
C,F,sCF=CHCOOH |}
|
et
|
12%
C,F,<C(O)COOH
3.3%
C,F,sCOOH
* The sum of the % values = 100
* The model predicts this will be the distribution of transformation products
L2oosoioaaeze 30
Le
8-2 Telomer B Alcohol
Biodegradation Screening Stu-dDui Pone t..s . |
28 Day "Ready" Biodegradation Screening Study
= Cold Test Material CyF,,CH,CH,0H
Test Systems + Non-acclimated municipal sludge
= 8-2 Telomer B Alcohol is the only carbon source
= Endpoints monitored : parent loss, fluoride
Began Dec. 2002
Laocsoiosoacezo 31
arr
8-2 TelomeBr Alcohol
Zi ggradation Screening Study - DuPont:
.
* Growthmedium:
Aerobic Ready Biodegradation (Modified OECD
301D Closed Bottle Test) (12/31/02 - 1/28/03)
OECD 301D mineral medium ~~ 20
without yeast extract
3g
Em
Inoculumsource:
32 Sw
POTW, fresh sludge
<o
(Incubated f0o-r28 days) 0
o Conclusion:
3el R_ams gems et
Kile siu+dg8.e2 TooBmAkoehorl|
8-f 2 TBA is not readily
biodegradable.
Leosoiosoaoco
o Ts ww wm mw
Days after the initiation
32
Telomer Research Program
BLL FT
K
Biodegradation Screening Study - DuPon=t> = |
e Growth medium:
Aerobic Ready Biodegradation (Modified OECD 301D Closed Bottle Test) (12/31/02 - 1/28/03)
OECD 301D mineral medium ~~ #
without yeast extract
w
o Inoculum source:
POTW, fresh sludge
a2 by
<
g _ (Incubated f0o-r28 days) 2
* KeOybservation:.
No defluorination occurred.
Sf] 8 Afctivaated sstlua+d68:22gTTBoeAk s saturata ed minora dmeedsium
-
o
5
10
15
2
2
0
Days after the initiation
33
|
re
LAC TdF
SL
El
:
a TL eg aIT ey
Accelerated Screening Study
= Cold Test Material CgF,,CH,CH,0H
= Test Systems
+ Acclimated industrial sludge
= yeast extract as additional carbon for co-metabolism = Endpoints monitored : parent loss, fluoride, fluorinated
acids
Began July 2002, Completed January 2003
I
34
_
BiBoCdC egrTadA atiF onTScrGeening
Study
Sis =DuPont.
o Growth Medium:
E2-BSMYE (2 g/L of yeast
extraacst additional
tn
carbon)
~7
Inoculum source:
2
Industrial WTP (28 days;
TAS50-51-52; 7/ -8/1 16/9 02)
3"
5"
StaCornctofi 8-2nTBgA: =<
~800 ppb
Fd
Observation:
5
82TBAhasbeenrapidly ~~
biotransformed
3
o
ETT
~"oA--daAKpicltcedeebldaecbrkaracattelrecidaucBluietuor+de2e+mg5:rM2 TaNdBaaACtNi+o
n
82
TB
A
Ts
ww
-- ws ow
Oooore tation
35
8-2 Telomer BAlcohol ia
ELIE creening Study -DuPon ik
o Growth Medium:
Accelerated Biodegradation
E2-BSMYE (2 g/L of yeast
extract as additional
carbon)
o Inoculum source:
EEKi vaca cure2ANaN + 8:2 TBA
=
ee
--
Industrial WTP (28 days;
4
TA50-51-52; 7/19 - 8/16/02)
2
e Starting Conc of 8-2 TBA:
g
~800 ppb
5
o Observation:
2
A net increase of 60 ppb of *
. fluoride over 28 days.
2
ETT
Doveafter theinflation
36
|
CRCTA FT
i
BiodegradationScreening Study - DuPo 2
Accelerated Screening Study : Identified Transformation Products*
FICF).OHOH.ON
~ Mass Balance** (%)
5 F(CF,)sCH,COOH
2
i
}
$2 | F(CF,),CF=CHCOOH
>10
583
}
38
FeFargoo
<2
8
F(CF,);COOH
04
* Only these four transformation products were monitored for. Other potential transformation
products were not determined.
** Mass Balance was not a primary objective and was not achieved
37
|
TRP is actively and aggressively conducting work and
analyses on telomer-based products, treated articles and
processes
Protocols and procedures are being developed
Significant analytical challenges remain
The TRP believes telomer-based products are safe for
their intended uses and is committed to continued work
to support this conclusion.
38
Mo LTE ELLE TTL
Letter of Intent Comments
8-2 Alcohol Program
Regulatory Items and Actions
EE
"
|