RM2 EXIT BRIEFING ON
CHLORINATED PARAFFINS AND OLEFINS
September 1,1993
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Chlorinated Paraffins and Olefins RM2
Workgroup Members
Blake-Hedges, Lynne
Brandt, Ethel
Brooks, David
Brooks, Edward
Dillman, Susan
Dutrow, Betsy
Lipnick, Bob
Lynch, David
Macek, Gregory
Margosches, Elizabeth
Medici, Andrea
Metz, Fred
Miller, Patrick
Murray, Tom
Smrchek, Jerry
Spitzer, Martin
Watford, Darlene
Williams, Richard
TS-779
TS-778
TS-778
TS-794
TS-798
TS-798
TS-796
TS-779
TS-779
TS-796
LE-132P
TS-779
TS-778
TS-779
TS-796
7409
TS-798
RD-675
260-7241
260-2853
260-3501
260-3754
260-5375
260-3978
260-1274
260-3911
260-9597
260-1511
260-7524
260-0684
260-1267
260-1873
260-1268
260-4342
260-3989
260-2577
E231
E401
E447I
E515A
E311
G012NE
E431F
E320
E343B
E305
WIC#8
E351A
E441C
E321
E423
3134CY
NEG012
NE306
EETD/RIB
CSRAD/RAB
CSRAD/AIMB
OPPT/CCD
CMD/TPD
CMD/TPD
HERD/EEB
EETD/EAB
EETD/CEB
HERD
OGC/PTSD
EETD/ICB
CSRAD/RAB
EETD/EAB
HERD/EEB
PPD/PAB
CMD/TPD
ORD/OER
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TABLE OF CONTENTS
Summary 1
I. Overview and Background 3
Significant Milestones .. . 3
Physical-Chemical Data .T.~ .... 77777777 17777. 777!3~
Production and Uses 4
Fate and Transport 4
Releases 4
Substitutes 4
II. Ecological Risk 5
Strategy 5
Substances of concern 5
Hazard 5
Regulations 6
Releases 7
Exposures: Monitoring 7
Exposures: CPIA Survey of Formulators 8
Risk Characterization 10
Screening Results 10
EXAMS II Results .10
CASM Results 12
Economic Assessment 12
Foreign Government Assessments 16
Further Research 16
1. Monitoring 17
2. Sediment toxicity testing 18
3. Investigating Formation ofDioxin During Metalwortdng 18
4. Characterizing End-User Disposal Technologies and Practices 18
5. Fish Toxicity Testing 19
6. Assessing Potential Effects on Terrestrial and Avian Life 19
7. Determining Distribution of CP/Os 19
8. Assessing Potential for Dioxin Formation 19
HI. Human Health Risk 20
Metalworkers 20
Subsistence Fisheaters 21
Manufacture of Resinous Long Chain CPs 21
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IV. Options and Recommendations 22
Option 1 22
Option 2 22
Option 3 23
Option 4 24
Option 5 24
Recommendation 25
D'iScussi6h"77T/\Trr;r:T7"^
TRI Listing 25
Monitoring 25
Master Testing List 26
Referral to OSHA 26
Referral to Region 5 26
Referrals to Agency Dioxin Workgroup 27
Interchangeability of Elements within Options 27
Metalworking Fluid Cluster 28
Appendix 1: Foreign Assessments 29
Overall level of Concern 29
General State of Knowledge 30
Regulations and Recommendations 30
Ecological Toxic Thresholds 31
Water Concentrations 32
Transportation in the Environment 33
Persistence and Degradation 34
Substances of Concern 35
Dioxin Formation 35
Sources of Release 36
Production and Use 36
References 38
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Summary
The RM2 investigation looked at both ecological risks, the major concern, and human
health risks.
The ecological assessment was advanced in four areas. First, it was established that the
substances of greatest concern are short chain (C10.13) chlorinated paraffins (CPs) and Olefins
metalworking fluids, and are essentially indistinguishable from CPs in toxicity, persistence, use
and disposal.
Second, the investigation determined that virtually all ecologically significant releases of
CP/Os to the environment are from metalworking operations discharging to water -- and that all
of those releases are contained in the water fraction of water soluble cutting fluids discharged to
water after separation from the oil phase.
Third, the hazard analysis was revised based on new toxicity and bioconcentration
studies, and on policy decisions by OPPT Division Directors, yielding the folloving values.
1. Lowest level of concern concentration: ........ 0.03 /ig/1
2. Mid-level of concern concentration: .............. 0.11 /ig/1
3. Highest level of concern concentration: ......... 0.7 /ig/1
4. Most likely range of concern: .............. 0.11 to 0.7 /ig/1
5. NOEC: [[[ 1.0 to 5.0 Mg/l
6. GMATC: [[[ 3 to 7 Mg/l
7. LOEC: [[[ 8.9
Fourth, in-house analysis of Survey data covering sales of short chain water soluble
cutting fluids in major markets suggests that CP/Os pose relatively low ecological risk. The
analysis estimates that 186, or 75 percent, of 248 localities within the four States that consume
the greatest amounts of metalworking fluids have in-stream concentrations below the lowest
level of concern (0.03 /ig/1); 28 fall within the low range of concern (0.03 < 0.11 /ig/1); 26 within
the "most likely" range of concern (0.11 < 0.7 /ig/1); five between the upper bound of the level
of concern and the lowest estimated No Observed Effect Concentration (0.7 < 1.0 /ig/1); and
two within, and one just above, the low range of the estimated NOEC (1.0 < 3.0 /ig/1), and at or
below the lowest estimated Geometric Maximum Acceptable Toxicant Concentration. Fourteen
percent fell within or above the "most likely" level of concern. These estimates do not consider
the relative insolubility of CP/Os. Taking partitioning from the water column to sediment into
account reduces these estimated in-stream concentrations by 14 to 56 percent.
An aquatic simulation model projects low probability of any effect to any trophic level at
a water concentration of 1.0 /ig/1, a level exceeded in only three of the 248 localities. An
economic benefits model applied to these results estimates that reducing CP concentrations
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There are some human health concerns, particularly among metalworkworkers. Based
upon a number of "high end" exposure assumptions, there may be as many as 157 U.S. excess
lifetime cancer cases. The investigation also concluded that there may be an individual excess
lifetime cancer risk as high as 5 x 10"*, in a few of the highest in-stream concentration areas,
among indigent people who subsist primarily upon fish they, catch. Although the nature of the
population at risk raises an "environmental equity" concern, the small number of people involved
renders the population risk negligible. There may also be a lifetime individual excess cancer risk
~as high as 10'3lirm>hg~a 'veryrsrnall'populati6n15f workers"employed in "manufacturing resinous""
long chain CPs.
Although unevaluated in this assessment, CP/Os in metalworking fluids also pose two
potential exposures to dioxin/furans. The first is to metalworkers as a result of using
chlorinated fluids at high temperatures; the second is to the general population as a result of
incinerating spent fluids.
Finland, The Netherlands and The United Kingdom recently completed assessments of
CPs. Each concluded that CPs probably pose little risk in their countries. Finland and The
Netherlands recommended additional research to develop more release information. An
impending assessment in Canada may recommend defining CPs as "toxic". A 1991 Swedish
proposal to phase out use of CPs in Europe, voted on this past June, was not adopted.
Five options were considered for closing the RM2 investigation. Irrespective of the
option selected, it is recommended that OPPT (a) refer the occupational risk to OSHA, (b)
refer the dioxin issues to EPA's Dioxin Workgroup, and (c) advise Region 5 of the subsistence
fish-eater risk. The options are:
Option 1: Close with no further action.
Option 2: Negotiate voluntary agreements with industry to: (1) promote pollution
prevention practices by reducing use of short chain CPs, and reducing discharges
to water; and (2) conduct i^earch - especially surface water monitoring and
sediment toxicity testing -- to -ddress remaining uncertainties.
Option 3: List on TRI and dose with no further action.
Option 4: List on TRI, seek funding from the Water Office to monitor CP/Os in high use
areas, and add CP/Os to the Master Testing List (MTL).
Option 5: Regulate aggressively with information-gathering, public notification, and
restrictive authorities of SARA §313 and TSCA §§4, 8 and 6 to discourage use of
short chain CP/Os in metalworking fluids.
Option four is recommended. It is also suggested that a "metalworking fluid" cluster be
added to the Design for the Environment/Use Cluster hopper for a start in FY 94 or 95.
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I. Overview and Background
This report is in four parts. This first part provides general background information.
The second addresses ecological risks posed to aquatic life from concentrations of CPs in
surface water resulting from industrial releases. This was the major concern emerging from
RM1. The third part covers carcinogenic risks to human health. This was believed to be a
"minor concent at R^
part presents risk reduction options and recommendations.
Significant Milestones
1977: CPs nominated for testing by ITC.
1982: Testing agreement between OTS and Consortium published.
1983: §8(e) Notice submitted by Consortium based on testing results.
1985: HERD ecological hazard and risk assessments completed.
1985: OTS Decision Memorandum recommending monitoring.
1988: OTS-initiated monitoring of Sugar and Tinkers Creeks completed.
7-3-91: RM1 Decisions: (Ref.# 9) Enter RM2; approach industry to (a) request
better information about releases; (b) present the rationale for additional
testing; (c) clarify whether industry agreed to treat test results on most
toxic category of CPs as applicable to all CPs; and (d) pursue pollution
prevention remedies.
9-16-91 Initial meeting with Chlorinated Paraffins Industry Association (CPIA) to
discuss Letters of Concern.
6-18-92: Proposal received from CPIA offering to (a) conduct a Survey of
^ Formulators to obtain better information on releases, and (b) continue
&' and expand on-going efforts to promote pollution prevention and waste
minimization.
6-25-92: OPPT ECMR Decision: Follow-up on CPIA proposal.
6-21-93: CPIA Survey of Formulators received.
Physical-Chemical Data (Ref.#s 7 and 47)
Chemical name: Chlorinated Paraffins
Molecular Formula: C10.14Hl7.2iClM
CAS Number: 63449-39-8
Molecular Weight: 411 for C12H,,C17
Log P: 5.47-7.30 (M for C1(M3 Cl 63% Cl)(6.32 GAvg)
Water Solubility: 95-470 /zg/1 (M)
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Production and Uses (Ref.#s 10, 21 and 34)
1992 domestic sales were in the neighborhood of 65 million pounds (Ref.# 34). Taking
exports and inventories into account, this is in line with production figures reported by CP
producers for the years 1987 through 1990. Demand is expected to remain relatively stable over
the foreseeable future. All, or virtually all CP/Os are produced by four companies: Occidental
JPetroleum, with plant capacity of JO million Ibs.; Keil Chemical Division of Ferro Corp, with
plant capacity of 50 milliori I&T^Dl^FCKeTnicairwith^^
Corp., with 12 million.
Roughly half of all CPs produced are used as extreme pressure additives in metalworking
cutting fluids; another 20 percent as primary and secondary plasticizers in plastics; 12 percent as
flame retardants in rubber; nine percent in paint; six percent as plasticizers in adhesives, caulks
and sealants; and three percent in miscellaneous other uses.
Fate and Transport (Ref.# 20)
CP/Os that are incinerated are destroyed (although dioxin may be formed in the
process). For the remainder, the high soil organic carbon partition coefficient and low water
solubility results in strong sorption to soils and sediment. Consequently, CP/Os that are
landfilled are assumed unlikely to migrate or leach to groundwater. Releases to water therefore
probably constitute essentially the only source of ecologically significant exposures. Because of
their insolubility, the bulk of CP/Os released to water are expected to partition to suspended
solids and sediment. Other potential sources are volatilization from land and water, and air
particulate dispersion. The likelihood of transfer from solids and sediments is unknown.
Releases (Ref.#s 21 and 44)
About 55 percent of all CP/Os released to the U.S. envkonment are discharged to water,
less than one percent is released to air, and the remaining 44 percent is recycled, incinerated or
landfilled where, for the reasons noted above, they are unlikely to create environmental
exposures. Metalworking Quid end-users are responsible for virtually all releases to water.
End-user releases of short chain CP/Os to water are comprised almost entirely of those
remaining in the water phase of water-soluble cutting fluids, after the water has been separated
from the oil prior to discharge. All "straight" (non-water-soluble) oils and the oil phase of all
water soluble oils are believed to be recycled, incinerated or landfilled.
Substitutes (Ref.#s 10 and 21)
Only general information has been found on substitutes for CPs. Substitutes for use in
cutting fluids is the primary concern, because metalworking accounts for almost all releases to
water and most occupational exposures. Possible substitutes in this area include chlorinated fats,
fatty acids and esters, sulfurized additives, chlorosulfurized additives, phosphate thiophosphate
additives, overbased sulfonate salts, oil soluble borates, lead compounds, and cryogenic fluids.
Most sources agree that while substitutes are available for CP/Os in some metalworking
applications, in general they are not entirely satisfactory.
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II. Ecological Risk.
Strategy
The RM2 ecological investigation assessed the magnitude of risk posed by CPs in
circumstances in which that risk js believed to be both most likely and most severe. Based on
information generated before ancTduiring"FOvl2rit was determih^lh^nHb^"t;ii^nWtances' arise"
when various forms of aquatic life, the most sensitive organisms, are exposed to short chain CPs,
the most toxic form, in areas where metalworking operations, the major source of releases, are
most heavily concentrated. Focussing the investigation in this manner permitted a realistic
assessment of the greatest ecological risks likely to occur. The two major tasks in this effort
were to (a) obtain agreement on the magnitude of the hazard, and (b) develop estimates of in-
stream concentrations in those geographic localities in which the greatest amounts of CP/Os are
released.
Substances of concern
The RM1 analysis (Ref.# 8) concluded that the greatest risk was posed by short chain
CPs with 58% chlorination. Based on confirmation by the Division Directors of CCD, HERD
and CSRAD (Ref.# 32) that these were the substances of greatest concern, the RM2
investigation concentrated on short chain (C10.13) CPs. Conversations with CP producers
revealed that olefins (chain length C12) are also used in metalworking fluids. Since olefins are
structurally similar to CPs, there is no reason to believe they are less toxic than short chain CPs:
they were therefore included.
Hazard
-*!f
Chronic toxicity drove the CP/O ecological assessment. CCD, HERD and CSRAD
Division Directors reviewed analyses of the hazard (Ref.#s 25 and 28) and revised the
estimates that emerged from RM1 to the values shown below.
RM1 Exit RM2
Levels of concern 0.006-0.01 /xg/1 0.03-0.7, closer to 0.7
LOEC 0.6jig/l . 8.9jig/l
NOEC Not found 1.0-5.0, closer to 5.0 fj.g/1
Estimated NOEC « 0.1 /ig/1 Not applicable
GMATC" 1.2 to 2.4 /ig/1 3 to 7, closer to 7 /ig/1
Margins of exposure 60-100 10-100, closer to 10
''Geometric Maximum Acceptable Toxicant Concentration: the square root of the product of
the LOEC and NOEC.
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Estimates derived from the Division Director conclusions yield the following significant
hazard and concern numbers:
1. Lowest level of concern concentration:*' ..... 0.03
2. Mid-level of concern concentration:*' ............ 0.1 /xg/1
3. Highest level of concern concentration :(e> ...... 0.7 /zg/1
4. Most likely range of concern:(d) .......... 0.11 to 0.7 /tg/1
6. GMATC: [[[ 3 to 7
7. LOEC: [[[ 8.9
» Lowest GMATC/highest MOE = 3/100.
w Mid-range GMATC/mid-range MOE = 5/45.
(c) Highest GMATC/lowest MOE = 7/10.
<« Greater weight given to high end GMATC, low end MOE.
Regulations (Ref.# 19)
Regulations under the Clean Water Act prohibit any releases of used oil to water that
(1) cause a sheen to appear on the surface, (2) violate applicable water quality standards, or (3)
cause sludge or emulsion to be deposited beneath the surface of the water or on adjoining
shorelines. Indirect dischargers must meet POTW-imposed restrictions on the concentrations of
"Fats, Oil and Grease" (FOG) allowed in facility effluent. These restrictions are typically in the
50 to 250 ppm range. The highest found by the Workgroup, in Detroit, is 2,000 ppm. Even this
highest level, however, precludes discharges with oil content above 0.2 percent.
In September of 1992, concluding a series of proposals and promulgations that
commenced in 1978, OSWER promulgated a final rule (Ref.# 19) entitled Identification and
Listing of Hazardous Waste; Recycled Used Oil Management Standards. That rule stipulates that:
1. To encourage recycling, EPA will not list recycled used oil as hazardous waste.
2. Recycling includes reuse for any purpose, including oil being re-refined or being
processed into fuel.
3. All used oil is presumed recyclable; therefore neither the generator nor anyone
else who handles the oil, prior to the person who ultimately decides that the oil is
not recyclable, is required to take that possibility into account.
4. Used oil disposal (as opposed to recycling) must be done in compliance with all
applicable regulations, including the requirement to determine whether the used
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5. There is a rebuttable presumption that any oil - including oil that might
otherwise be recycled -- containing more than 1,000 ppm of halogens, is oil that
has been mixed with chlorinated hazardous waste, and must therefore be treated
as hazardous waste.
6. Because metalworking fluids to which chlorinated extreme pressure additives (i.e.,
CP/Os) have been added may exceed the 1,000 ppm halogen limit without having
_... _.,. o^^'mixeli with'fralzaTdoWw^
from the rebuttable presumption. Specifically, metalworking fluid end-users who
enter into a tolling agreement with used oil refiners/processors to re-refine and return
the oil for further use are not required to rebut.
Releases
The number and diversity of metalworking operations made it infeasible to acquire direct
CP/O release data from end-users. Based upon restrictions imposed under CWA and RCRA,
described above, the RM2 analysis assumed that no metalworking fluid end-user can legally
discharge, directly or indirectly, any "straight" oil, or the oil fraction of any water soluble oils.
Almost all CP/Os released to water are therefore assumed to be those remaining in the water
phase of CP/O-bearing spent water-soluble oils after separation and treatment prior to
discharge.
It is also assumed, because of the RCRA exemption described in # 6, above, that
metalworking fluid end-users now have a powerful incentive to establish tolling arrangements
with professional processor/refiners to periodically pick up, reclaim and return for recycled use,
all used oils containing CP/Os.
Exposures: Monitoring (Refs.# 1, 20 and 35)
Concentrations of CP/Os in water has been the critical information gap throughout
OPPTs assessment. Until the results of the Survey discussed in the next section became
available, a few monitoring studies ~ completed in the late 1970s and mid 1980s - provided the
best estimates of the distribution and concentrations of CPs in water. The most comprehensive
work was done in the British Isles in 1980 by Campbell and McConnell. They detected short
and intermediate chain (Clo.2o) CPs above 0.5 /ig/1 in three of 18 observations in marine water ~
but with one observation, in the outer Hebrides, as high as 4.0 jig/1. In freshwater remote from
industry, they found concentrations above 0.5 /tg/1 in one of 16 observations, but in freshwater .
proximate to industry they found concentrations above 0.5 jtg/1 in 16 of 25 observations - with ,
one as high 6.0 jig/1. These findings suggest that short chain CPs may be atmospherically
transported long distances, but will be found consistently, and in higher concentrations, near the
sources of discharge.
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OPPTs 1986 monitoring of Sugar Creek, near Dover Chemical's manufacturing facility,
found concentrations of short chain CPs at 0.21 /ig/1 in particulates in water at the outfall, and
0.3 fig/I in particulates in water upstream from the outfall. The latter is suspected to have
resulted from overflows from a now-closed lagoon. Monitoring of a metalworking fluid end-user
on Tinkers Creek, did not detect CPs in either filtered water or particulates. This is believed to
be due to the difficulty of detecting CPs in complex mixtures of halogenated organics.
4 '"r"r*""Snort cfiain CPTwere^etected'in thlTHouston SHijpTCKannel'in 1978 aTlevels ranging
from less than 1.0 /ig/1 to one measurement at 1.5 /xg/1. The highest concentrations were found
in 1977 near a Diamond Shamrock facility on the Grand River, where concentrations were as
high as 3.0 pg/1 in the stream both above and below the plant.
The existing monitoring work has three drawbacks. First, the analytical limits of
detection and quantitation have been in the vicinity of 0.2 and 0.5 /*g/l, respectively - both
falling within the "most likely" range of the current levels of concern, but above the low range.
Second, the RM2 release assessment (Ref.# 21) indicates that the highest in-stream
concentrations will be found in areas with extensive metalworking fluid end-users: none of the
monitoring work expressly targeted those areas. Third, the data are now quite old: during the
interim, in response 10 new regulations, changes may have occurred in disposal practices.
Exposures: CPIA Survey of Formulators
To fill this void, the RM1 exit decisions instructed the RM2 investigation to obtain better
information from industry on CP releases . In response, the four CP producers each provided
detailed manufacturing process information. In addition, following a series of discussions with
members of the RM2 Workgroup, CPIA volunteered (Ref.# 14) to conduct a survey of CP/O
metalworking fluid formulators. The RM2 investigation had by that time determined that
virtually all ecologically significant releases of CP/Os occur as a result of discharges of spent
short chain water soluble cutting fluids. The purpose of the Survey, therefore, was to obtain
data from metalworking Quid formulators reflecting:
1. the amount of short-chain (Clo.,j without regard to chlorination) CP/Os used in
metalworking fluids in 1991;
2. the proportion that went into water-soluble metalworking fluids; and
3. the amounts of CP/O-bearing water-soluble metalworking fluids sold in the major
geographic markets.
It was anticipated that when the Survey data were received, EETD would use
assumptions, awareness of technologies and practices, and models, to estimate how much of the
CP/Os entering major markets ultimately found their way into specific bodies of water, and the
resulting in-stream concentrations.
The survey results were received (Ref.# 38) on June 21st. More than 70 percent of
estimated total domestic sales of short chain CP/O-bearing water-soluble metalworking fluids
were reported. Thirty-nine percent of estimated total domestic sales were reported to have
8
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been sold in the four highest consumption States: Michigan, Ohio, Indiana and Illinois. The in-
house analysis therefore focussed on these four States. In order to estimate CP/O
concentrations in specific bodies of water, EETD required sales data identified at the city level.
Forty-two percent of total reported sales in the four highest consumption States were reported
by city. These city-specific data, covering 178 cities, were therefore used by EETD, as described
above, to estimate:
1. the amounts of CP/Os released to individuaTPOTWs, assuming 90 percent
removal via pre-discharge separation and treatment (Ref.# 44);
2. the amounts released from those POTWs, assuming an additional 90 percent
removal (Ref.# 45 and 52); and
3. the resulting concentrations in particular streams, based upon flow rates.
The analysis reflects the best current estimate of CP/O in-stream concentrations in areas
with the highest concentrations. Uncertainties nevertheless remain including, among the more
prominent, the following.
1. The assumption that all water soluble oils are separated and treated before
discharge is based primarily upon inferences drawn from regulatory requirements.
2. There is no information on the likelihood or extent of illegal disposal of spent oil.
3. The analysis does not account for any adverse impacts that may result from
concentrations of CP/Os in sediment.
4. The Survey did not achieve complete coverage. Some of the fluids reported sold
in the four States that were not reported by city may, in fact, have gone to cities
v for which sales were reported.'
5. No adjustment was made for any destruction of CP/Os that may occur during
metalworking operations.
6. Metalworking facilities' pre-discharge CP/O removal efficiency may be better or
worse than 90 percent, but is more likely to be better.
7. In the absence of removal efficiency data for CPs, removal efficiency estimates
for "Fats, oil and grease" were used as surrogates. There are no empirical data
to determine the validity of this assumption.
8. Some double-counting occurred. The total volume of CP/O releases reported for
cities served by more than one POTW was attributed to each POTW. .
1 In attempting to adjust for this possible source of error, by pro-rating the unreported
sales on the basis of population distribution, we found that sales reported by city matched almost
precisely what would have been predicted on the basis of population distribution.
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Risk Characterization
Screening Results (Ref.#s 45 and 51)
Initial risk estimation results are presented in Figure I, which shows the number and
proportion of localities estimated to have in-stream concentrations below, within and above the
three levels of concern". As shown, 186 localities2, or 75 percent of the total, are estimated to
"have"uvstream concentra'tionf Below!Ke low^^ level 6f"c"6ncefn (0:037Tg/l)r62," or 25'percent,
were above that level. Of those 62, 28 fell within the low range of concern (0.03 < 0.11 pg/1);
26 within the "most likely" range of concern (0.11 < 0.7 fig/1); five between the upper bound of
the level of concern and the lowest estimated No Observed Effect Concentration (0.7 < 1.0
/jg/1); and two within, and one just above, the low range of the estimated NOEC (1.0 < 3.0
/jg/1), and at or below the lowest estimated Geometric Maximum Acceptable Toxicant
Concentration. All together, 14 percent of the total fell within or above the "most likely" level of
concern.
EXAMS II Results (Ref.#s 45 and 52)
The results described above, and reflected in Figure I, do not take into account the
insolubility of CP/Os. In order to assess the impact of partitioning from the water column to
sediments, the EXAMS II surface water model was used. Time and resource constraints
precluded applying EXAMS II to all 178 cities, but it was applied to the two cities with the
highest in-stream CP/O concentrations, and to three of the remaining that fell within the highest
62.
City Pre-partitioning Post-partitioning
estimated estimated
concentration concentration
Romeo, MI 3.12 ng/\ 1.77 Mg/l
Warren, MI 2.91 ng/[ 2.49 /xg/l
Adrian, MI 0.30 Mg/l 0.06 /tg/1
Bremen, IN 0.11 jig/1 0.08 /zg/1
Seymour, IN 0.035 /ig/1 0.03
EXAMS II consistently predicted lower CP/O water column concentrations, due to
removal of CP/Os via adsorption to sediments and volatilization, than those estimated in the
screening results. Reductions in concentrations ranged from 14 to 56 percent.
2 The total number of localities add up to more than the 178 cities for which data were
repotted because several cities were serviced by more than one POTW. In those instances the total
amount of CP/Os released from that city was attributed to each receiving POTW.
10
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0
C
V
U
b,
200
190
180
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
Frequency of CP Concentrations
For II* OH, MI, IN
186
oo
c
n
m
28
26
KXXXXXXX
<0.03
>=0.03-<.ll
CP Surface Water Concentration (ppb)
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CASM Results (Ref.# 33)
To characterize the extent and probability of impacts from CP/O exposures, and provide
some indication of the ecological significance, EEB applied the Comprehensive Aquatic
Simulation Model (CASM) to three hypothetical concentrations -- 10, 5 and 1 /xg/1. CASM is a
complex multi-species model which represents the direct and indirect effects of toxic substance
-exposures-to-algal-biomass, invertebrates, forage-fish and-toppredator^fish.populations in.a---__
typical northern lake ecosystem. It does not take into account the potential effects on exposure
to bioconcentration. Forage fish and top predators, especially, could be receiving higher CP/O
exposures than CASM predicts by ingesting aquatic invertebrates and fish with CP/O residues.
CASM may therefore not provide a conservative estimate of ecological risk.
Figures two through four, on the following pages, show the projected results at 10, 5 and
1 jigA respectively. Figure two shows that at 10 fig/I, there would be major losses - a 50
percent reduction in forage fish, for example, is virtually certain. Figure three indicates that
damage would also be significant at 5 jig/1, with about a 40 percent probability of 25 percent
reductions in both forage and predator fish and among invertebrates.
At 1 /ig/1 (Figure 4) CASM projects a low probability of any effect to any trophic level.
There is near zero probability of 50 percent or greater loss at any trophic level. There is about
a 17 percent probability of a 25 percent loss of forage fish, and about a five percent probability
of a reduction of that magnitude in algal biomass. The probability of 25 percent reductions in
invertebrates or predator fish approaches zero.
Economic Assessment (Ref.#s 22)
EETD/RIB applied an economic benefits model to the results of the CASM analysis in
order to estimate the value of reducing CP concentrations from each of the three hypothetical
levels to zero in three areas ~ the Houston Ship Channel in Texas, the Schuylkill River in
Pennsylvania, and Sugar Creek in Ohio. At the hypothetical concentration of 1 jig/1 - a level
higher than estimated to be present in the waters of all but three of the 248 localities in the
Survey - the economic benefits model estimates annual gains ranging from $100,000 to
$5,600,000 in Galveston Bay, the highest risk area modelled, with expected values, under the two
most likely assumptions, of $1,700,000 and $1,000,000. The estimated expected annual benefits
of reducing hypothetical concentrations from 1 /tg/1 to zero in the Schuylkill River and Sugar
Creek were $16,400 and $471, respectively.
12
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F igure 11
Pelagic Community Blomass Reduction
CP « 0.01 mg/l
20-... 40 60 80
Percent Biomass Reduction
100
i
IPhyto
Zoop
+ Forage
3E Piscivore |
Figure 9. Bioaass reduction in four trophic levels at 10 ppb exposure
13
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Figure III
Pelagic Community Biomass Reduction
CP = 0.005 mg/l
20 -v 40 60 80
Percent Siomass Reduction
100
Phyto
Zoop
Forage
Piscivore
Figure 8. Biomass reduction in four trophic levels at 5 ppb exposure
-------
Figure IV
1
i
1
1
I
i
I 0.8
; >»
S 0.6
20.4-
0.2 -
0.
T
c
Pelagic Community Biomass Reduction
CP = 0.001 mg/l
.^>.
"
^U-
i
20 *.. 40 60 80 100
Percent Biomass Reduction
Phyto Zoop * Forage 3E Piscivore
Figure 7. Biomass reductions in four trophic levels at 1 ppb exposure
15
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Foreign Government Assessments (Ref.#s 6, 12, 18 and 40)
Environmental Agencies in Finland (Ref.# 6), The Netherlands (Ref.# 12) and The
United Kingdom (Ref.# 18) have recently completed assessments of risks posed by CPs.
In brief, all three countries concluded that CPs were unlikely to pose much of a problem,
_if.anv.^injheiijespective countries;, Fmlajid^ndjrhe^Netherlands felt that more information
was needed on releases to the environment, and recommended efforts 16~gerierafe~it; "none"* ""
recommended restrictive regulation.
The Netherlands document, and in all probability the Finnish and U.K. documents as
well, were prepared in order to inform discussion about a proposal to abandon use of CPs in
Europe. In 1991 Sweden placed a proposal before the working group on diffuse sources of the
Paris Commission (PARCOM) to phase out CPs by the signatory nations over a three to ten
year period. It is unclear what the practical consequences would be if that proposal were
adopted, since PARCOM is not believed to be a UNEP, EC or other governmental authority.
In any event, the proposal was voted on and not adopted at a joint meeting of the Oslo and
Paris Commissions held in Berlin on June 14-19, 1993. It may be reconsidered at the next
meeting, a year from now. (Ref.# 40)
Appendix 1 presents quotes from the three assessments reflecting conclusions reached by
each Agency in eleven areas: (1) overall level of concern; (2) general state of knowledge; (3)
regulations and recommendations; (4) ecological toxic thresholds; (5) surface water
concentrations; (6) transportation in the environment; (7) persistence and degradation; (8)
substances of concern; (9) dioxin formation; (10) sources of release; and (11) production and
use.
Canada is ulso investigating potential risks posed by CPs. Environment Canada is
expected to publish a final assessment within the next few weeks. That assessment may
conclude that chlorinated paraffins may be present in the Canadian environment at levels which
could have an immediate or long-term harmful effect on the environment. If such a
determination is made, chlorinated paraffins would then be defined as "toxic" under the
provisions of the Canadian Environmental Protection Act (CEPA), Section ll(a). Substances so
defined are placed on Schedule 1 of the Act, for consideration for possible development of
regulations to control any aspect of their life cycle, from the research and development stage
through manufacture, use, storage, transport and ultimate disposal.
Further Research
This section discusses eight additional fact-finding activities that might be undertaken to
address issues about which there is insufficient information to permit definitive conclusions. The
eight efforts are listed below from high to low in order of their perceived importance. The
discussion following the listing presents a brief rationale for each activity and, in some instances,
provides cost estimates and recommendations as to who might undertake the work.
16
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1. Monitor for CP/Os in the water column in high consumption areas identified in
the Survey;
2. Test for effects of CP/O concentrations in sediment to benthic organisms;
3. Ascertain the potential for forming dioxin during metalworking;
4. Characterize-spent-oil-disposal technologies-and practices among-metalworking-
operations;
5. Test for chronic effects of short and intermediate chain CPs on fish;
6. Evaluate the potential for adverse effects in terrestrial and avian species;
7. Assess potential long-range distribution of CP/Os via atmospheric and/or aquatic
transport; and
8. Evaluate the potential for dioxin formation during incineration c.f spent oil.
1. Monitoring (Refs.# 37 and 42)
The highest priority is to obtain monitoring data to corroborate or refute the findings of
the Survey. Unless and until such monitoring is conducted, the uncertainties discussed earlier
will limit confidence in conclusions drawn from the Survey. Those conclusions may either under
or overstate the actual risk.
...One problem with past monitoring has been that the level of quantification for CPs has
been at^about 0.5 /ig/1 in relatively clean water, whereas the need is to quantify concentrations
occurring in highly complex waters at about 0.1 /xg/1, the low end of the most likely level of
concern. To this end, CMD has recently spent about $20,000 to determine the feasibility of
sampling and analyzing at the lower level. This work is currently on hold pending an OPPT
decision to go forward. CMD estimates that another $30,000 to $40,000 will be required to field
test the new procedures in relatively clean and highly contaminated waters, prior to monitoring
those areas of the country where metalworking fluids are used most extensively. The actual
monitoring program will cost considerably more.
It is recommended that the Office of Water be asked to conduct the monitoring program
as a component of EPA's Contaminated Sediment Management Strategy.
17
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2. Sediment toxicity testing (Ref.#s 2, 36 and 46)
Because no suitable protocol existed at the time, the testing agreement negotiated by
OTS with the Consortium of chlorinated paraffins producers in 1982 did not call for testing the
effects of CP concentrations in sediment. All assessments of the effects of CP/Os on aquatic life
are therefore based upon CP/Os in the water column. The concern is heightened by the fact
that CP/O concentrations in sediment are two tq^ three ordersjrf magnitude jiigher than in the
water column. T~"~~1*"* '-"ITr-" '-'"'" -« '"'' ~"
HERD has now identified and provided test protocols (Ref.# 46) that are suitable for
determining acute and chronic effects of sediment concentrations of CP/Os on freshwater,
estuarine and marine amphipods. The American Society for Testing and Materials as well as
the EPA Research Lab in Newport, Oregon, has been involved in developing these protocols.
The cost of administering a 28 day chronic test is in the range of $30,000 to $40,000. In
addition, the protocols would need to be modified somewhat for use with CP/Os, and would
have to be written to conform to OPPT validation parameters and reporting requirements.
It is recommended that sediment toxicity testing be added to the Master Testing List
(MIL).
3. Investigating Formation of Dioxin During Metalworking (Ref.# 13)
Inadvertent production of dioxins or furans in the course of using CP/O-bearing cutting
fluids is a concern. Dioxin/furans may be generated when chlorinated substances are heated to
200° centigrade in an oxygenated environment. All three conditions are met during
metalworking with CP/O-bearing fluids.
While the details have not been worked out, it would be possible to analyze samples of
original and spent oil from a few worksites that employ varying technologies, to ascertain
whether, and if so in what amounts, dioxin/rurans are produced.
It is recommended that this potentially serious concern be brought to the attention of
the Agency's Dioxin Workgroup.
4. Characterizing End-User Disposal Technologies and Practices
Although almost all releases of CP/Os to water occur at metalworking facilities, no effort
has yet been made to determine how, and with what removal efficiency, these operations treat
their spent cutting fluids. This information is important for two reasons.
First, the RM2 analysis relies heavily upon assumptions made about the proportion of
CP/Os in the original fluid that remains in the water phase after separation and treatment.
This probably varies from one operation to another, depending upon size, capitalization,
function of the facility, and other factors. Second, establishing realistic waste minimization goals
will require knowing the amount of CP/O removal that is typically achieved and theoretically
possible.
18
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5. Fish Toxicity Testing (Ref.#s 3, 5, 25, 27, 28 and 46)
This concern also arises from testing conducted by the producers' Consortium. During the
depuration phase of a Trout Bioconcentration Test, all of the fish died that had been previously
exposed to 15.0 /xg/1 for 168 days, and several died that had been exposed to 3.0 /ig/1. This
unexpected event raised concern that traditional chronic toxicity testing may have failed to detect the
true threshold simply because the fish were not exposed long enough. Mitigating this concern to
^
the nominal concentration was also 3.0 /tg/1 in order to determine if the effects would be repeated
no mortalities occurred, even though the dosages and durations were essentially the same.
HERD has identified a full life cycle fish protocol (Ref.# 46), which also contains a partial
life cycle protocol as an addendum, that is suitable to address this concern. The full life cycle test is
preferred, and would cost about $150,000 to $200,000 to administer, with an additional $75,000 to
$100,000 needed to analyze the results. The partial life cycle could be administered for $50,000 to
$100,000, with the same analytical costs. HERD/EEB has contracted to have testing guidelines
drafted for both protocols: drafts are expected by the end of the year.
6. Assessing Potential Effects on Terrestrial and Avian Life (Ref.#s 1, 31 and 49)
This concern arises primarily from monitoring conducted in 1980 by Campbell and
McConnell (Ref.# 1) in the U.K. and in 1992 by the Institute of Environmental Research in
Stockholm (Ref.# 31), in both of which CP concentrations were found in a variety of terrestrial and
avian species. This has raised concern that the same situation may prevail in the U.S., and has
prompted the suggestion that monitoring of wildlife be undertaken here. No cost estimates have been
developed.
One consideration that lends this a somewhat lower priority than the concerns expressed above
is a comparison (Ref.l 49) of the residue levels found in animal tissue by both studies, with toxicity
threshold levels found for animals in the literature. That comparison found the residue levels to be at
least
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III. Human Health Risk (Ref.#s 47, 48, 50, 51, 52 and 53)
Metalworkers
Cancer is the predominant human health hazard. There is no developmental toxicity
n44hj3j£pi^d^cjw _
exposures of metalworkers via inhalation of CPs in mist generated during use. There is a
moderate concern for this risk, and a much lower concern for dermal exposures.
Combining risks to metalworkers from inhalation and dermal exposures yields a high end estimated
upper bound of 157 U.S. excess lifetime cancer deaths.
More than 300,000 metalworkers may be exposed. Projected excess cancer cases from
inhalation exposures to just the short chain CPs could be as high as one to two cases per year
(or 110 cases per work lifetime) in an estimated occupational subpopulation of 160,000 workers.
Exposures to the intermediate and long chain CPs are each expected to yield less than an
average of one excess cancer case per year ~ or as high as 28 cases per work lifetime for the
intermediate chain and two for the long chain in estimated subpopulations of 41,900 and
185,000, respectively.
Risks from dermal exposures are estimated to be low because absorption is low. Risks
from dermal exposures, however, are added to the inhalation risk to give a composite risk. The
high end estimated risk from dermal exposures to short chain CPs is 17 lifetime excess cases
which, added to the 110 for inhalation of short chain CPs and the 30 for inhalation of
intermediate and long chain CPs, yields a total upper bound estimate of 157 lifetime excess
cancer cases among metalworkers due to exposures to CPs.
The following exposure assumptions make this a high end estimate.
1. The number of workers exposed are derived from the National Occupational
Exposure Survey. These are high-end estimates.
2. Exposures to CPs were derived from surrogate data collected by OSHA on oil
mist exposure during metalworking operations. All metalworking fluids were
assumed to contain 10 percent CPs. This assumption is probably an
overestimate.
3.. The oil mist inhalation exposures are based on actual monitoring data collected
by OSHA over a 13-year period. OSHA compliance data may be biased toward
the high end since they are predominantly from inspections resulting from
employee complaints, or inspections of facilities targeted because of high
exposures.
4. The use of personal protective equipment is unknown. In the absence of data, it
was assumed protective equipment is not used.
20
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The upper bound estimate of 157 excess lifetime cancer cases is based upon an assumed
mist inhalation exposure to CPs of 1.2 mg/day. It should be noted that exposures at the OSHA
oil mist PEL of 5.0 mg/m3, under the same assumption of ten percent CP content, would be 5.0
mg/day, and would thus yield higher risks.
"Subsistence FisHeaters
There is a possibility of potential cancer risks to subsistence fisheaters (indigent people
whose diet consists primarily of fish they catch and eat). Modeled data indicate individual upper
bound cancer risks could be as high as 5 X 10"* in the highest in-stream concentration areas.
The size of the populations at risk in these areas is unknown, but certainly too low to pose more
than a negligible population risk. In addition, the model used to estimate CP releases by end-
users does not take into account any possible destruction of CPs which may occur during use.
The nature of the population (i.e., indigent) makes this a potential "environmental equity"
concern.
Manufacture of Resinous Long Chain CPs
There may be an individual lifetime excess cancer risk as high as 10'3 among a very small
population of workers employed in manufacturing resinous long chain CPs.
21
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IV. Options and Recommendations
Five options were considered for closing the RM2 investigation. Irrespective of the
option selected, it is recommended that OPPT (a) refer the occupational risk to OSHA, (b) refer
the dioxin issues to EPA's Dioxin Workgroup, and (c) advise-Region 5 of the subsistence fish-eater
risk. These three recommendations are not separately and repetitively enumerated in the
-following option-descriptions __-,_ .. .
Option 1: Close with no further action.
Pros:
a. Action is reasonably consistent with RM2 findings.
b. Immediately and definitively closes CP/O investigation.
c. Frees OPPT resources for other purposes.
d. Avoids awkwardness of rulemaking without a strong risk case.
e. Objections from external groups are unlikely.
Cons:
a. Does nothing to reduce releases of substances known to be toxic,
persistent and bioaccumulative.
b. Residual questions regarding risk remain unanswered.
c. Substances satisfying TRI criteria remain unlisted.
Option 2: Negotiate voluntary agreements with industry to (1) promote pollution
prevention practices to reduce use of short chain CPs, and to reduce discharges
of CP/Os to water and, (2) conduct research especially surface water
monitoring and sediment toxicity testing to address uncertainties remaining
after RM2.
Pros:
a. Accommodates concern that CP/Os are present at levels of concern in a
few localities.
b. Addresses residual questions regarding risk.
c. Avoids awkwardness of rulemaking without a strong risk case.
d. Based on Survey experience, Industry may be amenable. Holding TRI
listing and other steps in abeyance provides additional incentive.
22
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Cons:
a. Leaves CP/O investigation open.
b. Requires additional OPPT resources.
c. Negotiations may not be successful.
d. Substances satisfying TRI criteria remain unlisted.
e. Voluntary written agreements may be unenforceable.
f. Voluntary agreements may yield information of uncertain quality.
Option 3: List on TRI and close with no further action.
Pros:
a. Immediately and definitively closes CP/O investigation.
b. TRI listing will discourage use of CP/Os.
c. Satisfies concern for listing substances that meet TRI criteria.
d. Avoids awkwardness of risk-based rulemalcing without a strong risk case.
e. OPPT resources are freed for other purposes.
Cons:
a. Other than listing, does nothing to reduce releases of substances known to
be toxic, persistent and bioaccumulative.
b. Residual questions regarding risk remain unanswered.
c. Industry may object to listing on grounds that Survey results suggest
relatively little risk.
d. Industry may ask why they were encouraged to conduct the Survey - as a
potential alternative to TRI listing - if the decision to list was to be based
solely upon hazard, without regard to the Survey results ("fair play" issue).
23
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Option 4: List on TRI, seek funding from the Water Office to monitor CP/Os in high use
areas, and add CP/Os to the Master Testing List (MTL).
Pros:
a. TRI listing will discourage use of CP/Os.
b. ..Satisfies.concern for_Usting.subsjancesjthat meetJTRIcriteria.
c. Potentially addresses residual questions regarding risk.
d. Avoids awkwardness of risk-based rulemaking without a strong risk case.
Cons:
a. Leaves CP/O investigation open.
b. Industry may object to listing on grounds that Survey results suggest
relatively little risk.
c. Industry may raise "fair play" issue.
d. OW may be unwilling to fund monitoring.
Option 5: Regulate aggressively with information-gathering, public notification, and
restrictive authorities of SARA §313 and TSCA §§4, 8 and 6 in order to
discourage use of short chain CP/Os in metahvorking fluids.
Pros:
a. Effectively and immediately closes the investigatory phase.
b. Aggressive actions will effectively discourage use of CP/Os.
c. Addresses residual questions regarding risk.
d. Results of promulgated regulations are enforceable.
e. Satisfies concern for listing substances that meet TRI criteria.
24
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a. Justifications for risk-based rulemakings could be hard to establish.
b. Results would take longer to achieve via rulemaking than under voluntary
agreements.
c. Rulemakings would consume more OPPT resources than any of the other
"* optionsr* ' * ' ~ - ' "-
d. Industry may object to listing on grounds that Survey results suggest
relatively little risk.
e. Industry may raise the "fair play" issue.
Recommendation
Option 4: List on TRI, seek funding from the Water Office to monitor CP/Os in high use
areas, and add CP/Os to the MTL. Refer the occupational risk to OSHA, and
the dioxin issues to EPA's Dioxin Workgroup, and advise Region 5 of the
subsistence fish-eater risk.
Discussion
TRI Listing
. Listing on TRI is recommended because CP/Os satisfy the listing criteria. Although
CPIA and ILMA will be unhappy about the fact that they were encouraged to undertake the
Survey of Formulators (which they proposed as an alternative to listing) without being informed
that the listing decision would be based solely upon hazard - and therefore would not take the
Survey results into account -- the principle of listing all substances that satisfy the TRI criteria is
overriding. While this principle is considered paramount, it should be recognized that listing
under these circumstances may diminish industry's enthusiasm for additional voluntary efforts.
Monitoring
As discussed earlier, eight areas were identified in which additional research could be
considered. Of these, the two most important are (1) monitoring surface waters in areas with
high in-stream concentrations to corroborate or refute the findings of the Survey; and (2)
conducting tests to determine the toxic effects of CP/O concentrations in sediment.
There are theoretically four ways to obtain the monitoring: (1) request industry to
undertake it voluntarily; (2) require industry to undertake it under a TSCA §4 rule; (3) fund it
out of OPPT; or (4) ask OW to fund it. The likelihood that industry would voluntarily agree to
25
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monitoring -- without at least the credible threat of a §4 rule ~ is diminished by the decision to
list on TRI. A §4 test rule is conceivable, but OPPT may be unwilling to invest the necessary
resources and effort. Funding the effort out of OPPT is also unlikely. While OPPT has spent
about $20,000 to determine the feasibility of this monitoring effort, and an additional $30,000 to
40,000 will be requested for this purpose, the cost of the actual monitoring (estimated at several
hundred thousand dollars) is prohibitively expensive for OPPT. That leaves the fourth
^possibility, of funding by_OW._ EETDjs currently exploring whether OW can be induced to
conduct this monitoring, or use their authoriiies to have"STaTes^olb71h^cohjuhcT:i6h"with""EPA's
Contaminated Sediment Management Strategy.
Master Testing List
The two most likely means of obtaining the sediment toxicity testing are either a
voluntary agreement by industry to test, or a §4 test rule. For the reasons noted above, a
voluntary undertaking seems unlikely. It is therefore recommended that CP/Os be added to the
MTL.
Referral to OSHA
The most significant potential human health risk is occupational. In the absence of
reliable hard data, several "high end" assumptions were applied to yield the possibility that as
many as 157 excess lifetime cancer cases could occur among metalworkers. The number of
cases would be much higher, moreover, if metalworkers were operating at OSHA's mist PEL.
For this reason, it is recommended that the referral be strongly worded and emphatic (although
not so emphatic as a §9(a) referral). Nevertheless, in view of the many other hazards associated
with metalworking fluids, and their complicated nature, no referral - regardless of how emphatic
-- is likely to trigger any CP-specific action by OSHA nor, indeed, any oil mist-specific action.
The question then arises as to OPPT's responsibility. One possible answer is discussed below, in
the subsection entitled Metalworking Fluid Cluster.
Referral to Region 5
The only potential general population risk is to "subsistence" fish eaters - indigent people
whose primary source of food is the fish they catch. This is primarily an "environmental equity"
concern. The highest estimated upper bound individual excess lifetime cancer risk is on the
order of 5.0 x 10"*. This is in the city estimated in the Survey as having one of the highest in-
stream CP/O concentrations in the country: most other cities have far lower concentrations.
When this highest individual risk is multiplied by any believable estimate of the numbers of
people that might be involved, the population risks become negligible. Since most of the cities in
question fall within the north central region, it is recommended that Region 5 be notified of the
potential problem.
26
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Referrals to Agency Dioxin Workgroup
Dioxin/furans may be generated when chlorinated substances are heated to 200°
centigrade in an oxygenated environment. Since CP/O-bearing cutting fluids are by definition
chlorinated substances, the possibility of inadvertently producing dioxins or furans occurs
whenever the temperature of these fluids is elevated to 200°. That possibility arises in two
situations: during use as cutting fluids and during incineration of spent fluids. Production
*during"use"poses-a-risk*to-metalworkersrwhile-incineration-may-add-;to-the-general-population
risk created by incinerating chlorinated substances. It is recommended that both concerns be
referred to EPA's Dioxin Workgroup, as the most appropriate body to address them.
Interchangeability of Elements within Options
Each of the five options lays out a broad approach, ranging from what is close to a pure
"drop" through (a) negotiated voluntary agreements; (b) listing on SARA §313; (c) listing plus
in-house monitoring and rule-generated testing; and, finally, to (d) aggressive regulation under
multiple authorities. While it is possible to "mix and match" elements from different options to
some extent, each option basically reflects a different judgment about (a) the decree of risk; (b)
the importance of reducing that risk; (c) the importance of obtaining more information about
the risk; (d) the importance of listing CP/Os on TRI; and (e) the value of fostering industry's
interest in voluntary promoting good stewardship, waste minimization and further research.
Given the risk case, a "presents or will present" finding could be hard to make. Rulemaking
under Option Five may therefore be largely limited to listing on TRI and information-gathering.
In this light, Option Four can be viewed as a "do-able" sub-set of Option Five, with built-in
mechanisms to determine whether the game is worth the candle. Option Three reflects an
opinion^ that the game is not worth the candle if OPPT and/or OW have to expend significant
extrtamural or FTE resources. Option Two would seek to induce industry to undertake both
risk reduction and information-gathering efforts, but such cooperation may be hard to come by
if, as irOQptions Three through Five, CP/Os are listed. Option One is essentially a drop with an
emphatic referral to OSHA.
27
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Metalworking Fluid. Cluster
The CP/O investigation has historically focussed primarily upon ecological risks, and the
options presented largely reflect that concern. The recent RM2 finding that there may be
significant occupational risks raises the question of the appropriate OPPT response. A referral
OSHA is straightforward but is frankly unlikely to move that Administration to do anything they
lha^ejdme^ OSHA did was considered inadequate -
" ~
and further assuming that OPPT considers itself responsible for reducing the resdual
occupational risk - what should the Office do?
One possibility would be to enter "metalworking fluids", qua metalworking fluids, into the
Design for the Environment (DfE)/Use Cluster hopper, for a possible start in FY 94 or 95.
The arguments for this include:
1. the CP/O investigation could be closed;
2. many components in metalworking fluids pose human health risks, and GPs are
probably not the most significant;
3. solutions to occupational exposures may entail remedies other than eliminating
constituent parts; and
4. listing CP/Os on TRI would not be a disadvantage, because (a) OPPT would not
be focusing exclusively upon CP/Os, and (b) the Office would be negotiating
agreements with metalworking fluid formulators and end-users, rather than CP/O
producers.
28
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Appendix 1: Foreign Assessments
Selected Quotes in Eleven Topic Areas Culled from Assessments of Chlorinated
Paraffins by Environmental Agencies in Finland (Ref.# 6), The
Netherlands (Ref.# 12) and The United Kingdom (Ref.# 18)
Overall level of Concern " ""
Finland:
"It may be concluded that the environmental hazard caused by CPs in Finland is rather small."
(p. 36)
The Netherlands:
"Environmental concentrations in the Netherlands are expected not to exceed (maximum
permissible concentrations)", (p. IV)
"Based on scanty information on exposure and effect levels it is concluded that chlorinated
paraffins do not seem to present a significant risk to humans or ecosystems in The Netherlands."
(P- 43)
"In spite of the lack of data, the risk of chlorinated paraffins at the present assumed level of
emissions is considered small, if present at all." (p.41)
The United Kingdom:
"Chlorinated paraffins are generally of moderate toxicity to aquatic organisms and are unlikely
to cause problems in aquatic ecosystems unless spills of the chemical occur. Short chain length
paraffins with a low level of chlorination do pose a hazard to aquatic invertebrates." (Summary)
"Chlorinated paraffins are, generally, only moderately toxic to aquatic organisms but in certain
cases, such as Daphnia magna, do pose a definable hazard during usage. Temporary risk to
aquatic organisms is possible from large spills." (p. 39)
The levels of chlorinated paraffins found in waters close to industry could cause potential
effects in fish over a long period of exposure." (p. 39)
29
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General State or Knowledge
Finland:
"The occurrence of CPs in the environment is still limited and consequently, no risk conclusions
can be drawn" (p. 16).
The Netherlands:
"Information on the effects of chlorinated paraffins is scarce whereas data on exposure in The
Netherlands are lacking. This lack of information seriously hampers a sound risk evaluation."
(P- 40)
The United Kingdom:
"The information on chlorinated paraffins is fairly comprehensive except for a lack of
information atmospheric levels." (p. 39)
Regulations and Recommendations
Finland:
"Without any data on the presence of CPs in the Finnish biota and on the basis of limited
information obtained from the recent literature survey, it is impossible to draw any definite
conclusions on the hazardous effects or the degree of accumulation of CPs in the Finnish
environment. However, due to the relatively small consumption and the low water solubility of
the CPs, the environmental hazards would seem to be rather small. On the other hand, CPs are
one of the many harmful sources of chlorinated products. Therefore, the following studies are
recommended to be done the near future:
Measurements of dioxin formation in steel industry and, if needed, investigations
of dloxine sources.
Measurements of Adsorbable Organic Halogens (AOX) in effluents and
sediments near some metal, plastic and paint factories and, if needed,
investigation of the sources of chlorinated substances.
Measurements of AOX in leachates from landfills and, if needed, identification of
the main chlorinated compounds.
Studies of pH dependency of chlorinated substances in leachates." (pp. 34-35)
30
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The Netherlands:
"There are no standards and guidelines for chlorinated paraffins in force in The Netherlands.
(P- 2)
"Chlorinated paraffins are not considered 'black-list' substances or 'priority substances', but have
been placed on the listjaf 'attention substances'." (p. 2) ^
"...since chlorinated paraffins are rather toxic (especially,those with a short carbon chain and a
high chlorine content) and may be persistent under natural conditions, these compounds may
need further attention. In order to indicate the potential exposure it is recommended to make
an inventory of the use and associated release of (short chain) chlorinated paraffins in The
Netherlands, and preferably in Europe." (p. 43)
The United Kingdom:
"Chlorinated paraffins, as organohalogen compounds, have been identified by the Commission of
the European Communities as being potential List II candidates, as defined under the
Dangerous Substances Directive."
"Chlorinated paraffins, as organohalogen compounds, have also been identified by the
Commission of the European Communities as being potential List I candidates, as defined
under the Protection of Groundwater Against Pollution Caused by Certain Dangerous
Substances Directive."
"The UK Environmental Protection-Regulations 1991 has identified chlorinated paraffins, as
halogenated compounds, as a risk group of substances for release into land and the air."
"Chlorinated paraffins were identified as one of the priority substances for the discussion at the
Fourth International Conference on the Protection of the North Sea." (p. 1)
Ecological Toxic Thresholds
Finland:
"There is limited information on the behavior and effects of CPs on aquatic biota." (p. 31)
The Netherlands:
"For the aquatic environment a tentative maximum permissible concentration of 1 pg.1'1 has been
derived for the shorter chain grades (C^ 17), based on LC50-values for crustaceans which
appear to much more sensitive than fish." (p. 40)
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The United Kingdom:
"Long term studies with rainbow trout have shown mortality to occur at 10/ig/l after 47 days for
Cereclor 42 and at 10/ig/l after 71 days for Chlorez 700." (p. 38)
In a continuous flow experiment over 21 days, complete mortality olDaphnia ntagna occurred at
16.3/ig/lwithin-6 days. A static study led to a calculated 48 hour ECX for immobilization of
550/xg/l. Comparing the figure at which complete mortality occurred with the measured water
concentrations used...it can be seen the LC100 /concentration ratio is of the order 32.6 for the
general case and 2.72 for the worst case data." (p. 38)
Water Concentrations
Finland:
"In Finland, no data is available on the degree of CP contamination of lakes and rivers,
sediments, fish and mammals." (p. 33)
"It may be assumed that, due to their low water solubility and pattern of use, only small amounts
of CPs reach the aquatic environment with industrial effluents." (pp. 33-34)
The Netherlands:
"No figures for the occurrence of CPs in the Dutch environment have been found." (p. IV)
"The predicted concentration in The Netherlands was estimated to be far below the detection
limit: about 0.001 /tg.1"1, corresponding to about 0.007 ng.l'1 in surface water containing 30 mg of
suspended matter per 1." (p. 11)
The United Kingdom:
"Half the (marine) waters (sampled by Campbell and McConnell in 1980) show C10.X chlorinated
paraffins at 0.5-4 /tg/1...chlorinated paraffin levels in non-marine and fresh waters in industry
free areas-range from 0-l/ug/l...(levels in) waters receiving industrial/domestic effluent are 1-
6Mg/l." (p. 16)
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Transportation in the Environment
Finland:
"Chlorinated paraffins are non-volatile and highly lipophilic, which restricts their transportation
in the environment. Since they are easily adsorbed to suspended solids in industrial effluents,
they are likely to be found in sediments near the discharge point." (p. 19)
The Netherlands:
"... it is concluded that advective transport and transformation of chlorinated paraffins may play
a relatively important role." (p. 10)
"Campbell and McConnell stated that because of the involatility the CPs cannot be transported
and dispersed by atmospheric air movements and assumed that transport by water probably is
the only large-scale dispersion mechanism. This contradicts with the McKay model calculations
in this report, indicating that advective import and export through air is very important. It also
is disagreement with their (Campbell & McConnell's) suggestion that the concentrations of
chlorinated paraffins in sediments (up to 1.0 mg.kg'') in remoter areas may be due to
atmospheric transport of chlorinated paraffins from the source area." (p. 13)
The United Kingdom:
"No experimental data could be found, in the literature, for distribution of chlorinated paraffins
in the environment. " (p. 13)
"Products containing chlorinated paraffins are likely to be disposed of to landfills and to a lesser
extent by incineration. The latter process should result in complete destruction of chlorinated
paraffin material because of its relatively low thermal stability. Removal from products in
landfills by leaching is likely to be slow..." (pp. 7-8)
"...low water solubility and tight binding to sediment would suggest that chlorinated paraffins
probably are not leached through soils at appreciable rates." (p. 9)
"...because of the low vapor pressure and low thermal stability (destroyed before volatilized),
evaporation and atmospheric transport probably have a very small role in the distribution of
chlorinated paraffins in the environment." (p. 9)
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Persistence and Degradation
Finland:
"An extensive study was taken up by Zitko & Arsenault on the biodegradation of CPs in the
estuarine sediments. They observed that degradation is maximal in sediments under anaerobic
conditions." (p. 19)
"The longer the carbon chain, the slower the biodegradation." (p. 19)
The Netherlands:
"Information on the persistence and bioconcentration is scanty. CPs are expected to
(bio)degrade in sediment and soil, whereas secondary photolysis in the atmosphere cannot be
ruled out. Reported calculated half-life times are approx. 5 days and 1 day, respectively.
However, the actual half-life times in the natural environment will be much lower. The
biodegradation rate has been shown to decrease with increasing carbon length and chlorine
content, (p. IV)
The United Kingdom:
"...it would appear that chlorinated paraffins do not undergo hydrolysis, oxidation or otherwise
react at significant rates under ambient temperature and relatively neutral conditions. Thus it
would appear that these compounds are fairly chemically stable under environmental conditions.
* * *
However, the chlorinated paraffins can be catalytically dehydrochlorinated in the presence of
iron oxides as well as other inorganic compounds and the possibility of this process occurring in
nature seems quite feasible. Unfortunately, no experimental data are available on the chemical
stability of chlorinated paraffins under sir-minted environmental conditions." (p. 11)
"Chlorinated paraffins were found to degrade under both aerobic and anaerobic conditions.
Biodegradation occurred more rapidly under anaerobic conditions. It was concluded that
extensive biodegradation, in the environment, could be envisaged for chlorinated paraffin grades
containing less 50% Cl." (p. 13)
"Biodegradation was...found to be dependent on the structure of the compound being tested as
well as the degree of chlorination. Shorter chain length paraffins with low levels of chlorination
were found to be degraded rapidly and completely. Biodegradation occurred more rapidly
under anaerobic conditions than under aerobic conditions. (Summary)
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Substances of Concern
Finland:
"It is believed that short chain CPs cause toxic and physiological effects at lower exposure rates
than do long chain CPs." (p. 32)
The Netherlands:
The toxicity of CPs is inversely related to chain length. Therefore in risk evaluation the
attention has primarily been focused on the shorter chain grades." (p.IV)
"The bioconcentration factor decreases with increasing molecular weight and decreasing
lipophilicity; short-chain CPs with a high level of chlorination show the highest
accumulation/retention potential. However, the relatively low levels found in higher organisms
do not indicate the occurrence of biomagnification." (p. IV)
The United Kingdom:
"There appear to be differences between short and long chain chlorinated paraffins and also
differences also occur due to degree of chlorination of a particular paraffin. LCM values in fish
are lowest for short chain length paraffins with a low level of chlorination. It was found that
short chain length paraffins (C10.|3) with a low level chlorination had the highest uptake in the
bleak." .Jp. 39)
Dioxin Formation
"The total emission of dioxins from Finnish incineration plants is about 3 g y"1. * * * The
dioxin emissions are not caused only by CPs but also by other chlorine containing wastes." (p.
34)
The Netherlands:
No references.
The United Kingdom:
No references.
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Sources of Release
Finland:
"Due to lack of measurements, the route of chlorinated paraffins (CPs) to the Finnish
environment are not yet known. Consumption patterns and the low water solubility of CPs
suggest that the main part of CPs are bound to products or end up at landfills, (p. 36)
The routes of CPs into the Finnish environment are not very well known. It may be assumed
that, due to their low water solubility and pattern of use, only small amounts of CPs reach the
aquatic environment with industrial effluents. Furthermore, due to their low solubility in water,
CPs are rapidly accumulated in sediments and possibly also in biota. A greater part is brought
to landfills where paints, plastics, cutting oils and other wastes are deposited. Leaching of CPs
from landfills is believed to be a slow process. However, there have been no thorough studies
on leaching of CPs from landfills. Minor quantities of CP-containing wastes are incinerated in
the waste treatment plant in Riihimeki and Turku, and some cutting oils in scraps end up in the
steel industry in Finland." (p. 34)
"It is believed that during waste incineration CPs, due to their low thermal stability, will not
escape as exhaust gases. CPs decompose at temperatures between 300 and 400 <>C whereas the
decomposition temperature of PCBs is about 800 o C." (p. 28)
The Netherlands:
"...no emission data on CPs in the Netherlands are available. * * * The major emissions are
likely to occur through use and disposal of products containing chlorinated paraffins." (p. IV)
The United Kingdom:
"Chlorinated paraffins are released to the environment mainly as a result of consumption and
disposal losses. No release figures were available for the UK." (Summary)
The major environmental release of chlorinated paraffins comes from the use and disposal of
products which contain them. This occurs through use, through disposal to landfill, or through
discarded lubricant oils being washed into watercourses." (p. 8)
Production and Use
Finland:
"No chlorinated paraffins are produced in Finland." (p.20) [The major use (68 percent) in
Finland is in special paper production. Only four percent is used in cutting fluids.] (pp. 22-23)
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The Netherlands:
"In the Netherlands no production of CPs takes place. The major application in the Netherlands
is their use as a secondary plasticizer for PVC. Other applications are plasticizer, lubricants and
flame retardants applied in paints, coatings, rubber, oils, etc.
[In The Netherlands use of CPs as a secondary plasticizer in PVC accounts for 70 percent of
-total consumption.-]-(p.-4)] -
The United Kingdom:
"Only one plant produces chlorinated paraffins in the United Kingdom at Runcorn, Cheshire.
The annual production of chlorinated paraffins in the UK is approximately 50kT." (Summary)
"The main use for chlorinated paraffins in the UK is currently as a secondary plasticizer for
flexible PVC." (p. 6)
"Non PVC applications of CPs are numerous and diverse, but can be summarized as utilizing
their properties as plasticisers, lubricants and flame retardants..." (p. 6)
"One important factor is that about 50% of the chlorinated paraffins used as extreme-pressure
additives belong to the group that is most environmentally hazardous, i.e., the group having a
chain length of C10.13." (p. 6)
37
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References
(Asterisks denote CBI)
1. Chlorinated Paraffins and the Environment. 1. Environmental Occurrence; Campbell, Ian
and McConnell, George; Environmental Science and Technology; Vol. 14, No. 10;
.Qctober, J98Q. ___ ^
2. Chlorinated Paraffins: Responses to the Interagency Testing Committee; Environmental
Protection Agency (EPA), OPTS; 47 FR 1017; January 8, 1982.
3. Hazard Assessment for Chlorinated Paraffins: Effects on Fish and Wildlife; Health and
Environmental Review Division, Environmental Effects Branch; January, 1985.
4. Chlorinated Paraffins - DECISION MEMORANDUM; Existing Chemical Assessment
Division, Risk Analysis Branch; August 15, 1985.
5. Risk Assessment for Chlorinated Paraffins: Effects on Fish and Wildlife; Health and
Environmental Review Division, Environmental Effects Branch, Toxicology Section;
December 18, 1985.
6. The Use of Chlorinated Paraffins and their Possible Effects in the Environment; Finland
National Board of Waters and Environment; March 1, 1990.
7. RM1 ICB Form; Economics, Exposure and Technology Division, Industrial Chemistry
Branch; undated.
8. RM1 Decision Package: Chlorinated Paraffins - Environmental Risk Assessment; Existing
Chemical Assessment Division, Risk Assessment Branch; June 12, 1991.
9. Meeting Notes: OTS Existing Chemicals Management Meeting; July 29, 1991.
10. RM-2 Scoping; Chlorinated Paraffins: Industry/Use Profile; Economics, Exposure and
Technology Division, Regulatory Impacts Branch; December 3, 1991.
11. Handbook for the Management of Used Metalworfdng Oils Containing Chlorinated Paraffin;
Chlorinated Paraffins Industry Association; January, 1992.
12. Report no. 710401016: Exploratory Report Chlorinated Paraffins; The Netherlands
National Institute of Public Health and Environmental Protection; April, 1992.
13. Conditions for Production of Trace Levels of Dioxins from Chlorinated Paraffins;
Economics, Exposure and Technology Division, Industrial Chemistry Branch; May 8,
1992.
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14. Proposed Plan for the Collection of Information and the Development of a Pollution
Prevention Campaign Relating to the Environmental Release of Chlorinated Paraffins
During Its Manufacture, Processing and Use in Metalworking Fluids; Chlorinated Paraffins
Industry Association; June 18, 1992.
15. Meeting Notes: OPPT Existing Chemicals Management Meeting; June 25, 1992.
T£ Draft Report: £nvirimrnmtdl~P&ea&~anft~ttc ~
Chlorinated Paraffins; Economics, Exposure and Technology Division, Chemical
Engineering Branch; July 1, 1992.
17. Hazard Effect Levels from Ecological Hazard Assessment for Chlorinated Paraffins; Health
and Environmental Review Division, Environmental Effects Branch; July 22, 1992.
18. Environmental Hazard Assessment: Chlorinated Paraffins; United Kingdom Department
of the Environment, Directorate for Air, Climate and Toxic Substances; August, 1992.
19. Hazardous \vaste Management System; Identification and Listing of Hazardous Waste;
Recycled Used Oil Management Standards; Final Rule; Environmental Protection
Agency; 57 FR 41566; September 10, 1992.
20. Chlorinated Paraffins: Summary of Environmental Fate and Exposure: Economics,
Exposure and Technology Division, Exposure Assessment Branch; September 14, 1992.
21. Pollution Prevention Scoping for Chlorinated Paraffins; Economics, Exposure and
Technology Division, Chemical Engineering Branch; September, 1992.
i
22. ... Ecological Benefits Assessment Results for Three Chloroparaffin Case Study Sites;
Economics, Exposure and Technology Division, Regulatory Impacts Branch; November
^20, 1992.
23. Review of Hazard Effect Levels for Chlorinated Paraffins (CPs); Chemical Control
Division; December 9, 1992.
24. Estimated Aquatic Toxicity of Chlorinated Paraffins based on the use of Structure Activity
Relationships (SAR): Health and Environmental Review Division, Environmental Effects
Branch; December 22, 1992.
25. EEB Response to Ed Brooks' Questions on Chlorinated Paraffin Tests; Health and .
Environmental Review Division, Environmental Effects Branch; December, 24, 1992.
26. Risk Issues on Chlorinated Paraffins; Chemical Screening and Evaluation Branch, .Risk
Assessment Branch; January 4th, 1993.
27. Follow-up Questions Regarding Hazard Effect Levels for Chlorinated Paraffins (CPs);
Chemical Control Division; January 5, 1993.
39
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28. EEB Response to Second Set of Questions on Chlorinated Paraffin Tests by Ed Brooks;
Health and Environmental Review Division, Environmental Effects Branch; January 29,
1993.
29. Draft Final Report: Statistical Analysis of Mortality and Fecundity Data from Continuous
Flow Toxicity Testing of a Chlorinated Paraffin to Daphnia Magna: Health and
Environmental Review Division, Health Effects Branch; January 29, 1993.
30. EEB Response to the Second Set of Questions; Chemical Control Division; February 1,
1993.
31. Chlorinated and Brominated Persistent Organic Compounds in Biological Samples from the
Environment; Jansson, Bo, et al; Environmental Toxicology and Chemistry; Vol. 12, pp
1163-1174; 1993.
32. Conclusions from 2-3-93 Meeting on Ecological Hazard of Chlorinated Paraffins (CPs);
Memorandum from Charles M. Auer to Joseph A. Cotruvo and Joseph J. Merenda;
February 22, 1993.
33. Draft Chlorinated Paraffins Ecological Risk Characterization; Chemical Screening and
Risk Assessment Division, Risk Assessment Branch; February 24, 1993.
34. * 7992 Sales of Chlorinated Paraffins and Chlorinated Alpha Olefins; Chlorinated
Paraffins Industry Association; March 3, 1993.
35. Summary of Monitoring Data on CPs in Water Column; Chemical Control Division,
Existing Chemical Branch; March 16, 1993.
36. Draft Memorandum: Ecological Test Methods for Persistent Bioaccumulators; Health and
Environmental Review Division, Environmental Effects Branch; April 14, 1993.
37. "Chlorinated Paraffins," EPA Contract 68-DO-0137, Work Assignment 33. MRIproject No.
9802-33-01; Midwest Research Institute; June 1, 1993.
38. * Draft Report: Report of the Formulators Survey; Chlorinated Paraffins Industry
Association; June 21, 1993.
39. * List of Cities in which CP Sales were Reported; Chlorinated Paraffins Industry
Association; June 22, 1993.
40. Proposed PARCOM Decision on Chlorinated Paraffins; Communication from Hans-Georg
Neuhoff, Deputy Secretary, Oslo and Paris Commissions to Robert J. Fensterheim,
Executive Director, CPIA; June 22, 1993.
41. * Chlorinated Paraffins Occupational Exposure Assessment Update; Economics, Exposure
and Technology Division, Chemical Engineering Branch; June 30, 1993.
40
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42. CMD Chlorinated Paraffins Monitoring; Chemical Management Division, Technical
Programs Branch; July 8, 1993.
43. * CPIA Survey Coverage; Chemical Control Division; July 19, 1993.
44. * Draft Chlorinated Paraffins (CPs) Environmental Release Assessment; Economics,
^ Exposure and Technology Division, Chemical Engineering Branch; July, 1993.
45. Estimation of CP Surface Water Concentrations Using CPIA Survey Results; Economics,
Exposure and Technology Division, Exposure Assessment Branch; July 13, 1993.
46. HERD'S Position Regarding Availability and Feasibility of Chlorinated Paraffins Test
Protocols, with Six Attachments; Health and Environmental Review Division,
Environmental Effects Branch; July 16, 1993.
47. Measured Log P Values for C10-C13 Chlorinated Paraffin Commercial Mixtures and
Comparison of QSAR-Predicted and Measured Bioconcentration Factors in Fish; Health
and Environmental Review Division, Environmental Effects Branch; July 22, 1993.
48. Tables for Upper Bounds on Human Lifetime Excess Cancer Risks; Health and
Environmental Review Division, Health Effects Branch; July 28, 1993.
49. Chlorinated Paraffins: Toxicity to, and Residues in, Terrestrial Species; Chemical
Screening and Risk Assessment Division, Risk Assessment Branch; July 29, 1993.
50. Table of Risk Calculations for Potential Exposure to Short-Chain Chlorinated Paraffins via
Ingestion of Contaminated Fish; Health and Environmental Review Division, Health
Effects Branch, Health Effects Branch; August 9, 1993.
>
51. Chlorinated Paraffins/Human Health Briefing Paper; Chemical Screening and Risk
Assessment Division; August 11, 1993.
52. Estimation of Short Chain CP Surface Water Concentrations Using CPIA Survey Results;
Economics, Exposure and Technology Division, Exposure Assessment Branch; August
25, 1993.
53. Table of risk calculations for end users of metalworking fluids (MWF's) exposed to chart-
chain chlorinated paraffins via mist inhalation; Health and Environmental Review
Division, Health Effects Branch, Health Effects Branch; August 27, 1993.
41
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