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United States
Environmental Protection
Agency
Office of Toxic Substances
Exposure Evaluation Division
Washington. DC 20460
EPA 560/5-87-012
February 1988
Toxic Substances
Chlorinated Paraffins
A Report on the Findings
from Two Field Studies
Sugar Creek, Ohio
Tinkers Creek, Ohio
Volume I - Technical Report
i
10 15 20 25
RETENTION TIME (MINUTES)
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35
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CHLORINATED PARAFFINS
A REPORT ON THE FINDINGS FROM TWO FIELD STUDIES
SUGAR CREEK, OHIO AND TINKERS CREEK, OHIO
Prepared by:
The EPA Chlorinated Paraffins Exposure Technical Team
and
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110
Battelle Columbus Division
Washington Operations
2030 M Street, N.W.
Washington, D.C. 20036
for the:
Office of Toxic Substances
Office of Pesticides and Toxic Substances
U.S. Environmental Protection Agency
Washington, D.C. 20460
JANUARY 22, 1988
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DISCLAIMER
This document has been reviewed and approved for
publication by the Office of Toxic Substances, Office
of Pesticides and Toxic Substances, U.S. Environmental
Protection Agency. The use of trade names or commercial
products does not constitute Agency endorsement or
recommendation for use.
11
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AUTHORS AND CONTRIBUTORS
The information contained in this report reoresents the
joint efforts of several organizations and many individuals.
Names of the principal authors and the contributions of the
various organizations are summarized below.
The EPA Chlorinated Paraffins Exposure Technical Team—
Defined the objectives of the study; developed the Quality
Assurance Project Plan; selected the field study sites;
guided the study from the conceptual design through
final documentation; and compiled and edited the draft and
final study reports. The technical team members included:
Ms. Sarah Shapley, Coordinator
Dr. Carol Bass
Dr. Nancy Chiu
Ms. Susan Dillman
Ms. Therese Dougherty
Ms. Mary Frankenberry
Dr. Joseph Glatz
Mr. Richard Hefter
Mr. Tom Murray
Mr. Roger Swarup
Dr. Gary Thorn
Principal EPA Task Managers: Mr. Tom Murray
Ms. Mary Frankenberry
Principal EPA Project Officers:
Dr. Joseph J. Breen
Ms. Cindy Stroup
OTS Quality Assurance Officer: Ms. Eileen Reilly-Wiedow
Midwest Research Institute—Developed and validated an
existing analytical method for measuring chlorinated
paraffins of different chain lengths in water, suspended
solids, sediment and biota; conducted reconnaissance
surveys of the field study sites; contributed to the
statistical analysis of the reconnaissance survey data and
the preparation of the field study design; supervised the
collection of samples from the field study sites; prepared
quality control samples; performed the necessary laboratory
analysis of field samples; and prepared draft and final
reports on the analytical method development. Key Midwest
Research Institute staff included:
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Mr. David Steele, Principal Work Assignment Leader
MS. Karin Bauer
Mr. Arbor Drinkwine
Ms. Leslie Moody
Mr. Paul C. Constant, Program Manager
Mr. Jack Balsinger, Quality Assurance Coordinator
PEI Associates—Under contract to Midwest Research Institute,
PEI Associates conducted reconnaissance surveys of the
field study sites; collected all field samples; and prepared
field study reports. Key PEI Associates Staff included:
Mr. Mike Arozarena Ms. Barbara Locke
Mr. Robert Hoye Ms. Judy McArdle
Mr. Thomas Janszen
Mr. T. Wagner, Quality Assurance Coordinator
Battelle Columbus Division - Washington Operations—
Developed the field study sampling design; participated
in the reconnaissance surveys and field surveys; provided
rigorous statistical analysis of the reconnaissance survey
data as part of the analytical method validation procedure;
and provided statistical interpretation of the field study
analytical results. Battelle's principal contributors were:
Mr. Robert G. Heath
Dr. Michael Samuhel, Project Manager
Ms. Barbara Leczynski, Project Manager
Dr. Jean Chesson, Project Manager
Ms. Ramona Mayer, Quality Assurance Administrator
IV
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ACKNOWLEDGMENTS
The Environmental Protection Agency (EPA) expresses its
appreciation to the managements and staffs of those industrial
facilities involved in these studies for their cooperation and
valuable assistance. EPA also acknowledges the cooperation
and valuable assistance of EPA Region V, especially Ms. Francine
Norling, and the State of Ohio EPA, especially Mr. John Estenik and
Mr. Eric Nygard.
Valuable advice was provided by Dr. Peter Schmid of the
Institute of Technology, Swiss Federal Institute of Technology
and University of Zurich and Dr. Ian Campbell of the Imperial
Chemical Industries Ltd., United Kingdom.
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PREFACE
This report details the results of two field studies whose
objective was to collect environmental information that would
help EPA determine, preliminarily, if chlorinated paraffins (CPs)
exist in selected water environments and at what concentrations.
The first waterbody selected for this study is a stream receiving
waste discharged from a CP manufacturer; the second waterbody is
a stream receiving discharge from a plant known to use lubricating
oils likely to contain CPs. The information gained from these
field studies will be coupled with that from other environmental
and health studies to collectively contribute to a risk assessment
for chlorinated paraffins.
These field studies were completed cooperatively by an EPA
Office of Toxic Substances Exposure Technical Team and under two
EPA contracts. The first is Midwest Research Institute, No.
68-02-4252, Work Assignment 53, "Chloroparaffins Environmental
Field Study." Mr. Tom Murray is the EPA Work Assignment Manager
and Dr. Joseph Breen, the EPA Project Officer. Mr. David Steele
is Midwest Research Institute's Work Assignment Leader.
The second contract is Battelle Columbus Division, No.
68-02-4243, WA# 2-33. Ms. Mary Frankenberry is the EPA Work
Assignment Manager and Ms. Cindy Stroup, the EPA Project Officer.
Dr. J. Chesson, Dr. Michael Samuhel, and Ms. Barbara Leczynski
were the Battelle Columbus Division Project Managers; they were
assisted by Mr. Robert Heath, consultant to Battelle Columbus
Division.
VI
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EXECUTIVE SUMMARY
This report presents the results of two field studies
conducted in 1986 by the Environmental Protection Agency to
measure chlorinated paraffins (CPs) in segments of two watersheds:
Sugar Creek, Ohio and Tinkers Creek, Ohio. The objective of
these field studies was to collect environmental information that
would help EPA determine, preliminarily, if chlorinated paraffins
exist in these watersheds and at what concentrations. These water-
sheds were selected for study because of their association with a
known CP manufacturer (Sugar Creek) and a user of lubricating
oils which commonly contain CPs (Tinkers Creek).
The results from these field studies will be combined with
other environmental and health data and collectively contribute
to an EPA risk assessment for CPs. The field study results are
summarized below:
Sugar Creek, Ohio
Analysis of the first of three sets of environmental samples
collected from this study site shows that chlorinated paraffins,
represented in this study by three technical mixtures (short-chain
C10-12 (50-60% Cl), medium-chain Ci4_i7 (50-60% Cl), and long-
chain C2Q-30 (40-50% Cl) CPs), are generally present at quantifiable
concentrations in the parts-per-billion to parts-per-million
range in both the discharge from the CP manufacturing plant and
in Sugar Creek downstream from the discharge. These CPs are most
prevalent in the sediment, suspended particulates, and biological
matrices. The findings that chlorinated paraffins are adsorbed
very strongly to sediments and suspended solids in water confirm
those of Campbell and McConnell (Campbell and McConnell 1980).
Where detected in the filtered water, these CPs were generally
present in trace (low parts-per-billion) amounts. Of the three
CPs addressed by this study, the long-chain C2Q-30 (40-50% Cl) CP
was found at the highest levels.
The highest CP concentrations were found in the surface
impoundment lagoon which sequesters the manufacturing plant
effluent before allowing it to discharge to Sugar Creek. Here,
nuantifiable concentrations as high as 170,000 pg/kg were found
in the lagoon sediments. Measurements made in the ditch which
carries the lagoon drainage to Sugar Creek showed concentrations
as high as 3,600 pg/kg in the sediments. Concentrations were
also recorded in Sugar Creek downstream from the drainage ditch
confluence ranging from trace levels to 21 ug/kg. Generally,
concentrations measured in the particulates were less than those
VI 1
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in the sediments and those measured in the filtered water fraction
less still. However, concentrations measured in the biological
matrices (mussels) ranged as high as 280 ug/kg in Sugar Creek
downstream from the drainage ditch. Few quantifiable concentrations
of CPs were found in Sugar Creek upstream of the influence of the
drainage ditch.
Because only one set of samples was analyzed, the statistical
significance of differences between the concentrations found
upstream of the drainage ditch and those found downstream from
the ditch cannot be properly tested. However, the relative
differences in CP levels, coupled with the consistency of the
chemistry, strongly suggest that the manufacturing plant and its
surface impoundment lagoon is a major contributor of CPs to Sugar
Creek.
Modeling estimates of in-stream concentrations of CPs
for Sugar Creek, calculated using actual environmental releases
measured during this field study, compare well with the actual
environmental levels measured in the stream. While too few field
data were collected during this study to'fully validate the
model, the correspondence between model predictions and field
measurements adds credibility to the further use of these modeling
techniques in predicting pollutant loadings in other areas to
which chlorinated paraffins of the types considered by this
report may be discharged.
Tinkers Creek, Ohio
Analysis of the first of three sets of environmental samples
collected from this study site failed to detect CPs in any of the
samples collected near the outfall of the lubricating oil user
or in the drainage network carrying its discharge to Tinkers
Creek. Most of the samples analyzed from this site, especially
the sediment samples, contained a variety of organic consti-
tuents which would have masked the presence of any CPs. Chlorinated
paraffins, however, were measured in the low parts-per-billion
range in one sample collected from the process wastestream of the
lubricating oil user located at this site.
Vlll
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CONTENTS
DISCLAIMER i i
AUTHORS AND CONTRIBUTORS i i i
ACKNOWLEDGMENTS v
PREFACE vi
EXECUTIVE SUMMARY vi i
CONTENTS ix
FIGURES X
TABLES xi
CHAPTER I. INTRODUCTION 1
Project Background 1
Study Objective 4
CHAPTER II. SITE SELECTION PROCESS 6
CHAPTER III. FIELD STUDY SITE 1 - SUGAR CREEK, OHIO.. 8
Description of the Study Area 8
Reconnaissance Survey 12
Field Study Design 14
Field Sample Collection 19
CHAPTER IV. FIELD STUDY SITE 2 - TINKERS CREEK, OHIO. 24
Description of the Study Area 24
Reconnaissance Survey 26
Field Study Design 27
Field Sample Collection 32
CHAPTER V. EXPERIMENTAL SECTION 35
Equipment 35
Sample Preparation 38
Standards Preparation 41
Methodology 41
Method Development and Validation Studies 42
CHAPTER VI. RESULTS AND DISCUSSION 44
Sugar Creek Study Area 44
Statistical Evaluation of Sugar Creek Data 56
Monitoring Versus Modeling Results 59
Tinkers Creek Study Area 63
CHAPTER VII. REFERENCES 64
APPENDICES
Appendix A
Appendix B
Appendix C
Aooendix D
Analytical Method
Analytical Method Validation Results
Sample Collection Protocol
Quality Assurance Project Plan
(Under separate cover)
ix
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FIGURES
Number Page
1 Commercially Available Chlorinated
Paraffins 2
2 Sugar Creek Study Site 9
3 Process Flow Diagram for the Manufacture
of Chlorinated Paraffins 11
4 Dover Chemical Corporation Wastewater
Treatment Process 13
5 Location of Sampling Points in the Dover
Chemical Impoundment and Drainage Ditch.... 16
6 Location of Sampling Points in Sugar
Creek 17
7 Tinkers Creek Study Site 25
8 Location of Sampling Stations A through C
at the Confluence of Tinkers Creek and
Deerlick Run 28
9 Location of Sampling Stations D through G
in the Tinkers Creek Study Site 29
10 HRGC/NCIMS Determination of Chlorinated
Paraffin Standards in Trip-Spiked Water
Sample. Sugar Creek, Station LI 39
11 HRGC/NCIMS Determination of Chlorinated
Paraffin Standards 40
12 CP Concentrations in the Dover Chemical
Surface Impoundment Lagoon 46
13 HRGC/NCIMS Determination of Chlorinated
Paraffins in Sediment Sample Collected
from Station L2, Surface Impoundment
Lagoon, Sugar Creek 49
14 CP Concentrations in the Dover Chemical
Drainage Ditch and Sugar Creek 51
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TABLES
Number
1 Station Locations for the Sugar
Creek Study Site 15
2 Samples Collected from the Sugar Creek
Study Site 18
3 Station Locations for the Tinkers Creek
Study Site 30
4 Samples Collected from the Tinkers Creek
Study Site 31
5 Sequence of Analytical Runs for Samples
Collected from the Sugar Creek Study
Site 36
6 Sequence of Analytical Runs for Samples
Collected from the Tinkers Creek Study
Site 37
7 CP Concentrations (ug/kg) in Sediment of
the Lagoon and Drainage Ditch, by Carbon
Chain-Length Groups and Cumulative Mass
Ranges 47
8 CP Concentrations (jig/L) in Filtrate and
Particulates, From Filtered Impoundment and
Drainage Ditch Water, By Carbon Chain-Length
Groups and Cumulative Mass Ranges 48
9 CP Concentrations (jig/kg) in Stream Sediment
by Carbon Chain Length Groups and Cumulative
Mass Ranges 52
10 CP Concentrations (pg/L) in Particulates From
Filtered Stream Water by Carbon Chain
Length Groups and Cumulative Mass Ranges.... 53
11 CP Residues (jag/kg) in Composite Mussel
Samples from Sugar Creek by Carbon Chain
Length Groups and Cumulative Mass Ranges.... 54
XI
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TABLES (Continued)
Number
12 Comparison of Preliminary Modeling,
Field Sampling Data and Modeling
Results Using Field Estimates of
Chlorinated Paraffins Loading
(Cjg-12 Short Chains) 61
13 Comparison of Preliminary Modeling,
Field Sampling Data and Modeling
Results Using Field Estimates of
Chlorinated Paraffins Loading
(C2Q-30 Long Chains) 62
XII
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CHAPTER I. INTRODUCTION
This report presents the initial results of two field
studies conducted in 1986 by the Environmental Protection Agency's
Office of Toxic Substances (EPA/OTS) under the Existing Chemicals
Program to screen selected waterbodies for the presence of chlor-
inated paraffins (CPs). The information gained from these field
studies will be coupled with that from other environmental
hazard and environmental exposure studies and collectively con-
tribute to an EPA risk assessment for this class of chemical.
PROJECT BACKGROUND
Chlorinated paraffins are saturated straight-chain hydro-
carbons ranging from 10 to 30 carbons in length and containing
20 to 70 percent chlorine by weight (CXH ( 2x-y+2 )c^-y) • Commercially
available CPs are complex mixtures of varied chain lengths and
chlorinated isomers which are distinguished by the average carbon
chain length and the degree of chlorination. These mixtures,
often described as a 9-cell matrix (Fig. 1), are marketed mainly
as high pressure lubricants, flame retardants, and secondary
plasticizers.
In 1977, in anticipation that the Interagency Testing
Committee (ITC) would recommend chlorinated paraffins for
environmental and health effects testing, a group of CP producers
formed the Chlorinated Paraffins Consortium. This Consortium,
in consultation with EPA, developed a phased testing scheme for
CPs. Independently, the National Toxicology Program (NTP)
tested two CPs for carcinogenicity. The ITC did recommend CPs
for testing, but the Agency published a decision in 1982 not to
require testing beyond those already undertaken by the industry
and the NTP.. In 1983, the results of the environmental testing
prompted the Consortium to submit a Notice of Substantial Risk
under section 8(e) of the Toxic Substances Control Act (TSCA).
After the test results were validated by EPA, it was decided that
hazard and exposure assessments and, subsequently, an environmental
risk assessment should be prepared.
In 1984, EPA completed a draft hazard assessment for CPs
(USEPA 1984) based in large part on the consortium data.
This assessment reported acute toxicity (Phase I) information
which showed chlorinated paraffins to be toxic to mussels and
rainbow trout at concentrations as low as a few parts per billion.
It also reported that the 58% chlorinated short-chain (C^o-12^
paraffin was the most toxic of the four formulations tested. The
assessment also reported the results of chronic toxicity
(Phase II, life cycle) studies on a variety of test species which
showed statistically significant (P _< 0.05) toxic effects at
measured concentrations of the 58% chlorinated short-chain
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40-50% Cl
50-60% Cl
60-70% Cl
ClO-12
C14-19
C20-30
//////////////
////////////// 5
i////////////////I
I////////////////
////////////// 7
I////////////////
8
FIG. 1. - Commercially Available Chlorinated Paraffins
The rows represent the different paraffin carbon chain-
lengths commonly manufactured. The columns represent
the range of percent chlorination commonly applied to
the paraffins. The resulting nine cells represent the
full array of chlorinated paraffin mixtures commercially
available.
Analytical measurements for this study are based on
standards obtained for the CPs which are shaded.
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(Cio-12) paraffin of less than 10 ug/L for sheepshead minnow,
daphnids, and mussels and at less than 20 ^jg/L for rainbow
trout, mysid shrimp, and marine algae. The chronic effects of the
short-chain 58% chlorinated paraffin included abnormal behavior,
growth effects, reduced reproduction and lethality.
The NTP test data showed clear evidence of carcinogenicity
in rats and mice, both sexes, for a C^2 (58% Cl) CP. It also
showed mixed results, ranging from no evidence to clear
evidence of carcinogenicity, for a C23 (43% Cl) CP.
While sufficient information was available to perform an
environmental hazard assessment, there was a paucity of inform-
ation with which to prepare an environmental exposure assessment.
Only three previous studies were available: two performed for
the Diamond Shamrock Corporation at its Houston, Texas, and
Grand River, Ohio, locations (Ramm 1978, Ramm 1977) and a third
by ICI Limited at selected sites in Great Britain (Campbell, 1980).
EPA also conducted a modeling analysis which predicted environmental
levels based on available release estimates and professional
judgement. These studies, while providing useful insight into
CP levels in environmental samples, fell short of providing the
specific data necessary to prepare an exposure assessment, i.e.
measurements of specific CPs quantitated in the low oarts-per-
billion range. This paucity of information prompted several
actions. First, an analytical method was sought that could
discriminate the various CPs shown in the 9-cell matrix (See
Fig. 1) with priority given to those for which specific toxicity
information was available. Further, it must be able to measure
these CPs in different environmental matrices, and surmount
any potential analytical interferences of other organochlorine
compounds. Second, the method of choice must be carefully
evaluated and validated using reliable standards. Third, the
method must be applied to field samples collected according to
a sound sample design.
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STUDY OBJECTIVE
The objective of these field studies was to collect
information that will help EPA determine, preliminarily, if
chlorinated paraffins exist in select water environments—i.e. in
the water column (including suspended material), sediment and/or
biological tissue—and, if so, at what concentrations. Because
chlorinated paraffins in the United States are used predominantly
in lubricating oils (50% of total U.S. consumption), site selec-
tions for this study were based on the assumption that if CPs
exist in the aquatic environment, they will most likely be found
in waters receiving discharge from CP manufacturers, processors
of CP-containing lubricating oils, and users of these oils.
Two areas were selected for study based on this premise:
Sugar Creek in Dover, Ohio, the site of a CP manufacturing plant;
and Tinkers Creek near Bedford, Ohio, the site of a lubricating oil
user.
A critical first step to the development of these field
studies was to develop and validate an analytical method
capable of measuring specific chlorinated paraffins in different
environmental matrices. Therefore, the following five additional
objectives were established, specific to this activity. The
analytical procedure must be able to:
o discriminate specific CPs (see Fig. 1), with priority
given to those CPs for which toxicity information was
available.
o reach a limit of detection in the low ppb range.
o obtain CP concentrations for replicate spiked samples
with a range percent (precision) of less than 30%
of the mean of these values.
o obtain CP concentrations with a percent difference
(accuracy) of less than 30% of the actual CP
concentration.
o establish a recovery efficiency in the range of
70-130%.
The study, therefore, consisted of the following tasks:
1. Develop, and validate with field samples, an analytical
method for measuring specific CPs in water, suspended
solids, sediment, and biota.
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2. Develop a Quality Assurance/Quality Control (QA/QC)
Project Plan (QAPP) and a field study and sampling design
for the study. (These were combined to form one
document.)
3. Conduct a reconnaissance survey of each study site.
4. Finalize the study and sampling designs with inform-
ation obtained from the reconnaissance surveys.
5. Collect field samples from the study sites following
the protocol described in the QAPP.
6. Perform the necessary laboratory analyses of the
samples collected from the field.
7. Analyze data; prepare results and conclusions.
8. Write draft and final reports.
The remainder of this report describes the development
of the analytical protocol, the field study selection process,
field sampling and the analytical results and conclusions of the
study. The Quality Assurance Project Plan for this study is
found in Appendix D and is available under separate cover (USEPA,
1986).
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CHAPTER II. SITE SELECTION PROCESS
The objective of these field studies was to collect information
that will help EPA determine, preliminarily, if CPs exist in
selected water environments and at what concentrations.
Field study sites were selected on the premise that if CPs
exist in the aquatic environment, they would most likely be found
in waters receiving discharge from CP manufacturers, processors
of CP-containing lubricating oils, and users of these oils.
Therefore, the prime criterion for selecting sites was the presence
of a discharger which fell into one of these three categories.
Beyond this, candidate sites were evaluated using the following
selection criteria.
1. A simple hydrology was preferred: one with few confound-
ing hydrologic influences and the appropriate environmental
media characteristics and conditions for collecting
water, sediment, and biological samples.
2. A single discharge scenario was preferred not only to
facilitate a classic upstream vs. downstream evaluation
but also to reduce the likelihood of matrix interferences
caused by other point source discharges.
3. Inclusion of an upstream site, remote from the influence
of any point source discharge, was preferred. This
upstream site would serve as a control site.
4. Good cooperation was needed at the EPA Region, State,
and facility level to promote effective planning and
field sampling.
All sites receiving discharge from known CP manufacturing
plants and lubricating oil processors were identified. After
careful consideration, the site that best met the selection
criteria was Sugar Creek, Dover, Ohio, which is the receiving
water for a CP manufacturer. No sites were selected to represent
lubricatinng oil processors because of hydrological complexity.
Considerable effort was then made to locate a potential
lubricating oil user site. Only one user site could be identified
and this site did not meet all of the selection criteria defined
for the study. However, as the only user site candidate, the
decision was made to sample this area with the understanding that
while it may not provide the depth of information expected from
the Sugar Creek site, any information collected there would
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advance EPA's current understanding of CP levels in the aquatic
environment. The lubricating oil user site is Tinkers Creek,
Bedford, Ohio.
These sites are described in detail in the following
sections.
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CHAPTER III. FIELD STUDY SITE 1—SUGAR CREEK, OHIO
DESCRIPTION OF THE STUDY AREA
Sugar Creek is located in east central Ohio. From its
source in Wayne County near Wooster, Ohio, it flows south-
southeast toward its confluence with the Tuscarawas River.
Near Beach City, Ohio, Sugar Creek is impounded. Here it
recharges the aquifer supplying the city of Canton's well
field.
The drainage basin of Sugar Creek is largely rural. It is
classified by the Ohio EPA as a warm water habitat. The focus
of this field study was on the lower four miles of Sugar Creek
from below Strasburg to its mouth with the Tuscarawas River.
A map of the Sugar Creek study area is given in Figure 2.
VJaste Inputs
The only point source discharges to this segment of Sugar
Creek are from the Dover Chemical Corporation facility (River
Mile(RM) 1.8) and the city of Strasburg wastewater treatment
plant (RM 7.3). Acid mine drainage from Goettge Run (RM 1.8) is
a principal nonpoint source of pollution.
Dover Chemical Corporation was the outfall of interest to
this study. Dover Chemical Corporation is a major manufacturer
of chlorinated paraffins, with an annual production capacity
of 45 million oounds. As such, Dover Chemical produces about
21% of the total U.S. production (SRI 1986). Dover Chemical
is located at 15th and Davis Streets in Dover, Ohio. At present,
Dover Chemical continuously ounvos approximately 2.2 mgd of water
from two of their four wells and discharges 1.6-1.8 mgd of water.
The Dover Chemical facility employs about 90 people and at the
time of the study was operating 24 hours a day, 10 days on and 4
days off.
Chlorinated Paraffins Process Description
At a tvoical CP manufacturing plant, such as Dover Chemical,
chlorine gas and paraffin are continuously reacted to form the
chlorinated paraffins. Generally, excess chlorine (5-15%) must
be used because the chlorination reaction is not 100%. Manufacture
of resinous chlorinated paraffins requires the use of a solvent
(usually carbon tetrachloride) during the chlorination process.
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DOVER
CHEMICAL
SURFACE
IMPOUNDMENT
.INFLUENT
CANAL
SUGAR CREEK
z
I DD |
DOVER0 I
'CHEMICAL D r
D°
HI
DOVER
CHEMICAL
CORPORATION
NOT TO SCALE
FIG. 2 - Sugar Creek Study Site
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Conventional soluble stabilizers may be blended with the
chlorinated oaraffin product to protect it from undue dehydro-
chlorination if elevated temperatures are encountered for
extended periods of time during storage and subsequent use.
Generally, up to 5%, by weight, of stabilizer is added.
Resinous products are piped from the reactor to a solvent
stripping unit. Here, the product is passed through a degasser
to vaporize the carbon tetrachloride. The carbon tetrachloride
is then condensed and reused while the freed chlorine is used to
produce sodium hypochlorite (bleach). After the chlorinated
paraffin has passed through the degasser, it is deposited on a
conveyor belt for water cooling with well water until hardened.
The resin dust from the grinding operation is collected
by two dry dust collectors and then sold for use in making
resin. The water used for cooling is sent to the treatment
system.
Liquid chlorinated paraffins are manufactured in a batch
reaction kettle. After reaction, the chlorinated paraffins
are sent through a degasser for removal of hydrogen chloride
gas which is used to make hydrochloric acid (HC1). The other
product of this reaction is free chlorine gas which is used to
make sodium hypochlorite. When the concentrations of gases in
both by-products are too low to form their end products, they are
water scrubbed. This scrubbing water is then sent to the water
treatment system.
Chlorinated paraffins are oackaged and shipped by a variety
of methods. Liquid products are piped from the reactor to a
holding tank from which they are packaged in steel drums or
shipped, in bulk, by tank truck or rail car.
Chlorinated paraffin resin is ground, screened, and stored
in fiber drums and multiwall Kraft bags prior to sale.
A schematic of a typical process for the manufacture of
chlorinated paraffins is shown in Fig. 3.
Dover Chemical Corporation's Uastewater Treatment Process
Wastewater consists of noncontact cooling water, boiler
blowdown ion exchange regenerant, scrubber water, and floor
drainage. All wastewaters with the exception of noncontact
10
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•-PAMFFIN
SOLVENT
COOLING
HATER
REACTOR
—COOLING
HATER
(C
CHLORINE
STABILIZER-
—STAJILIIEI
SOLVENT
STRIPPER
QQUID RESINOUS
CP CP
TO ATWSPHERE
- ^
^11 >^
J.
VENT 6ASES
(HCL 4 tt2 * I
CHLORINATED
X
Y
HCL
STORAGE
HEAT
EXCHANGER
•D
•AG
DRUM
SOLVENT
FIG. 3 Schematic of Process Followed in the Manufacture
of Chlorinated Paraffins (Source: PRI 1984)
11
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cooling water enter a 10,000 gallon settling tank which overflows
into a limestone neutralizing bed. This first settling tank is
equipped with both a rotating oil skimmer and a continuous belt
skimmer. Oil and grease accumulated by the skimmers are
transferred to a separation tank. The aqueous portion is
returned to the first settling tank. Solids from the first tank
are pumped to a 20,000 gallon tank for further separation. This
tank is occasionally drained of the aqueous layer which is
subsequently passed through an activated carbon bed prior to
pumping to the first settling tank. '7ater passing through the
limestone bed flows to the second settling tank which is equipped
with an oil boom and underflow weir prior to discharging over a
4-ft rectangular weir with end contractions. Noncontact
cooling water enters the second settling tank. The discharge
flows several yards through a pipe and then enters a narrow
canal. This canal carries the discharge to a surface impound-
ment lagoon. Discharge from the lagoon flows through a small
ditch to Sugar Creek.
The surface impoundment lagoon is owned by the Dover
Chemical Corporation. The impoundment is 8.6 acres in area and
is approximately 23 ft deep in most places. It contains a
captive population of fish, frogs, and turtles. The impoundment
has flooded in the past, overflowing into Sugar Creek; however,
no such incidents have occurred in the last 2 to 3 years.
A simple schematic diagram of the Dover Chemical Corporation
Wastewater Treatment Process is given in Fig. 4.
RECONNAISSANCE SURVEY
Qn August 12 and 13, 1986, a field team of Midwest Research
Institute (!"!RI) and PEI Associates personnel and Robert Heath,
consultant to Battelle Columbus Division, conducted a
reconnaissance survey of the Sugar Creek field study site.
The objectives of this reconnaissance visit were twofold:
(1) to collect field samples for use in estimating the recovery
efficiency and precision of the analytical method for CPs
which was being validated at the time by MRI, and (2) to obtain
the areal information necessary to prepare an efficient study
design for the area.
In support of the first objective, water and sediment
samples were collected from three sites (stations) in Sugar
Creek.
o Site A - At Tuscarawas Poad, downstream from the Dover
Chemical facility discharge.
12
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FIRST SETTLING TANK
*r—I
°T.
ACTIVATED
CARBON BED
ffi
O
Q.
CO
O
UJ
§
20.000
GALLON
SEPARATION
TANK
SOLIDS
Ico
§
O
to
TO LANDFILL
ROTATING
QBELT
SKIMMER'
OIL CURTAIN
O tu
iu >
D <
L_
SEPARATION
TANK
ION EXCHANGE
REGENERATION BRINE
BOILER SLOWDOWN
SCRUBBER WATER
FLOOR DRAINAGE
NON-CONTACT COOLING WATER
-UNDERFLOW WEIR
4 FOOT RECTANGULAR WEIR
•——OUTFALL 001
•SUGAR
CREEK
LAGOON
• OUTFALL 001
FIG. 4 - Dover Chemical Corporation's Wastewater Treatment Process
13
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o Site B - Upstream of Dover Chemical facility discharge
under the bridge which carries the road to
Winfield.
o Site K - Route 39 downstream from Site A and just above
the confluence with the Tuscarawas River.
Sufficient water and sediment samples were collected to
allow for a series of analyses aimed at validating the analytical
method. Mussels were not collected at this time pending the
issuance of a collection permit. Instead, mussels purchased from
a Kansas City, Missouri, market were used for method validation.
(It is recognized that the extraction efficiency obtained by
analyzing mussel tissue spiked with CPs cannot be demonstrated
to exactly reproduce the recovery from mussels which have
ingested CPs while alive. This is an inherent limitation
when dealing with biota, which may metabolize or assimilate
an analyte. However, the analytical method incorporates
a sulfuric acid digestion step, which destroys the biological
matrix and can be expected to release CPs for extraction and
analysis in a manner similar to spiked samples.)
In support of the second objective, the team was able to
meet and review information about the area with the State of
Ohio EPA personnel. They also walked the Sugar Creek watershed
and visited the Dover Chemical facility. Permission was granted
by facility managers to collect, from their property, whatever
samples were necessary for the study. They reguested only that
samples collected during the study be split and shared with the
Dover Chemical Corporation and that any photographs taken be made
available to Dover Chemical management.
FIELD STUDY DESIGN
The design for this study established eight sampling
stations: four stations in Sugar Creek and four stations in the
lagoon and its effluent ditch. The station locations are
listed in Table 1 and shown in Figures 5 and 6.
The design called for the collection of a minimum of three
samples of water and three samples of sediment at each of the.
eight stations (Table 2). It also called for the collection of
biological samples at each sampling station, where available.
For each stream station, each sample was composed of
three subsamples collected along a stream transect to account
for any incomplete lateral mixing. Because the stream was shallow,
vertical mixing was assumed to be complete. Samples collected in
the lagoon were depth-integrated to account for incomplete vertical
14
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TABLE 1 - Stations Locations for the Sugar Creek Study Site
Station ID Location
Ll In the Dover Chemical Plant surface
impoundment lagoon near its effluent
to the drainage ditch.
L2 In the Dover Chemical Plant surface
impoundment lagoon near the influent
from the plant.
L3 In the Dover Chemical Plant surface
impoundment lagoon in the approximate
middle of the lagoon.
D In the lagoon discharge ditch immediately
above the point of discharge to Sugar
Creek.
B Sugar Creek upstream of Dover Chemical
and under the road to Winfield.
B1 Sugar Creek just upstream of Dover
Chemical discharge ditch.
A1 Sugar Creek just downstream from the
Dover Chemical Plant discharge ditch and
above the confluence with Goettge Run.
K Downstream from the Dover Chemical Plant
discharge and Goettge Run; just upstream
of the confluence of Sugar Creek and the
Tuscarawas Piver.
15
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t/1
©
DOVER
CHEMICAL
SURFACE
IMPOUNDMENT
o.
©
I
^
^77^
OUTFALL ^ II I
00, ///
1
4
./INFLUENT
^ CANAL
DISCHARGE
DITCH
y
FIG. 5 - Location of Sampling Points in the Dover Chemical
Impoundment and Drainage Ditch
16
-------
N
1
GOETTGE
RUN
JUNK YARD
FIG. 6 - Location of Sampling Points in Sugar Creek
17
-------
TABLE 2 - Samples Collected from the Sugar Creek Study Site
PLANT DISCHARGE
SAMPLE SET I
STATION LI L2 L3 D
MEDIUM:
Water 1111
Sediment 1111
Mussel -
QC Water 1* -
SAMPLE SET II SAMPLE SET III
Ll L2 L3 D Ll L2 L3 D
1111 1111
1 111 1 1 11
-___ ____
SUGAR CREEK
SAMPLE SET I
STATION B B1 A' K
MEDIUM:
Water 1111
Sediment 1111
Mussel 111-
QC Water 1* -
SAMPLE SET II SAMPLE SET III
B B'A'K B B'A'K
1111 1111
1111 1111
___'_ ____
* Equivalent in volume to 4 field samples
18
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mixing. This sample type (hereafter referred to as composite
sample) provided the most cost-efficient way of producing an
average concentration of CPs for a given volume of water at a
given time.
Mussels were selected over fish to represent the biological
community of Sugar Creek because past studies (Madeley and Birtley,
1980) have shown that mussels do not metabolize long-chain CPs,
at least to any great extent, while these same studies indicate
that fish will metabolize CPs to varying degrees. The estimated
bioconcentration factor (BCF) for CPs in mussels ranges in the
order of 24,000 to 41,000. The BCF for CPs in trout has been
reported to be between 3,500 and 5,200.
In the study design a mussel sample was defined as a
composite of the flesh of 8 to 10 individual specimens. This was
an estimate based on the size of the mussels purchased for the
methods development and validation work. (The mussels collected
from Sugar Creek during the actual field study were significantly
larger than those on which this design estimate was based.
Consequently, only one or two individual specimens were required to
constitute a sample.)
FIELD SAMPLE COLLECTION
The Sugar Creek field study was conducted from September 22
through 25, 1986. All sample collection activities were
conducted by PEI Associates under contract to the Midwest
Research Institute (MRI). The sampling was supervised by MRI and
compliance with the study design was monitored by a represent-
ative of Battelle Columbus Division. A representative of
Dover Chemical Corporation observed portions of the sampling
effort and received splits of all but mussel samples collected
from the field. Dover Chemical was actively producing CPs
at the time of the study.
The flow and suspended solids loading in Sugar Creek
during the study period were higher than those observed during
the reconnaissance survey. This was due primarily to intermittent
precipitation in the drainage area before and during the sampling
period. However, although flows were elevated, they were still
far below the mean flow which has been reported for the drainage
basin (330 cfs).
1 Because the lagoon retains the Dover Chemical discharge, no
direct temporal relationship can be drawn between the CP levels
found in Sugar Creek and the CPs produced by Dover Chemical
during the time of the field study.
19
-------
Sampling proceeded according to the Quality Assurance
Project Plan and followed the sample collection protocol described
in Appendix C.
A daily account of the field sampling effort follows:
September 23, 1986--Surface Impoundment Lagoon.
A QC sample equivalent in volume to four field samples was
collected at station LI from a depth of 11 ft and used to
prepare field spikes and field blanks.
Three discrete depth-integrated water samples, plus a split
sample for Dover Chemical, and a composite sample of three
individual sediment grab samples, plus a split sample for Dover
Chemical, were collected from each of the three lagoon stations
in the following order, L]_, 1,3 and L2 • This sampling order, i.e
from lagoon effluent to near the lagoon influent was chosen to
minimize possible cross-contamination of the samples.
Water depths at stations LI , L2 and 1,3 were 19 to 23 ft.
A depth-integrated sample was achieved by taking subsamples
from 2, 10 and 17-20 ft depths at each location. Temperatures
at these .depths were all between 21.5 and 22 C. The water was
clear to slightly cloudy at all locations.
Sediment was a mostly black to dark gray fine silt with some,
but not strong odor. Two of the samples taken at station 1,3 were
fine silt, light brown in color with no odor.
After collecting the water and sediment samples, the perimeter
of the lagoon was searched for mussels, but no evidence of mussels
was found.
All samples were then placed on ice in coolers; each cooler
contained samples from a single station plus the corresponding
sample data sheet. The coolers were then shipped by overnight
delivery to the MRI laboratory in Kansas City, Missouri.
Station D
Three discrete mid-depth water samples (plus a split
sample for Dover Chemical), each a composite of single grab
samples from three equidistant points across the small ditch,
were then collected. Then, three discrete sediment samples
(plus a split sample for Dover Chemical), each a composite
of single grab samples of sediment collected from the same three
points across the ditch, were obtained.
20
-------
The total width of the ditch at station D was 12 ft. The
water temperature at this site was 23.5 C. It was not possible
to measure the velocity of the water in the ditch at this site
because the water was too shallow and there were many
obstructions. However/ representatives from Dover Chemical
reported that they routinely measure the flow rate at the
outfall from the impoundment to be about 1.2 cubic feet per
second (cfs). This area was also searched for mussels; none
were found.
September 24, 1986 - Station K
To minimize possible cross-contamination of the Sugar
Creek samples, sampling began with the farthest downstream
station (K) and proceeded upstream. At station K, the field
crew collected three discrete mid-depth water samples (plus a
split sample for Dover Chemical), each a composite of single
grab samples taken from three equidistant points across the
stream. They then collected three discrete sediment samples
(plus a split sample for Dover Chemical), each a composite
of single grab samples of sediment collected from the same
three equidistant points across the stream. Sediment
consisted of gravel to fine brown silt with no odor. The water
temperature was 25 C.
The cross-sectional area of the stream was determined by
measuring the water depth at 2-ft intervals along a transect
of the stream and measuring the stream width. The cross-sectional
area was estimated to be 96 ft . The flow velocity was estimated
by measuring the time required for 12 floats (oranges) to travel
a distance of 100 ft. The estimated velocity ranged from 0.4 to
0.6 ft/s. The estimated flow was then calculated and fell within
the range of 38 to 58 cfs.
Considerable time was spent searching the streambed for
mussels. None were found, nor was there evidence (shells on
shore or in the water) of mussels. According to local residents,
mussels were generally absent from this stretch of the stream
because of the acid mine drainage from Goettge Run. They also
believed that a junkyard located just below station A1 had recently
contributed a spill of unknown magnitude to Sugar Creek which may
have affected the mussel peculations in the area.
Station A'
The field crew collected three discrete mid-depth water
samples (plus a split sample for Dover Chemical), each a
composite of single grab samples collected from three
equidistant points across the stream. They then collected
three discrete sediment samples (plus a split sample for
Dover Chemical). The sediment samples were collected
21
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approximately 15 ft upstream of the water samples because only
coarse gravel and cobble were oresent at the designated location.
The water temperature was 20.5°C. The stream width was 46
ft. The depth and velocity of the water was not measured
at this station because of interferences caused by a fallen tree
across the stream, sharp bends in the stream and deep water
pools. Because this station is immediately downstream from them,
an estimated stream flow can be made by adding the flows reported
for station B1 and the ditch carrying the impoundment discharge,
Using this approach, the flow rate for Station A1 was estimated
to be 40 to 68 cfs.
Station A1 was searched for mussels for several hours,
but only two mussels (family Unionidae) were found.
These were collected and immediately placed in coolers.
Station B1
The field crew collected three discrete mid-depth water
samples (plus a split sample for Dover Chemical) and three discrete
sediment samples (plus a split sample for Dover Chemical), each
a composite of single grab samples from three equidistant points
across the stream. The water temperature was 20.5°C. The cross-
sectional area of the stream was estimated by measuring the water
depth at 2-ft intervals along a transect of the stream. The flow
velocity was estimated by measuring elapsed time for 12 floats
to travel a distance of 100 feet. With an estimated cross-sectional
area of 55 ft and a flow velocity ranging from 0.7 to 1.2 ft/s,
the flow was estimated to range from 38 to 66 cfs.
The field crew searched the stream bed for mussels and
collected eight specimens (family Unionidae). Most of the mussels
were collected in a small portion of the stream situated on the
west side of a small island located about 150 ft upstream of
the designated station B1 location.
September 25, 1986 - Station B
Station B was designated as a Quality Control station.
Therefore, one QC sample, equivalent in volume to four field
samples, was collected. This sample was a composite of single
grab samples collected at mid-depth from three equidistant points
across the stream. From this QC sample, spiked and field blank
QC samples were prepared and set aside for transport to the
laboratory.
In addition to the QC sample, the field crew collected
three discrete mid-depth water samples (plus a split
sample for Dover Chemical) and three discrete sediment samples
(plus a split for Dover Chemical), each a composite of
single grab samples from three equidistant points across the
22
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stream. Water temperature was 20.5°C. The cross-sectional area
of the stream was again estimated by measuring the water depth at
2-ft intervals along a transect of the stream. The flow velocity
was estimated using the same procedure that was employed at the
other stream stations. The total width of the stream at this
station was 96 ft. The cross-sectional area was estimated to be
116 ft2. The flow velocity was estimated to be between 1.1 and
1.3 ft/s. The calculated flow ranged from 127 to 150 cfs. The
flow measured at this station was greater than the flow measured
at the downstream stations the day before. This was most probably
due to the contribution of precipitation which had occurred in
the upstream drainage basin.
Ten mussel specimens (family Unionidae) were collected from
this station. Most of these were collected along the west bank.
23
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CHAPTER IV. FIELD STUDY SITE 2—TINKERS CREEK, OHIO
DESCRIPTION OF THE STUDY AREA
Tinkers Creek is located in Northeast Ohio. From its
source, it flows south and then to the northwest toward its
confluence with the Cuyahoga River.
The drainage area of Tinkers Creek is largely industrial
and urban. The focus of this field study was on the upper
reaches of Tinkers Creek and tributaries in the Walton Hills
area. This area is called the Deerlick Run Drainage Network.
A map of the study area is given in Figure 7.
The tributaries to Tinkers Creek in the study area—Hukill
and Ferro tributaries and Deerlick Run and its South Branch—are
small surface streams 3 to 5 ft wide and several inches deep
at the points where they flow under Egbert Road. These streams
have gravel and silt substrates and are easily accessible.
Deerlick Run, at the point of its confluence with Tinkers Creek
is 8 to 10 ft wide, 6 in deep and has a shale bedrock and
coarse gravel substrate. Tinkers Creek, at its confluence with
the tributary Deerlick Run, is about 50 ft wide, 1 to 3 ft
deep and has a coarse gravel and shale bedrock bottom. Deerlick
Run and Tinkers Creek have relatively steep gradients with several
waterfalls and rapids. Flow is estimated at 100-150 cfs.
During the Spring, Tinkers Creek is a Class V Whitewater stream.
During summer low-flow conditions, about 80% of the volume of
Tinkers Creek is contributed by upstream sewage effluents.
Several oil spills and industrial releases have impacted
these tributaries in recent years. The Ohio EPA (OEPA)
has conducted monitoring and toxicity studies on these
streams. These studies indicate the presence of stream
pollution from many diverse sources in this area.
Waste Inputs
The S.K. Wellman Company, a metalworking facility located
in the study area, was the focus for this field study. This
company is a user of lubricating oils thought likely to
contain chlorinated paraffins as an additive. This company
operates a plant that manufactures clutch and brake friction
materials for trucks and heavy equipment. While Ohio EPA
officials could not confirm that CPs were used in the process,
other sources of information indicated that CP-containing oils
were used. Process wastewaters from S.K. Wellman, up until about
1984, were discharged directly to Hukill Tributary and ultimately
to Tinkers Creek. The plant now discharges to the city of
Bedford's Publicly-Owned Treatment Works (POTW). Pollutants
including heavy metals (mainly copper), ammonia, oil, grease,
24
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DIRECTION
OF FLOW
FIG
. 7 - Tinkers Creek Study Site - Deerlick Run Drainage
25
-------
acids, and bases are present in the process wastewater. Noncontact
cooling water and stormwater are still discharged from the plant
property through National Pollutant Discharge Elimination System
(MPDES) outfalls to Hukill Tributary that then flows a distance
of about 2 km before it enters Tinkers Creek. It is likely that
ground water carrying contaminants from past waste management
practices (e.g., surface impoundments) located on site also
enters this tributary to Tinkers Creek. This company employs
about 250 people.
In the study area, there are also at least 17 industrial
facilities including chemical manufacturers, metal fabricators,
concrete plants, drum recyclers, three facilities with hazardous
waste units regulated under the Resources, Conservation, and
Recovery Act (RCRA) and one facility at which EPA performed an
emergency response cleanup of hazardous waste. The hazardous
waste facilities are located in the close proximity to each
other. Many of these facilities also have nonpoint source
discharges to this network of tributaries to Tinkers Creek.
The tributaries of this network originate immediately
upgradient of these industrial facilities. Storm sewer outfalls,
runoff, ground-water inflow, and nonpoint source discharges are
the sources of flow. There are no non-impacted upstream control
sites. Tinkers Creek is impacted by POTW and industrial outfalls
upstream of its confluence with this network of small tributaries.
RECONNAISSANCE SURVEY
On October 1 and 2, 1986, a reconnaissance survey was
conducted in the study area by Mr. Tom Janszen and Mr. Bob
Hoye of PEI Associates. Additionally, a meeting was held
with Ohio EPA representatives on October 2, 1986, to discuss their
knowledge of the operations conducted at the S.K. Wellman
facility, the physical setting of this and other plants in the
area and their discharges to surface waters. The purpose of the
visit was to gather the information necessary to design a field
study for the area, including the sampling of surface waters,
sediments, and mussels for CP analysis.
In their meeting with the Ohio EPA, the representatives of
PEI Associates were able to obtain only limited information
about the proposed sampling area. However, they were able to
visit the proposed site, photograph prospective sampling sites,
and evaluate the hydrology of the area. Their efforts produced
the following information about the area:
o There was no evidence of mussels or any other macro-
invertebrates or fish in the proposed study area. In
the best judgement of the reconnaissance team, it was
unlikely that mussels would be found in- the area.
26
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o Because Tinkers Creek flows through the Cleveland
Metroparks Bedford Reservation in the proposed study
area, permission to take samples from Tinkers Creek
and Deerlick Run could only be obtained from the Metroparks
Administration.
o No special sampling gear would be required in implement-
ing the field study.
o Streams in the study area were generally accessible.
o Stream samples collected in the study area would likely
contain a variety of organic and metal constituents
from past and current operations in the area.
o Sediment samples would be limited due to predominantly
gravel and rock substrate. Some silt is obtainable
from upstream areas within the tributary network.
FIELD STUDY DESIGN
The field study design for the Tinkers Creek area was
developed without the knowledge of the frequency of
occurrence of discharged constituents in the study area or
the statistical parameters associated with these constituents.
Further, although the S.K. Wellman Company's process wastewater
was now discharged to a POTW, the design was developed based on
the expectation that because this change was within the last 2
years, some residual CPs could, in fact, still reside in the
sediments of the Hukill Tributary. Therefore, the design included
six sampling stations; two stations in Tinkers Creek, one on Deerlick
Run at its confluence with Tinkers Creek, and one each on Hukill
Tributary, Ferro Tributary, and South Branch Tributary where they
flow under Egbert Road. A seventh sampling station was established
to capture a sample of the wastewater discharged from the facility's
NPDES outfalls which are discharged directly to Hukill Tributary.
Finally, arrangements were made with the facility manager to
collect samples from the process wastestream inside the plant
before it is discharged to the POTW. The station locations
are listed in Table 3 and shown in Figures 8 and 9.
With the exception of stations G and H, the design called
for the collection of a minimum of three individual grab or
composite water and sediment samples (Table 4).
27
-------
DIRECTION
OF FLOW
Not to scale
FIG. 8 - Location of Sampling Stations A through C at the
Confluence of Tinkers Creek and Deerlick Run
28
-------
Not to scale
FIG. 9 - Location of Sampling Stations D through G
29
-------
! TABLE 3 - Station Locations for the Tinkers Creek Study Site
i
Station ID Location
A Tinkers Creek immediately upstream
of the Deerlick Run confluence.
B Tinkers Creek immediately downstream
from the Deerlick Run confluence.
C Deerlick Run at its confluence with
Tinkers Creek.
D Hukill Tributary downstream from
the S.K. Wellman discharge and at
Egbert Road.
E Ferro Tributary at Egbert Road.
F South Branch Tributary at Egbert
Road.
G S.K. Wellman's NPDES outfalls.
H Process wastestream inside the
S.K. Wellman facility.
30
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TABLE 4 - Samples Collected from the Tinkers Creek Study Site
SAMPLE SET I SAMPLE SET II SAMPLE SET III
STATION ABCDEFGH ABCDEFGH ABCDEFGH
MEDIUM:
Water 11111111 1111111- 1111111-
Sediment 111111 111111 111111
Biota* j__i____ ________ ________
QC Water** 1 1 - ___ ___ _
* In lieu of mussels, fish samples were collected
** Equivalent in volume to 4 field samples
31
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FIELD SAMPLE COLLECTION
The Tinkers Creek field study was conducted from
October 14-16, 1986. All sample collection activities were
performed by PEI Associates under contract to MRI.
The observed flow and suspended solids loading in Tinkers
Creek during the study period was lower than observed during
the earlier reconnaissance survey. The flow in Tinkers Creek,
a perennial stream, has wide seasonal variations and short-term
fluctuations reflecting the effects of precipitation events
in the drainage area.
Sampling of Tinkers Creek, its tributaries, and the outfalls
at S.K. Wellman proceeded according the QAPP and followed the
sample collection protocol described in Appendix C.
A daily account of the field sampling effort follows.
Tuesday, October 14, 1986 - Stations A and B
The PEI Associates field team arrived at the study site and
met with MRI personnel to review the QAPP. The field study team
then proceeded to Cleveland's Metroparks Bedford Reservation,
where stations A, B, and C were located. First, a visit was made
to the Ranger's Office to confirm permission (obtained earlier)
to take samples from Tinkers Creek within the Reservation.
Then, the team proceeded to the confluence of Tinkers Creek
and Deerlick Run.
Three discrete mid-depth water samples, each a composite
of single grab samples from three equidistant points across
the stream, were collected at stations A and B. Three discrete
sediment samples, each a composite of single grab samples
from three equidistant points along a transect of the stream,
were taken at station A. The substrate at station B consisted of
large boulders; little silt or gravel sediment was present
in mid-stream because of the high velocity of the water flowing
in this area. Therefore, the grab samples for each integrated
sediment sample were taken on or near the stream banks from
areas that are periodically submerged. Generally, sediment
collected from stations A and B consisted of gravel, shale,
and fine sand/silt with no odor.
The field team also collected a QC sample at Station A.
This QC sample, equivalent in volume to four field samples, was
a composite of single grab samples collected at mid-depth from
three equidistant points across the stream transect. From this
QC sample, MRI prepared the field spike and field blank QC samples
for transport back to the laboratory.
32
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Tinkers Creek is about 70 ft wide at station A and 25 ft
wide at station B. A thorough search for benthic organisms, such
as mussels and the larval and pupal forms of the order Diptera
(e.g., ChironoTnidae), was made along the stream and in the stream
substrate in the area of Stations A and B. No larval or pupal
insect forms of any type were found; no mussels or any other
benthos were observed.
The swift current prevented the safe access to points across
the stream necessary to measure flow. Water temperature at both
stations was 14°C. The sampling team completed the field activities
at dusk, approximately 7:00 p.m. The samples collected from
stations A and B were prepared for shipment by packaging them in
coolers with sufficient cushioning material and ice.
Wednesday, October 15, 1986 - Stations C, D, E, and F
The field study team proceeded to the confluence of Tinkers
Creek and Deerlick Run to collect samples at station C. Three
discrete mid-depth water samples and three discrete sediment
samples, each a composite of single grab samples from three
equidistant points across the stream were collected. Deerlick
run at this location was 8 to 15 ft wide and 6 to 8 in deep
with pools 1 to 1.5 ft deep. The substrate was mostly bedrock
shale. Loose sediment consisted of gravel, shale, and fine sandy
material with no odor. The station was then thoroughly searched
for larval insect forms; none were found. The nature of the run
(pools, riffles, falls, and shallow water) was not amenable to
flow measurement. This effort was, therefore, aborted. Water
temperature at station C was 9.2°C. Some minnows (family
Cyprinidae) were observed in the pools at this station.
The team returned to stations A and B to observe stream
conditions. While station B was still considered unsafe because
of the fast current, station A had improved sufficiently to
measure flow. The cross-sectional area of the stream was determined
by measuring the water depth at 2-ft intervals along a transect
of the stream. Stream width at this point was 69 ft. The
cross-sectional area was estimated to be 101 ft . The flow
velocity was estimated by measuring the time required for 12
floats (oranges) to travel a distance of 100 ft. The estimated
velocity ranged from 1.4 to 0.9 ft/s. The estimated flow at
station A was calculated to range from 90 to 140 cfs.
The field team proceeded to stations F, F,, and D, respectively.
Three discrete water samples and three discrete sediment samples
were collected at each station. Because the tributaries were so
small, compositing samples was determined to be unnecessary.
Therefore, each sample was a single grab sample. The creek beds
at each station were thoroughly searched for larval insect forms;
33
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none were found. No mussels or other benthos were observed.
These tributaries were very small streams 4 to 8 ft wide and
only a few inches deep. Water temperatures at stations D, E and
F were 8.9 , 9.4 and 11.3 C respectively.
At station D, the field team collected a QC sample, equivalent
in volume to four field samples, and used this sample to prepare
field spikes and field blanks.
The field team completed the necessary sample forms, packaged
the samples and shipped them by overnight delivery to MRI's
laboratory in Kansas City, Missouri.
In lieu of any other biological specimens, the field team
decided to collect two fish samples. Minnows (family Cyprinidae)
had been observed in several pools of Deerlick Run. Seining of
two Deerlick Run pools just upstream of station C yielded enough
biomass for a sample. The field team also conducted extensive
seining from station A to a point approximately 0.3 mi upstream
of station A. By dark, the team had collected enough biota for a
sample. The fish samples were packed in a cooler with ice and
the sample forms were completed.
Thursday, October 16, 1986 - Stations G and H
The field team met with the management of the S.K. Wellman
Company. After a brief discussion, the field team was allowed to
collect one grab sample of the process water which is discharged
to the City of Bedford's POTW. A split sample was given to the
management of S.K. Wellman.
S.K. Wellman also has three NPDES discharges, one which
carries parking lot and roof drain runoff and two which carry
noncontact cooling water. These outfalls occasionally contain
traces of oil. The field team collected two discrete water
samples (plus a split sample for S. K. Wellman). Each sample
was a composite of single grab samples collected from each of
the three NPDES discharge pipes.
34
-------
CHAPTER V. EXPERIMENTAL SECTION
A total of 52 field samples plus 12 QC samples from Sugar
Creek were received by the MRI laboratory. An additional
41 field samples and 12 QC samples were received from Tinkers
Creek. Each sample, identified by the barcode labeling system,
was inventoried as it arrived in the laboratory (See Tables C-l
and C-2, Appendix C). An inspection of the samples showed that
all were intact; all mussels survived.
As was shown in Tables 2 and 4, three sets of samples
were constructed such that the first set (Set I) consisted of the
first samples of each type of medium collected at each of the
field stations. The second set (Set II) consisted of the second
samples of each medium, etc. Subsets comprise all samples of a
given medium within a set. To enhance study efficiency and
minimize analytical costs, analyses were to be conducted in a
logical sequence of sets and subsets.
The results presented in this report reflect the analysis of
Set I from Sugar Creek (See Table 5) and Set I from Tinkers Creek
(See Table 6). Because biological samples were so limited at both
field study sites, their analyses were done independently. For
example, all mussel samples collected from Sugar Creek were
analyzed as a part of Set I as proposed in the study design.
The fish samples collected from Tinkers Creek are being held in
reserve, since their collection was not directly called for in
the QAPP.
Within sets, the extracted field samples and the QC samples
were quantified in random order, "blind" to the GC/MS analyst.
EQUIPMENT
GC/MS analyses were performed using a Finnigan MAT 4000 Gas
Chromatograph/ Mass Spectrometer system. This system was equipped
with a 30-M x 0.25 mm i.d. fused silica capillary column, a negative
chemical ionization source and a J & W on-column injector. The
system was interfaced with an Incos 2400 data handling system.
Operating conditions and parameters are listed in Appendix A,
Table A-l.
35
-------
TABLE 5 - Sequence of Analytical Runs for Samples Collected
From the Sugar Creek Study Site
(Analyses within each run were made in random sequence
and unknown (blind) to the operator; method blanks
were analyzed with each run)
RUN NO. SUBSET NO. OF SAMPLES
1 Filtered water 8 field samples
+ 4 QC field samples
2 Suspended Solids 8 field samples
+ 4 QC field samples
SET I
3 Sediment 8 field samples
4 Mussels 3 field samples
5 Mussels 2 field samples
5 Filtered Water 8 field samples
+ 4 QC field samples
6 Suspended Solids 8 field samples
+ 4 QC field samples
SET II
7 Sediment 8 field samples
8 Mussels not available
9 Filtered Water 8 field samples
1 10 Suspended Solids 8 field samples
SET III
11 Sediment 8 field samples
|
I
I 12 Mussels not available
36
-------
TABLE 6 - Sequence of Analytical Runs for Samples Collected
from the Tinkers Creek Study Site
(Analyses within each run were made in random sequence
and unknown (blind) to the operator; method blanks
were analyzed with each run)
RUN NO. SUBSET NO. OF SAMPLES
1 Filtered Water 7 field samples
+ 4 QC field samples
2 Unfiltered Water 1 in-plant sample
SET I 3 Suspended Solids 7 field samples
+ 4 QC field samples
4 Sediment 6 field samples
5 Biota 1 field sample
6 Filtered Water 7 field samples
+ 4 QC field samples
7 Suspended Solids 7 field samples
+ 4 QC field samples
SET II
8 Sediment 6 field samples
9 Biota not available
10 Filtered Water 7 field samples
11 Suspended Solids 7 field samples
SET III
12 Sediment 6 field samples
13 Biota not available
37
-------
This GC/MS system was calibrated prior to sample analysis
over a range which covered the expected sample concentrations.
The initial calibration was then checked, at a minimum daily,
with a midpoint calibration standard at the beginning of the
sample run. Additional calibration standards were analyzed if
instrument instability was noted.
SAMPLE PREPARATION
The first set of environmental samples collected from
Sugar Creek and Tinkers Creek were extracted and analyzed
following the protocol described in Appendix A. Sample
preparation v/as performed in MRI lab 315W. With the exception
of the mussel samples from Sugar Creek, samples were extracted
within 1 week of receipt. The mussel samples were stored at
-20°C. This holding time was appropriate since chlorinated
paraffins are very stable at moderate temperatures. A check
on the integrity of the samples was provided by analytical
comparison of the trip-spiked samples with the lab-spiked samples.
The trip-spiked samples were deionized water spiked in the
field, transported and stored with the environmental samples; the
lab-spiked samples were deionized water spiked just prior to
extraction. Results showed that little or no sample degradation
had occurred (see Figures 10 and 11). Analysis of the trip
blanks—deionized water taken from the lab to the field and
maintained, shipped, stored, and analyzed with the environmental
samples—demonstrated that contamination of the samples had not
occurred.
With each sample batch a method blank was analyzed. (A
method blank is a procedural blank, which is carried through the
entire procedure to check for contamination.) These consisted of
distilled water for the water samples, sodium sulfate for sediment,
and mussels and blank filters for suspended solids. The following
control checks were used during the analysis: a performance
sample was run prior to sample analysis; and if instrument
instability was noted, standards were run between every two
samples. Chlorinated paraffins were quantitated using the average
of the two response factors bracketing the samples.
Experience gained during sample analysis indicates that
Negative Chemical lonization Mass Spectrometry (NCIMS) is rather
unstable when environmental extracts are analyzed. Upon install-
ation of a new filament, a period of slow but steady decline in
sensitivity was noted. This was followed by a rapid deterioration
and burn out of the filament. Several filaments were burned out
during the course of analysis of the environmental samples. This
instrument behavior can be attributed to the complex nature
38
-------
5:86
16:86
15:66
28:86
25:86
38:88
SCAN
35:68 llfE
FIG. 10 HRGC/NCIMS Determination of Chlorinated Paraffin Standards
in Trip-Spiked Water Sample. Sugar Creek, Station Lj.
The spiking level was 50 ppb. (Midwest Research Institute)
39
-------
188.8-
RIC
5:08
18:88
15:88
28:80 25:08
38:60
35:00 TIME
FIG. 11 HRGC/NCIMS Determination of Chlorinated Paraffins Standards,
Paroil 1160, Paroil 152, and Paroil 142. (Midwest Research
Institute)
40
-------
of the extracts and to the methane environment in the mass
spectrometer source; it appears to be an unavoidable character-
istic of the source. The decline in sensitivity and short
filament life were successfully accounted for by systematically
analyzing external standards with the environmental samples.
A reliable internal standard needs to be developed to facilitate
the routine CP analysis of environmental sample extracts.
STANDARDS PREPARATION
The chlorinated paraffins measured at Sugar Creek and in
the S.K. Wellman wastewater were quantitated using three
standards provided by the Dover Chemical Corporation. These were
Paroil 1160 (Cio~Ci2)' 50-60% Cl; Paroil 152 (Ci4-C17), 50-60% Cl;
and Paroil 142 (C20~C30)/ 40-50% Cl (See Figure 11). These
standards came very close to duplicating the three CPs (See Fig.
1), which were of interest to this study. While the CPs in
the environmental samples were quantitated against these
three standards, it is recognized that some CPs represented by
adjacent cells in the 9-cell matrix (see Figure 1) and present in
the samples could be quantitated unintentionally. The nominal
concentrations of these solutions are listed in Appendix A, Table
A-2.
METHODOLOGY
At the beginning of the study, the following five objectives
were established for selecting an analytical procedure for this
study. The analytical procedure must be able to:
o discriminate specific CPs (see Figure 1).
o reach a limit of detection at or lower than 5 ng/g
(low ppb range).
o obtain CP concentrations for replicate spike samples
with a range percent (precision) of less than 30% of the
mean of these values.
o measure CP concentrations with a percent difference
(accuracy) of less than 30% of the actual CP concentra-
tion.
o establish a recovery efficiency in the range of
70-130%.
41
-------
For the most part, these five objectives were met by the
study.
Method Selection
A computerized literature search revealed two methods which
were capable of determining CPs in environmental media. The
first (Hollies et al., 1979) was a Thin Layer Chromatography
(TLC) method with argentation of the chlorine atoms for visualiza-
tion and quantitation. This method is chlorine dependent and has a
limit of detection of 0.5 ppb for water and 50 ppb for semisolid
matrices. This method can distinguish long-chain (C20~C30) and
shorter chain-length (^13-^7) CPs with chlorine contents of
42-45% (w/w). This method combines solvent extraction/partition
and column chromatography followed by TLC. It has been used by
some investigators (Campbell et al, 1980) to study CPs in
environmental media.
The second method (Schmid and Muller, 1985) appeared to
better meet the study objectives because it could differentiate
between various chain lengths and chlorine content CPs and
would be less affected by uncontrollable interferences. This
detection and quantification method combines High Resolution Gas
Chronatography/Negative Chemical lonization Mass Spectrometry
with Selected Ion Monitoring (HRGC/NCIMS/SIM). It was developed
using a CI^-CIQ, 52% chlorine CP (Witachlor 352). This quantifi-
cation method has a limit of detection in the low nanogram
range, and has been used by its authors to demonstrate the
presence of CPs in sewage sludge, human adipose tissue, and sediment,
However, the method had not been characterized as to precision
and accuracy.
After carefully reviewing both methods, the Schmid and
Muller procedure was selected for the study. Steps were then
initiated to validate the method around the parameters imposed by
the study objective and using available standards.
METHOD DEVELOPMENT AND VALIDATION STUDIES
A full description of the method validation studies and
a statistical evaluation of their results is included in
Appendix B.
In validating this method, two questions arose concerning
the chemical and thermal stability of CPs during sample prep-
aration and analysis using this method. The first concerned the
effect of an H2S04 treatment on the integrity of the CP compounds.
The second concerned the stability of CPs when encountering the
42
-------
high temperatures of the GC/MS analysis. Studies were, therefore,
initiated to answer these questions. The results of these studies
showed that neither the H2SC>4/silica chromatography step (Figure 1,
Appendix A) nor the GC/MS analysis had a deleterious effect on the
recovery of CP standards.
In the sulfuric acid digestion experiment, the mussel samples
collected from Sugar Creek were digested for one hour using 40%
sulfuric acid on silica gel. The effect of this acid treatment on
CPs was investigated by digesting standard solutions of CPs in
hexane for periods up to 2 hours. No detectable loss of CPs
was noted, as determined by GC/MS analysis of the solutions
before and after acid treatment.
In the thermal decomposition experiment, decomposition of
CPs was observed during preliminary studies using a heated
inlet. This prompted a change to ambient on-column injection,
which was incorporated in the final method. Although there
are heated zones in the GC/MS interface, the atmosphere is
inert. The calibration curves clearly demonstrate that
instrument response is linear with respect to CP concentration,
indicating that significant decomposition did not occur.
The original sample preparation and method was modified,
(See Appendix A), prior to method validation. The validation
procedure was based on actual field samples obtained from Sugar
Creek except mussels, which were purchased. The method vali-
dation indicated that some modification of the method was needed
before the actual field samples were analyzed. For samples of
suspended solids, a smaller final extract volume, larger injection
volumes or compositing was necessary to reach the desired sensi-
tivity. For tissue samples, a more vigorous H2SC>4 treatment was
necessary in order to more effectively remove interferences. No
modifications were necessary for water and sediment samples.
43
-------
CHAPTER VI. RESULTS AND DISCUSSION
As described earlier, the design strategy for the
chlorinated paraffin field study in both the Sugar Creek and
Tinkers Creek study areas called for the collection of three
duplicate sets of water and sediment samples (plus available
biological samples) and the analysis of samples, one set at a
time, until sufficient data had been derived to meet the
previously stated study objectives. In following this strategy,
only the first set of samples from each area was analyzed. The
Sugar Creek data, because of consistency in analytical results,
are judged to be adeguate to demonstrate the release of CPs into
the receiving stream and to provide guantitative measurements of
those levels and of CP concentrations in samples from the stream
environment.^
Analysis of Tinkers Creek samples was curtailed after one
set when other industrial pollutants, largely halogenated
aromatics, were found to be present in the sampled material at
concentrations which masked any CPs that may have been present.
SUGAR CREEK STUDY AREA
The Sugar Creek Study Area evaluation is based on a total
of 29 residue analyses among 19 field samples, coupled with
confirmatory analyses of 13 guality control samples. This
effort comprises 16 analyses among 8 water samples ( 8 each of
particulates and filtered water), 8 analyses of as many sediment
samples, and 5 analyses among 3 composite mussel samples.
1 Given the retentive nature of the Dover Chemical surface
impoundment lagoon and the array of CP products which are currently
being produced or have in the past been produced, CPs other
than those addressed by this study, are expected to be present in
the sediments and the particulates. In addition, weathering of
the three CPs that were measured may have also occurred. These
considerations would lead to the conclusion that, while CPs are
definitely present, the guantitated levels should be considered
as estimates of the total CP concentration. Because the lagoon
retains the Dover Chemical discharge, no direct temporal relation-
ship can be drawn between the CP concentrations found in Sugar
Creek and the CPs produced by Dover Chemical during the time of
the field study.
44
-------
The analytical results from the sampling at Sugar Creek
indicate that chlorinated paraffins, represented in this study
as short-chain C^o-12 50-60% Cl; medium-chain C^4_X7 50-60% Cl;
and long-chain C2Q-30 40-50% Cl, were generally present in
the low parts-per-billion range in most of the samples collected
from the surface impoundment, the drainage ditch; and downstream
from the drainage ditch in Sugar Creek.
Long-chain CPs were reported in the low parts-per-billion
range in two upstream sediment samples. Also, short-chain CPs
were found in the low parts-per-billion range in one water parti-
culates sample immediately upstream of the drainage ditch. With
these exceptions, chlorinated paraffin concentrations were not
measured in quantifiable amounts in Sugar Creek upstream of the
drainage ditch.
The highest concentrations of CPs were found in the impound-
ment sediment and in the biological samples collected downstream
from the drainage ditch. Quantifiable concentrations were also
measured in the particulate matrices. Where CPs were detected
in the filtered water (filtrate), they were found, inconsistently,
only in the impoundment and the drainage ditch water and only at
low parts-per-billion levels.
Of the three CPs addressed by this study, the long-chain
CP (C2Q-30' 40-50% Cl) was generally found at the highest levels.
These findings are consistent with the available literature
which reports that the microbial degradation of paraffins appears
to be related to the carbon chain length and percent chlorination.
Higher chlorinated (above 50%) and long-chain C20-30 compounds
resist degradation. Short-chain (Cio-ia) 49% Cl degrade
most readily (Madeley and Birtley, 1980). Also, these results
are consistent with studies of CPs which indicated that CPs
readily adsorb to sediments and particulate matter (Campbell and
McConnell, 1980, and Ramm, 1978).
Because it acts as a natural sink for particulate matter,
the highest CP concentrations in the study area were found,
within media, in the surface impoundment lagoon, especially its
sediment (Figure 12, Tables 7 and 8). Residues in sediment were
reportedly highest at the inflow end of the lagoon (1-2) (See
Figure 13) and lowest at the outflow end (L^). At all sampling
stations, the long-chain C20-30' 40-50% CP predominated, with
sediment concentrations as high as 170,000 ;ug/kg. Concentrations
45
-------
STATION
SHORT CHAIN
MEDIUM CHAIN
LONG CHAIN
40,000 T
50,000 SEDIMENT
170,000 I
S - 32,000
M - 34,000
L - 84,000
DRAINAGE
DITCH
NOT TO SCALE
SURFACE
IMPOUNDMENT
LAGOON
FIG. 12 CP Concentrations in the Dover Chemical Surface Impoundment Lagoon.
Values are not adjusted for method recovery. Sediment Concentrations
are in ug/kg; Particulates concentrations are in ug/L.
46
-------
Table 7 CP Concentrations (ug/kg) in Sediment* of the Lagoon and Drainage
Ditch, by Carbon Chain-length Groups and Cumulative Mass
Ranges (parenthesized)
Sampling
Location
LI
L2
L3
D
Number
of Samples
1
1 .
1
1
Cm - C17
(323-329; 357-363;
365-399)
16,000
40fOOO
32,000
1,200
C14 - C17
(399-419; 439-453;
475-487)
21,000
50,000
34,000
760
c?n - c-^n
(496-506; 512-517)
21,000
170,000
84,000
3,600
* CP concentrations are based on dry weight of sediment after removal of rocks. Values are not
adjusted for method recovery.
-------
OD
Table 8 CP Concentrations* (pg/L), in Filtrate and Particulates, from Filtered
Impoundment and Drainage Ditch Water, by Carbon Chain-Length Groups and
Cumulative Mass Ranges (parenthesized)
Sampling
Location
LI
L2
L3
D
Number
Of Samples Matrix
1 Filtrate
Particulates
Sum
1 Filtrate
Particulates
Sum
1 Filtrate
Particulates
Sum
1 Filtrate
Particulates
Sum
Cm- C19
(323-329; 357-363;
365-399)
Tr**
3.3
3.3.+Tr
0.25-0.51
2.8
3.0-3.3
0.39-0.57
2.3
2.7-2.9
Tr
2.3
2.3+Tr
CT 4— Ci7
(399-419; 439-453;
475-487)
ND***
3.8
3.8
Tr
2.4
2.4+Tr
Tr
2.6
2.6+Tr
Tr
1.5
1.5+Tr
Cy^-C^
(496-506; 512-517)
ND
11
11
ND
3.6
3.6
0.61
7.7
8.3
Tr
3.7
4.0
* = Values are not adjusted for method recovery.
*Tr = Trace (Cone, between 0.15 and 0.50 ug/L).
**ND = Not detected (Cone. <0.15 ug/L);
-------
RJC
t - r • r
-i 1 1 r
15:80
17:30
28:00
22:30
25:80
27:30
SCAN
38:68 TIME
FIG. 13 HRGC/NCIMS Determination of Chlorinated Paraffins
in Sediment Sample Collected from Station L,2/
Surface Water Impoundment Lagoon/ Sugar Creek.
(Midwest Research Institute)
Note: The 2 peaks to the right of the Chlorinated
Paraffin mass range are non-CP interferents.
49
-------
were intermediate for the medium-chain CP and lowest for the
short-chain CP.
Concentrations adsorbed to particulates filtered from
the depth-integrated water samples collected from the lagoon
were also highest for the longer chain CP, the highest
concentration being 11 jig/L at station L]_. There was no
discernible correspondence between residue levels in water
particulates and those in sediment from the respective sampling
stations.
Water samples collected from the lagoon were composites
of discrete grab samples integrated from depths of 2, 10, and
17-20 ft. Temperatures recorded at each station and at
these depths ranged from 21.5°C to 22°C. The water was clear
to slightly cloudy at all locations. The sediment was mostly
black to dark gray, a fine silt with some but not a strong
odor. Two of the three sediment samples collected from
station 1,3 were a light brown fine silt with no odor.
Chlorinated paraffin concentrations measured in the
filtered water fraction of the lagoon samples were near or
below the level of quantitation but were still reported for
at least one chain length in all samples. There was
no discernible correspondence between residue levels in
particulate material and in the respective filtrate of the
lagoon water samples. No mussels were available for analysis
from the lagoon.
In the ditch, which served as the drainage conduit for
the lagoon and therefore represented Dover Chemical Corporation's
point source discharge to Sugar Creek, CPs were detected in
each matrix analyzed (Figure 14, See Tables 9 and 10). Again,
the long-chain CP predominated with the highest concentration
(3,600 ug/kg) found in the sediment. Quantifiable concentrations
were found in the particulates, and trace or marginally
quantifiable concentrations were found in the filtered water
column. The water temperature at this station was 23.5°C.
The flow was reported as 1.2 cfs. In Sugar Creek, the receiving
stream, CPs were largely not detected above its confluence
with the Dover Chemical drainage ditch, but were measured in
quantifiable levels at stations downstream from this drainage
ditch (Tables 9, 10, and 11).
At the far upstream station (station B), the only
quantified value was 11 ug/kg of the long-chain CP found in
the sediment matrix. No CPs were detected either in the
filtered water fraction or the tissue of mussels (which were
collected along the west bank of the stream). A second
analytical run of mussels collected from this station revealed
50
-------
I
w
f
s
A
SHORT
ND
TR
ND
W
pptlti
ND
ND
TR
ND
LONG
ND
NO
11
ND*
1
/
N
f
W . Water
P « Particulates
S » Sediment
M = Mussel
9
H
P
S
*
SHORT
ND
0.3
TR
TR
ffDILM
ND
TR
TR
ND
LONG
ND
TR
8,1
ND«
SHORT
w ND
0.21
TR
ND ND
0.18 0.62
6.8 9.8
M 280 170
Limit of
Cbtaction
0.15
0.05
1.5
7.0
Limit of
diantitation
0.5
0.17
5.0
22.0
Units
ug/1
uq/1
ugAq
ugAg
TR » Trace
ND » Not detected
* - Data represents 2 analytical runs; all other
represent one run.
^~
»«t
W
SHORT EBllUM LOMG
W TR TR . 0.5
P 2.3 1.5 3.7
S 1.200 760 3600
M LONG
FIG. 14 CP Concentration in the Dover Chemical Drainage
Ditch and Sugar Creek. Values are not adjusted
for method recovery.
51
-------
Ul
K)
Table 9 CP Concentrations (ug/kg) in Stream Sediment*, by Carbon Chain-length Groups
and Cumulative Mass Ranges (parenthesized)
Sampling
Location
B
B1
A1
K
Number
Of Samples
1
1
1
1
Cin - Ci? Ci4 -Ci7
(323-329; 357-363; (399-419;439-453;
365-399) 474-487)
^jr\ifr^r^ rn.p.yf^f^r
Tr Tr
Tr 6.8
5.5-7.3 8.2
C?n - C^n
(496-506; 512-517)
11
8.1
9.8
21
* CP concentrations are based on dry weight of sediment after removal of rocks. Values are not
adjusted for method recovery.
** ND = Not detected (Cone. <1.5 ug/kg)
*** Tr = Trace (Cone, between 1.5 and 5.0 ug/kg)
-------
Table 10
CP Concentrations fyjg/L), Participates*, from Filtered Stream
Water, by Carbon Chain-Length Groups and Cumulative Mass Range,
(parenthesized)
Sampling
Location
B
B1
A1
K
Number of
Samples
1
1
1
1
Cin - C17
(323-329; 357-363;
365-399)
Tr**
0.27-0.30
0.20-0.23
Tr
c14 - c17
(399-419; 439-453;
475-487)
ND ***
Tr
0.16-0.20
0.20-0.24
C?n - C-^n
(496-506; 512-517)
ND
Tr
0.62
0.35
* Values are for particulate contributions only. CP residues were not detected in filtered
Stream Water (filtrate) samples. Values are not adjusted for method recovery.
** Tr = Trace (Cone, between 0.05 and 0.17 ug/L)
*** ND = Not detected (Cone. <0.05 ug/L)
-------
Table 11
CP Residues* (iig/kg) in Composite Mussel Samples from Sugar Creek, by Carbon
Chain-length Groups and Cumulative Mass Ranges (parenthesized)
Sampling
Location
n
B'
A1
K
Number of
Compos ite
Samples
1
1
1
0
Mussels Gin - C-|?
Per (323-329; 357-363;
Composite 365-399)
1 ND**
1 Tr***
2 280
— —
(~* ~ M- /~i^
i 4. 1 /
(399-419; 439-453;
475-487)
ND
ND
170
—
c™ - c,n
(496-506; 512-517)
ND
ND
180
—
* = Values are not adjusted for method recovery.
** ND = <7
*** Tr = >y<22
-------
trace levels of both the short and medium-chain CPs. Trace
amounts of the short-chain and medium-chain CPs were found in
the particulates and sediment matrices, respectively.
Water temperature at station B was 20.5°C. The flow
ranged from 127-150 cfs. The flow at this station was greater
than that measured the day before at downstream stations,
probably because of the contribution of precipitation occurring
in the upstream drainage basin.
At station B1, located just upstream of the drainage
ditch confluence, a quantified concentration (8.1 jug/kg) of
the long-chain CP was reported in the sediment sample, and a
low part-per-billion (0.3 pg/L) residue of short-chain CP was
reported for particulates in the water column. Otherwise,
concentrations in all matrices were reported as trace (Tr)
or not detected (ND). No CPs were detected in the filtered
water fraction. A trace value of the short-chain CP was
found in the composite mussel sample collected from this
site. These mussels were collected from a small portion of
the stream situated on the west side of a small island about
150 ft upstream of the location where the water and sediment
samples were collected. A second analytical run of mussels
collected from this station did not detect CPs of any chain
length. The water temperature at this station was 20.5°C.
Below the influence of the drainage ditch, quantifiable
concentrations of CPs wre measured in all matrices except the
filtered water fraction. At station A1, which was located
just downstream from the drainage ditch but above the influence
of Goettge Run, quantifiable concentrations of each of the
three CPs were measured in the composite mussel sample
collected from this site: 280 }ig/kg of the short-chain CP,
170 jag/kg of the medium-chain CP, and 180 jug/kg of the long-
chain CP. In the sediment matrix, concentrations of 6.8 and
9.8 pg/kg were reported for the medium and long-chain CPs,
respectively. Trace levels were reported for the short-chain
CP in this matrix. Because only coarse gravel and cobble
were present at station A", the sediment samples were collected
approximately 15 ft upstream of the point where water
samples were collected.
In the particulates matrix, quantifiable concentrations
were found for each chain length (0.21, 0.18, and 0.62 ug/L
for short-, medium-, and long-chain CPs, respectively). The
water temperature at station A1 was 20.5°C.
At the far downstream station (station K), CP concentrations
were also evident. As at all stream stations, no CPs were
detected in the filtered water matrix; however/ quantifiable
concentrations were found in the particulates and sediments.
In the particulates fraction, while only trace leve-ls of the
55
-------
short-chain CP were found, 0.22 pg/L and 0.35 ug/L of the
medium, and long-chain CPs, respectively, were measured. In
the sediments, 6, 8 and 21 pg/kg of the short, medium, and
long-chain CPs were reported, respectively. The sediments at
this station were gravel to fine brown silt with no odor. No
mussels were available for analysis from this site. The
water temperature was 20.5°C.
Statistical Evaluation of the Sugar Creek Data
As stated in Chapter I., the objective of this study was
to determine, preliminarily, if chlorinated paraffins exist
in selected water environments [here, the Sugar Creek study
area] and, if so, at what concentrations. The study data,
although necessarily limited to chemical analysis of one of
three replicated sets of water, particulates and sediment
samples from eight sampling stations plus mussels samples
from three of those stations, have been determined to be of
sufficient quality to meet the study objective. The
determination of sufficiency utilizes findings from the
method validation chemistry presented in Appendix B plus the
observed consistency of analytical results relative to the
type of environment sampled (i.e., surface impoundment, etc.)
From what is known about the behavior of CPs in an
aquatic environment (extremely low solubility, propensity to
adsorb to suspended particulates and sediment and to
bioaccumulate), one would expect that if CPs were present
in the study environment as the result of effluent discharge,
overall concentrations would be highest in the surface
impoundment, next highest in the outflow ditch, present but
at lower levels downstream from the ditch outflow, and lowest
or virtually absent upstream of the outflow. This, exactly,
was the outcome for reported concentrations in all sediment
and particulate samples, respectively, and for the three
mussel samples from Sugar Creek. Because of extremely low
solubility, CPs were not detected in filtered stream water
and barely so in impoundment and ditch water, a result not
inconsistent with expectations.
Reported CP concentrations in impoundment sediment (Table
7) ranged from 16,000 pg/kg of the short-chain (Cio-12^ CP
(station 1^) to 170,000 pg/kg of the long-chain (C2o-30^ CP
(station L2), with a median concentration of 34,000 pg/kg
(^14-17 ('P' station L^) . These concentrations averaged
approximately 30 times the respective chain-length concentration
reported in the ditch sample (Table 7). In turn, ditch sample
concentrations (median 1,200 pg/kg) were from 95 to 170 times
the highest concentrations reported in downstream sediment samples,
56
-------
Using the working eguations for the prediction of true
CP concentrations in sediment (3) from reported concentrations
(Y) and for calculation of 95% confidence limits for those
predicted values (Table B-8, Appendix B), it has been observed
that there is no overlap in the lower 95% confidence limits
for predicted true concentrations of the C^g-12 an<3 ^14-lT
CPs in impoundment samples and the respective upper 95%
confidence limits for predicted true concentrations in the
ditch sample. (There was some overlap of C2Q-30 confidence
limits as a result of lower precision for those estimates.)
Similarly, it has been determined for each carbon chain-length
group that there is no overlap between the lower 95% confidence
limit for the predicted true concentration in the ditch sample
and the upper 95% confidence limit for the highest predicted
true concentration in a downstream sediment sample (Station
K, Table 9). Thus, with the exception of the C2Q-30 CP i°
impoundment sediment, it has been demonstrated at the 95%
confidence level that true CP concentrations, as sampled,
were highest in impoundment sediment, intermediate in the
outflow ditch sediment, and lower downstream from the ditch
than in the ditch itself. Concentrations reported in sediment
samples upstream of the ditch outflow were generally numerically
lower than those for downstream samples, an exception being
the C2Q-30 value of 11 pg/kg for station B. (Rather than
attempt to test differences between upstream and downstream
sediment concentrations per se, a broader test that incorporates
all sampled media will be presented.)
CP residues adsorbed to suspended particulates resulted
in concentrations (pg/L) that tended to be numerically slightly
higher in unfiltered water samples from the impoundment than
in the sample from the ditch (Table 8). Concentrations
reported for unfiltered water samples downstream from the
ditch outflow were approximately one-tenth those for the
ditch. With one exception (the C^o_i2 CP' Station B1), all
reports for upstream samples were either "not detected" or "trace".
Concentrations reported for suspended particulates would
seem to be consistent with flow and dilution factors, especially
regarding the concentration decreases from outflow ditch to
stream. Apparently, there has been significant transport of
CPs via the impoundment as evidenced by concentrations in
unfiltered ditch water and the accumulated residues in ditch
sediment. Although it was not possible to develop eguations
for predicting true concentrations for suspended particulates,
it can be shown that if there were truly no differences
between impoundment/ditch concentrations and stream
concentrations, the probability that analytical variation
would, by chance alone, result in the highest values being reported
57
-------
for the four impoundment/ditch samples and the lowest values
for the four stream samples is approximately 0.01 (one chance
in a hundred).
Comparison of overall differences in CP concentrations
between stations upstream of vs. downstream from the ditch
outflow utilizes the reported total concentration of CPs in
each sediment, particulate, and mussel sample. The total
concentration in each sample was derived as the sum of its
^10-12' '--14-17 an<3 ^20-30 CP concentrations, using mid-range
values for reports of "trace" and "not detected".
For upstream stations B and B1 and downstream stations
A" and K, respectively, total CP concentrations were 14.6,
14.5, 19.8, and 35.6^ig/kg for sediment samples; 0.16, 0.47,
1.0, and 0.68 jjg/L for particulate samples; and 10, 21 and 630
jjg/kg in mussel samples, with station K providing no sample.
Thus, for each medium, the total of CP residue reported for
each sample is consistently higher in samples from the
downstream stations. If, in fact, there were no differences
within media between upstream and downstream true concentrations,
the probability that, by chance alone, analytical variation
would consistently result in downstream samples having the
higher reported concentrations is less than 0.01.
The validity of the foregoing comparisons of CP
concentrations requires the assumption that results were not
measurably biased either by sample collection or laboratory
procedures, including the order in which samples were collected
and/or analyzed. In this respect, the study protocol specified
standardized sample collection, handling, and analytical
procedures and, within media, that samples be processed and
analyzed in random order "blind" to the analyst (i.e., the
analyst did not know from which station a sample had been
collected). Water and sediment samples were collected over a
3-day period and mussels within a 1-day period. It would
seem unlikely that CP concentrations in sediment and mussels
would have changed measurably during the respective periods
or that particulate concentrations would have changed
sufficiently to alter the ranking of concentrations among
stations. Collection stations were not randomly located, but
rather strategically located to derive data needed to best
meet the study objective. Samples are considered to be
representative of the study environment at the time of collection,
In summary, the data indicate that chlorinated paraffins
do exist in the receiving stream in the area of the Dover
Chemical Plant, and that discharge levels from the drainage
ditch, plus the relative differences in residue between
upstream and downstream samples, are results sufficient to
58
-------
support the statement that the Dover Chemical Plant, via
its surface impoundment lagoon, is a source of CP residues in
Sugar Creek.
The reason that some quantifiable concentrations of CPs
were found upstream of the discharge ditch is not readily
apparent. There are no known CP manufacturers, processors, or
users of CPs upstream at this time. Further, Sugar Creek is
impounded upstream which would likely sequester any CPs
adsorbed to particulate matter, should they be present. On
the other hand, the Dover Chemical surface impoundment lagoon
has reportedly overflowed in the past. These incidences would
likely carry CP-laden particulates to the stream upstream of
the discharge ditch. Also, because the lagoon is in direct
contact with a shallow aquifer, CPs could be reaching Sugar
Creek through ground water recharge. Additional study is
needed to test these hypotheses.
Monitoring versus Modeling Results
Where environmental measurements are scant, mathematical
models can oftentimes provide estimates that can bridge the
information gap that exists between environmental concerns and
sensible risk management decisions. This was the case in
1985, when, in an effort to supplement a limited monitoring
data base on CPs, a preliminary modeling analysis was performed
to estimate CP concentrations in three watercourses: Sugar
Creek, Ohio; Schuykill River, Pennsylvania; and Galveston
Bay, Texas (Versar 1985, GSC 1985). This modeling effort,
based on reasonable production estimates and professional
judgment, produced estimates of environmental CP concentrations
that were generally consistent with available environmental
monitoring data.
The 1986 Sugar Creek field study, because it measured
actual environmental release information from a CP manufacturer,
provided an opportunity to repeat the modeling analysis for
Sugar Creek, using measured environmental release information.
It also provided an opportunity to compare, directly, estimated
results generated by the model with actual field measurements.
The following discussion first describes the 1985 modeling
effort in Sugar Creek and then compares this preliminary
analysis with the 1986 effort using new monitoring information.
The 1985 modeling analysis was performed to estimate CP
loadings to Sugar Creek based on CP release estimates (PEI,
1984) and best engineering judgment. The CP release estimates
did not differentiate the chlorinated paraffins of various
carbon chain length and degree of chlorination.
59
-------
The Exposure Analysis Modeling System (EXAMS) was used
to estimate the concentrations of CPs in surface water,
sediment, and biota. Two compartments were assumed for
modeling purposes: (1) Sugar Creek before it enters the
Tuscarawas River (3000 m long with a mean stream flow of
330 cfs) and (2) the Tuscarawas River downstream from the
confluence of Sugar Creek (13,000 m long with a mean
stream flow of 1,740 cfs). The model assumed complete and
uniform mixing within each compartment. The model was run
under controlled (CP removal during waste treatment) and
uncontrolled (no CP removal) release scenarios.
Two CPs were selected for modeling based on their physico-
chemical properties. These were the short-chain (Cj^), highly
chlorinated CP Chlorowax 500-C and the long-chain ^24),
highly chlorinated CP Chlorowax 70.
The controlled release rates of Chlorowax 500-C and
Chlorowax 70 were derived individually by multiplying the
estimated uncontrolled release rate (1.7904 kg/yr) by a
removal factor based upon the organic carbon partition
coefficient. The estimated controlled releases of Chlorowax
500-C and Chlorowax 70 were 63.06 and 0.35 g/day, respectively
(Versar 1985, GSC 1985).
The modeling analysis was then repeated using the actual
environmental releases of short-chain and long-chain CPs,
measured during the 1986 EPA field study at Sugar Creek. The
field data used for this analysis were the CP releases measured
at station D, the drainage ditch which carries the Dover
Chemical plant's waste discharge to Sugar Creek. The releases
(loadings) measured during the 1986 field study were 0.97
and 1.46 g/day for the short-chain and long-chain CPs
respectively. The measured loading of the short-chain CP is
significantly lower than the estimated loading (63.0 g/day)
used in the 1985 preliminary modeling study by GSC. Although
no statistical significance can be attributed to these data,
the results showed that the model estimates were comparable
with the monitoring data.
A comparison of the 1985 preliminary modeling estimates,
the modeling estimates using input from the 1986 field study
and the actual concentrations measured in the field is given
in Tables 12 and 13 for the short-chain and long-chain CPs,
respectively. While too few field data were available for
this to be considered a full validation of the model, the
correspondence between model predictions and field measurements
suggests that the modeling approach provides a reasonable
measure of CP concentrations in the receiving water environment.
60
-------
TABLE 12 - Comparison of Preliminary Modeling, Field Sampling
Data and Modeling Results Using Field Estimates
of Chlorinated Paraffins Loadings (C^Q_^2' Short Chain)
Load
Water Suspended Benthic
Column Particulates Sediments Biota
(g/day) (jug/L) (jag/kg)
(jjg/kg)
Original Model
Estimates in
1985 GSC Report1
63.0
0.007
23.1
125.0
9,690
Model Estimates
Using Input from
1986 Field
Sampling ^
0.97 0.001
0.37
1.98
155
1986 Field Sampling
Data
0.97
ND-
Trace
6.4
280
1 Based on Best Engineering Judgment
2 Loading Based on Cone, of CPs Dissolved in
Water and Sorbed to Suspended Solids Being
Released to Sugar Creek
3 Detection Limit = 0.15 jug/L
4 Trace = 0.05 - 0.17 jig/kg
61
-------
TABLE 13 - Comparison of Preliminary Modeling, Field Sampling
Data and Modeling Results Using Field Estimates of
Chlorinated Paraffin Loadings (C2Q-30' Long-chain)
Water Suspended Renthic
Load Column Particulates Sediments Biota
(g/day) (jig/L) (jig/kg) tyig/kg) (jig/kg)
Original Model
Estimates in
1985 GSC Report1 0.35 8.06E-05 4.64 25.07 15,300
Model Estimates
Using Input from
1986 Field
Sampling2 1.46 3.37E-04 19.4 105.00 64,000
1986 Field Sampling
Data 1.46 ND3 0.35 21.0 180
Based on Best Engineering Judgment
Loading based on concentrations of CPs dissolved in
water and sorbed to suspended solids being released
to Sugar Creek
3 Detection Limit = 0.15
jjg/L
62
-------
Due to the scant field data, it is also not possible to
determine the reasons for the differences that exist between
the field measurements and model estimates.
The comparison of the 1986 monitoring data with the
updated modeling estimates using measured releases illustrates
that, given a correct CP discharge loading, the model is a
predictive tool that can be used with some confidence in
other aquatic systems, where monitoring data are lacking.
Until further study is made, this predictive ability must be
considered limited to the chlorinated paraffins of the types
considered by this report and the water/solids systems of the
kind dealt with by this study.
TINKERS CREEK STUDY AREA
The analytical results of the Tinkers Creek samples
indicate that chlorinated paraffins, represented by the short-
chain Cio_20f 50-60% chlorine, the medium-chain Ci4_}7, 50-
60% chlorine and long-chain C2Q-30' 40-50% chlorine CPs,
could not be detected in any of the samples collected from
the S.K. Wellman NPDES outfalls or waters receiving direct
discharge from the plant. These waters included the network
of tributaries which make up the Deerlick Run drainage network
and Tinkers Creek. Most of these samples, especially the
sediment samples, contained a variety of organic constituents
at high enough concentrations to mask the presence of any
CPs. These interferences, largely halogenated aromatics,
essentially raised the limit of detection of the method. In
other words, if CPs were present, they could not be resolved.
These interferences could be attributed to the highly
industrialized nature of the Tinkers Creek area. (Water
temperatures measured in the area ranged from 9 to 14°C. The
substrate consisted of fine silt or gravel with no odor.
Flow was immeasurably slow in the tributary network. Flow
was measured as 90 to 140 cfs in Tinkers Creek.)
Chlorinated paraffins, however, were detected in the
sample collected from the process wastestream inside the S.K.
T'Teliman plant. This sample was collected near the end of the
assembly process just before the wastestream is discharged
from the plant to the main POTW interceptor. CP concentrations
were measured as follow: short-chain CP, 8.1 ug/L; medium-
chain CP, 1.3 ug/L; and long-chain CP, 2.2 jjg
pg.
/L.
63
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CHAPTER VII. REFERENCES
Campbell, I. and McConnell, G. "Chlorinated Paraffins and the
Environment," 1. Environ. Sci. Technol. 1980, 14, 1209-1215.
- - - -
Feller, V. An Introduction to Probability Theory and its
Applications ; 3rd ed . Wiley, New York, 1968. Vol. I.
General Software Corp. 1985 "Modeling of chlorinated paraffins
in their aquatic ecosystems," Landover, Maryland.
Hollies, J.I., Pinnington, D.F., and Handley, A.J. "The
determination of chlorinated long-chain paraffins in water,
sediment and biological samples," Anal . Chim. Acta 1979, 111 ,
201-213. *^*
Madeley, J.R. and Birtley, R.D.N. "Chlorinated paraffins and
the environment." 2. Aquatic and Avian Toxicology, Environ.
Sci. Technol. 1980, 14, 1215-1221.
- - -
PEI Associates, Inc. 1984, Exposure Assessment of Chlorinated
Paraffins, Washington, D.C.
Ramm, Alan E. personal communication to Jack Borror concerning
sediment and biota sampling, November 21, 1978.
Ramm, Alan E. personal communication to Jack Borror concerning
results of Chlorowax investigations in Grand River, July 19, 1977,
Schmid, P.P. and Muller, D. "Trace level detection of
chlorinated paraffins in biological and environmental samples
using gas chromatography/mass spectrometry with negative-ion
chemical ionization," J. Assoc. Off. Anal. Chern. 1985, 68,
427-431. ~ """*" ~~
Snedecor, G. and Cochran, W. "Statistical Methods," 7th ed .
Iowa State University Press, Ames, Iowa, 1980.
SRI, International, "1986 Directory of Chemical Producers, USA,"
Menlo Park, California. 1986.
U.S. Environmental Protection Agency, "Hazard Assessment for
Chlorinated Paraffins: Effects on Fish and Wildlife," Health
and Environmental Review Division, March 1984.
U.S. Environmental Protection Agency, "Chloroparaf f ins
Environmental Field Study, Quality Assurance Project Plan,"
Washington, D.C. 1986.
Versar Inc. "Preliminary Exposure Assessment for Chlorinated
Paraffins," Springfield, Virginia, 1985.
64
-------
The approach used in analyzing and evaluating the CP method
validation data was taken from: Heath, R.G., Harless, R.L.,
Gross, M.L. , and Lyon, P.A.; Dupuy, A.E. Jr., and McDaniel,
D.D. Determination of 2 ,3 ,7 ,8-Tetrachlorodibenzo-p_-dioxin
in Human Milk at the 0.1-10 Parts-Per-Trillion Level:
Method Validation and Survey Results. Anal. Chem. 1986,
58, 463-468.
65
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APPENDIX A
ANALYTICAL METHOD
-------
TABLE OF CONTENTS
Section
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
FIGURES
A-l
Heading
Paqe
TABLES
A-l
A-2
A-3
A-4
Scope and Application A-2
Summary of Method A-2
Definitions A-2
Interferences A-4
Apparatus and Equipment A-5
Reagents and Standard
Solutions A-7
GC/MS Performance Criteria A-8
Quality Control Procedures A-l2
Sample Preservation and
Handling A-13
Sample Preparation and
Extraction A-13
Cleanup Procedures A-17
Instrumental Procedures A-18
Data Reduction A-20
Extraction and Cleanup
Procedures for Chlorinated
Paraffins A-3
HRGC/NCIMS Operating Conditions for
CP Analysis A-6
Concentration Calibration Solutions A-9
SIM Mass Ranges for CP Analysis A-10
Typical Daily Sequence for CP Analysis A-19
A-l
-------
1. SCOPE AND APPLICATION
This method provided procedures for the detection and
semiquantitative measurement of chlorinated paraffins in
water, suspended solids, sediment, and mussel tissue.
Chlorinated paraffins measured with this method are Cin~c12'
50-60% Cl ; C14-C17, 50-60% Cl; and C20-C30, 40-50% Cl.
2. SUMMARY OF METHOD
Figure A-l presents a schematic of the analytical procedures
used for determining chlorinated paraffins in water, sediment,
suspended solids, and mussel tissue. The method requires
sample preparation, extraction of chlorinated paraffins,
cleanup, concentration, and determination by high resolution
gas chromatography/negative chemical ionization mass
spectrometry/selected ion monitoring (HRGC/NCIMS/SIM).
3. DEFINITIONS
3.1 Concentration Calibration Solutions
Solutions containing known amounts of analytes. These
calibration solutions are used to determine instrument
response of the analytes as a function of mass.
3.2 Sample Batch
A sample batch consists of up to 10 environmental samples
of the same matrix, one laboratory method blank, and two
internal quality control samples (one spiked and one
unspiked). Additional QC samples (e.g., field QC samples,
trip QC samples) may be added to a sample batch where
appropriate.
3.3 Laboratory Method Blank
This blank is prepared in the laboratory and contains
all of the analytical reagents in required quantities
and is carried through the performance of all analytical
procedures except addition of a sample aliquot to the
extraction vessel. A minimum of one laboratory method
blank will be analyzed with each batch of samples.
3.4 Laboratory Method Spike
This sample consists of an aliquot of matrix to which
a known amount of analyte is added. All analytical
procedures are performed on this spike. A minimum
of one laboratory spike is analyzed with" each batch of
samples to monitor recovery for that batch.
A-2
-------
Water
(1 L)
i
r
Sediment
(AJ100 g)
Dry
Suspended
Solids
Extract
With
Hexane
Soxhlet
Extraction with Hexane
I
Concentrate
I
Analyze
Column Chromatography:
H2SC>4/Silica Column,
Alumina Column
Biota
(A/100 g)
Homogenize, Dry
Extract with
Hexane H2SC>4/
Silica Slurry
Cleanup
FIG. A-l Extraction and Clean-Up Procedures for
Chlorinated Paraffins
A-3
-------
3.5 Field QC Samples
A sample collected in the field, homogenized, and
divided into four aliquots. Two of the aliquots are
spiked in the field (field spikes) and two are left
unspiked (field blanks). The field blanks are spiked
in the laboratory at the same level as the field
spikes, analyzed, and compared to the field spikes to
monitor analyte behavior during transportation and
storage.
3.6 Trip QC Samples
Blank matrix samples prepared in the laboratory, taken
and maintained on the sampling trip. Half of the
samples are spiked in the field and the remaining half
left unspiked. The samples are transported, stored,
and analyzed in the laboratory in the same manner as
the environmental samples. These samples are used to
monitor contamination of the environmental samples.
For this method, deionized water served as the trip
sample matrix.
3.7 Performance Sample
A standard solution of analytes prepared by the work
assignment Quality Control Coordinator (QCC) at a
concentration unknown to the analyst. This sample was
analyzed by the analyst and the results reported to
the QCC for evaluation. This sample was designed to
measure instrument performance.
4. INTERFERENCES
Chemicals which elute from the HRGC column within the
retention time windows of the chlorinated paraffins and
produce ions within the mass ranges scanned are potential
interferences. Because low levels (sub ppb) of chlorinated
paraffins were anticipated, the elimination of the
interferences was essential. High purity reagents and
solvents were used and all equipment was thoroughly cleaned.
Because chlorinated paraffins are used as plasticizers,
contact with plastics (except polyethylene) was avoided.
Polyethylene gloves were worn during sample preparation to
avoid contamination of the samples. Laboratory method
blanks were analyzed to demonstrate the absence of contami-
nation that would interfere with the measurement of
A-4
-------
the chlorinated paraffins. Column chromatographic procedures
were used to remove co-extracted sample components; these
procedures were performed carefully to minimize loss of
chlorinated paraffins during attempts to increase their
concentration relative to other sample components.
5. APPARATUS AND EQUIPMENT
5.1 The GC/MS system was a Finnigan MAT 4000 equipped with
an Incos 2400 data system. Operating conditions and
parameters are listed in Table A-l.
5.2 HRGC Column
A 30-m x 0.25-mm i.d. fused silica capillary column
coated with DB-5 (0.25 urn) was used for analysis of
chlorinated paraffins. '
5.3 Miscellaneous Equipment
5.3.1 Nitrogen evaporation apparatus with variable
flow rate.
5.3.2 Balance capable of accurately weighing to
0.01 g.
5.3.3 Balance capable of accurately weighing to
0.0001 g.
5.3.4 Water bath equipped with concentric ring cover
and capable of being temperature controlled.
5.3.5 Stainless steel spatulas or chemical spoons.
5.3.6 Magnetic stirrers and stir bars.
5.4 Glassware
5.4.1 Separatory funnels, 2-L
5.4.2 Kuderna-Danish (KD) apparatus
5.4.3 Soxhlet apparatus
5.4.4 Erlenmeyer flasks
5.4.5 Minivials
2-ml borosilicate glass with conical-shaped
reservoir and screw caps lined with Teflon-
faced silicone disks.
A-5
-------
Table A-l HRGC/NCIMS Operating Conditions for CP Analysis
Mass spectrometer
Mode:
lonization gas:
Ionizer pressure:
Electron energy:
Emission current:
Electron multiplier voltage:
SEV:
Source temperature:
Overall SIM cycle time:
negative chemical ionization
methane
0.7 torr
70 eV
0.3 mA
-1700 V
ID'7
170°C
3 sec
Gas chromatograph
Column coating
Film thickness:
Column dimensions:
Helium linear velocity
Helium head pressure:
Injection type:
Injector temperature:
Interface temperature:
Injection size:
Initial temperature:
Initial time:
Temperature program:
DB-5
0.25 jjm
30 m x 0.25 mm ID
^25 cm/s
8 psi
on-column
ambjent
300 C
1 ^
80 C
2 min
80°C to 320°C at 10°C/min
A-6
-------
5.4.6 Powder funnels—glass
5.4.7 Chromatographic columns for the silica and alumina
chromatography—champagne minicolumns with
30 mL reservoirs (Supelco).
5.4.8 Carborundum boiling chips; extracted for 6 h
in a Soxhlet apparatus with benzene and air dried.
5.4.9 Glass wool, silanized (Supelco); extracted
with methylene chloride and hexane and air dried.
5.4.10 Glassware Cleaning Procedure
The glassware was cleaned using the procedures
outlined in Appendix B, section 4.3 of the
Chlorinated Paraffin Environmental Field Study
Quality Assurance Project Plan (QAPP) (Appendix
D).
REAGENTS AND STANDARD SOLUTIONS
6.1 Column Chromatography Reagents
6.1.1 Alumina Woelm B (Woelm Pharma) activated at 130°C
for 48 h or longer.
6.1.2 Silica Gel
High purity grade, type 60, 70/230 mesh. The
silica gel was extracted in a Soxhlet apparatus
with methylene chloride for 10 h (minimum of
two cycles per hour). It was then air dried and
activated by heating in a foil-covered glass
container for at least 24 h at 130 C.
6.1.3 Silica gel impregnated with 40% (by weight)
sulfuric acid. Two parts (by weight) concentrated
sulfuric acid was added to 3 parts (by weight)
silica gel (extracted and activated) in a
glass screw cap bottle. It was tumbled for 5
to 6 h, shaking occasionally until free of
lumps.
6.1.4 Sulfuric acid, concentrated; ACS grade, specific
gravity 1.84.
6.2 Sodium sulfate, granular, anhydrous. Extracted with
methylene chloride for 16 h (minimum of 2 cycles per
hour) air dried and then heated for longer than 4 h in
a shallow tray at 400 C. It was cooled in a desiccator
and stored in a 130 C oven.
A-7
-------
6.3 Solvents
High purity, distilled in glass; methylene chloride,
hexane, diethyl ether, acetone, and isooctane. High
purity solvents were dispensed from Teflon squirt
bottles.
6.4 Concentration Calibration Solutions
Three chlorinated paraffin standard materials (Paroil
142, Paroil 152, and Paroil 1160) were required.
Portions of the standards were accurately weighed and
dissolved in isooctane to produce concentration calibra-
tion solutions at the concentrations shown in Table
A-2.
7. GC/MS PERFORMANCE CRITERIA
Single run limited mass range selected ion monitoring analyses
of the chlorinated paraffins were carried out with the
instrumental conditions and parameters outlined in Table
A-l. All nine mass ranges given in Table A-3 were sequentially
scanned in a single run with a total elapsed time of
approximately 3 s.
7.1 Tuning and Mass Calibration
The mass spectrometer was tuned on a daily basis prior
to sample analysis using perfluorotributylamine (FC-43).
For reproducibility of the relative abundance
measurements, the abundance ratio of the m/z 414:
m/z 633 ion was adjusted to 1:3 (j^lO%).
7.2 Initial Calibration for Chlorinated Paraffin Analysis
Initial calibration was required before any samples
were analyzed for chlorinated paraffins. Initial
calibration was also required if any routine calibration
did not meet the required criteria listed in Section
7.3.
7.2.1 Tuned and calibrated the instrument with FC-43
as outlined in Section 7.1.
7.2.2 The four concentration calibration solutions
listed in Table A-2 were analyzed for the initial
calibration phase.
7.2.3 Using the HRGC and MS conditions in Table A-l
and the SIM monitoring parameters given in
Table A-3, 1 uL of each of the four concentration
calibration solutions were analyzed.
A-8
-------
Table A-2 Concentration Calibration Solutions
Concentration in calibration solutions Qug/mL)
CP
CS1 CS2 CS3 CS4
Paroil 142 100 50 20 10
Paroil 152 100 50 20 10
Paroil 1160 100 50 20 10
A-9
-------
Table A-3 SIM Mass Ranges for CP Analysis
Nominal
Mass range scan time (s) CP
324-329 0.34 C10-12
359-364 0.34
367-372 0.34
393-401 0.34
401-420 0.35 C14_17
441-454 0.34
477-488 0.36
498-503 0.36 C2Q-30
514-518 0.34
A-10
-------
7.2.4 The response factors for each mass range were
computed using the computational method in
Section 13.1.
7.2.5 The mean RF and the standard deviation were
then calculated.
7.3 Criteria for Acceptable Initial Calibration
7.3.1 The standard error (%)
four calibration standa
323-329 357-363
7.4 7.6
399-419 439-453
7.2 7.5
512-517
16.5
of the mean RFs for the
rds were:
365-371 391-399
5.6 4.4
475-487 496-502
4.8 6.6
7.3.2 The SIM traces for all ions used for quantitation
must present a signal-to-noise (S/N) ratio of
23 as measured from the integrated areas in
the appropriate retention time windows.
7.4 Routine Calibration
Routine calibration was performed at the beginning of every
day before actual sample analyses were performed and after all
samples for the day were analyzed. Additional calibration
during the day may have been employed if instrument
instability was suspected.
7.4.1 One (1) pL of concentration calibration solution CS2
was injected as the initial calibration check on each
analysis day.
7.4.2 The RF for each ion range in the concentration
calibration solution was computed.
A-ll
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7.5 Criteria for Acceptable Routine Calibration
7.5.1 The measured RF for all cells was within _+30%
of the average mean calculated in Section 13.1.1.
7.5.2 If this criterion was not met, a second attempt
was made before repeating the entire initializa-
tion process.
QUALITY CONTROL PROCEDURES
8.1 Summary of QC Analyses
8.1.1 Initial and routine calibration and instrument
performance checks.
8.1.2 Analysis of a batch of samples with accompanying
QC analyses: up to 10 environmental samples
of one matrix type plus QC analyses including
one method blank, and one spiked blank. Addi-
tional QC samples, including field spikes,
field blanks, trip spikes, and trip blanks may
be included in a batch of samples.
3.2 Performance Evaluation Solutions
Prior to sample analysis, a solution provided by the
work assignment quality control coordinator containing
known amounts of chlorinated paraffins was analyzed.
The accuracy of measurement for performance evaluation
samples was in the range of 70-130% of true value.
8 .3 Laboratory .Method Blanks
A minimum of one laboratory method blank was generated
with each batch of samples. The method blank was
generated by performing all steps detailed in the
analytical procedure using all reagents, standards,
equipment, apparatus, glassware, and solvents that
would have been used for a sample analysis. For
sediment, suspended solids, and biota samples, the
matrix was omitted. Deionized water was substituted
for environmental water.
8.3.1 An acceptable method blank exhibited no positive
response in the characteristic ion ranges
monitored.
8.3.1.1 If the above criterion was not met,
solvents, reagents, apparatus, and
glassware v/ere checked to locate and
eliminate the source of -the contamina-
tion before any further samples were
extracted or analyzed.
A-12
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8.3.1.2 If new batches of reagents or solvents
contained interfering contaminants, they
were purified or discarded.
8 . 4 Spiked Samples
8.4.1 Method Spikes
A minimum of one method spike was generated with each
batch of samples. A method spike is generated by per-
forming all steps detailed in the analytical procedure
using all reagents, standards, eguipment, apparatus,
glassware, and solvents that would be used for a sample
analysis. For sediment, suspended solids, and biota
samples, the matrix was omitted. Deionized water was
substituted for environmental water. These samples
were spiked with known amounts of chlorinated paraffins
prior to extraction.
8.4.2 Field Spikes
Field spikes were analyzed using the method at the
frequency specified in the experimental design contained
in the main body of the QAPP (Appendix D).
8.4.3 Trip Spikes
Trip spikes were analyzed using this method at the
frequency specified in the experimental design con-
tained in the main body of the QAPP.
9. SAMPLE PRESERVATION AND HANDLING
Water and sediment samples were maintained at 8°C or lower until
extraction. Mussel samples were maintined at -20°C until extrac
tion. Sample extracts were stored at 8°C or less until analysis
0. SAMPLE PREPARATION AND EXTP.ACTION
10.1 Extraction of Water Samples
10.1.1 Filter water through a 0.45 p filter (Type HA,
Millipore, 47 mm) in a millipore filtration
apparatus. Use a 2-L suction flask to receive
the filtrate. Use suction by aspiration to
facilitate the process.
10.1.2 Rinse the sample jar with a 250-mL portion of the
filtrate and pass through the filter again. Note
For samples with a large amount of particulate,
more than one filter may be needed "if filtration
becomes slow.
A-13
-------
10.1.3 Measure the volume of the filtrate using a 500-mL
graduated cylinder and pour back into the sample
jar.
10.1.4 Transfer the filter to a clean 4-oz jar using
forceps. Retain for determination of suspended
solids as detailed in section 10.4.
10.1.5 Transfer 1,000 mL of the filtrate into a 2-L
separatory funnel.
10.1.6 Add 60 mL of hexane, stopper, invert and vent the
funnel. Shake the funnel for 2 minutes vigorously
enough to form an emulsion.
10.1.7 Allow the phases to separate, drain the aqueous phase
into a 1,000-mL Erlenmeyer flask and the hexane phase
into a 250-mL Erlenmeyer flask.
10.1.8 Transfer the aqueous phase back into the 2-L
separatory funnel and add another 60 mL of hexane
to the 1,000 mL Erlenmeyer flask to rinse the
flask. Add the rinse to the separatory funnel
and shake again for 2 min.
10.1.9 Repeat step 10.1.7.
10.1.10 Discard the aqueous phase.
10.1.11 Add enough (10-20 g) anhydrous sodium sulfate to
the hexane extract to remove the water.
10.1.12 Transfer the hexane extract to a 250-mL Kuderna
Danish (KD) flask equipped with either a 5- or
10-mL receiver. Complete the transfer with
three rinses of hexane, 10-20 mL each.
10.1.13 Add several carborundum chips and place a 3-ball
Snyder column into position.
10.1.14 Concentrate the hexane to about 5 mL on a steam
bath.
10.1.15 Transfer the concentrated hexane extract to a
4-dram vial using a Pasteur pipette. Complete
the transfer using three rinses of hexane (about
0.5 mL each).
10.1.16 Proceed to the sulfuric acid/silica cleanup
(Section 11.1).
A-14
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10.2 Extraction of Sediment Samples
10.2.1 Transfer the sediment sample (1 kg) to a clear Pyrex
baking dish (12 in x 12 in x 2 in) with a stainless
steel snatula.
10.2.2 Drain and discard the excess water.
10.2.3 Dry the sediment by placing it in an oven (65-70°C)
for 48-60 h. Stir the sediment occasionally to
facilitate drying and to break up large clumps.
10.2.4 Break the sediment into a fine powder using a mortar
and pestle, if necessary. Remove large rocks with a
pair of forceps.
10.2.5 If necessary, sift the sediment through a screen to
remove particles greater than 1 mm.
10.2.6 Weigh 100 g (±0.1 g) of the sediment into a clean
8 oz jar.
10.2.7 Add 100 g (±0.1 g) of anhydrous sodium sulfate to
the sediment sample and mix with a spatula.
10.2.8 Load the sediment/sodium sulfate mixture into a Soxhlet
flask containing a pad of glass wool.
10.2.9 Add 200 mL of hexane to a 200-mL round bottom flask,
add several carborundum chips and extract the sample
for 16 h.
10.2.10 Allow the apparatus to cool and manually cycle any
remaining hexane in the sediment. Remove the 250-mL
flask from the apparatus. Discard the sediment.
10.2.11 Transfer the hexane to a 250-mL KD flask. Complete
the transfer with three 10-mL rinses of hexane. Con-
centrate to about 5 mL and transfer to a 4-dram vial
using a Pasteur pipette. Complete the transfer with
three 0.5-mL rinses of hexane. Cap with a Teflon-
lined lid.
10.2.12 Proceed to the sulfuric acid/silica cleanup (Section
11.1).
10.3 Preparation and Extraction of Mussel Samples
10.3.1 Open the mussel with a sharp knife by cutting the
muscles attached to the shell next to the hinge.
A-15
-------
10.3.2 Scrape and transfer the tissue to a tared 500-mL
beaker.
10.3.3 Drain off any residual water and remove any plant
tissue.
10.3.4 Open and add enough mussels to obtain at least 100 g
of tissue.
10.3.5 Homogenize the tissue in a Waring blender. A homo-
geneous viscous liquid should be obtained.
10.3.6 Transfer the tissue homogenate to a clear Pyrex
dish (12 in x 12 in x 2 in) using a stainless steel
spatula.
10.3.7 Slowly add 3 times the sample weight of anhydrous
sodium sulfate to the homogenate, stirring frequently
with a spatula.
10.3.8 Allow the mixture to dry until it is free flowing.
This step may take several days.
10.3.9 Load the tissue/sodium sulfate mixture into a Soxhlet
flask to an equivalent weight of 100 g of mussel
tissue. Extract for 16 h with 450 mL of hexane.
10.3.10 Cool and remove the round bottom flask. Discard the
tissue/sodium sulfate mixture.
10.3.11 Add 10-20 g of anhydrous sodium sulfate to dry the
extract.
10.3.12 Add 20 g of 40% (w/w) sulfuric acid on silica gel,
and let stand for 1 h with occasional swirling.
10.3.13 Transfer the extract to a 250-mL KD flask. Complete
the transfer with three 20-mL rinses of hexane.
Concentrate to about 5 mL.
10.3.14 Transfer the concentrated extract to a 4-dram vial.
Complete the transfer with three 0.5-mL rinses of
hexane.
10.3.15 Concentrate the extract to about 0.5 mL with a gentle
stream of nitrogen. Cap with a Teflon-lined lid.
10.3.16 Proceed to the alumina cleanup step. (Section 11.2)
10.4 Extraction of Suspended Solids
10.4.1 Weigh the filters obtained in step 10.1.4 to the
nearest 0.1 mg.
A-16
-------
10.4.11 Load the filters into a Soxhlet flask containing a
pad of glass wool.
10.4.2 Proceed with extraction and cleanup beginning with
step 10.2.9.
11. CLEANUP PROCEDURES
11.1 Sulfuric Acid/Silica Cleanup
11.1.1 Prepare the columns (champagne minicolumns with
30-mL reservoir, Supelco Inc.) by inserting a
small pad of pesticide-grade glass wool (DCMS
treated, Alltech Associates).
11.1.2 Rinse the columns and glass wool with three
aliquots each of acetone and hexane in that
order.
11.1.3 Add 1.0 g of 40% (w/w) sulfuric acid/silica to
the column. Layer about 1 cm of anhydrous
sodium sulfate on top of the bed.
11.1.4 Wet the column with enough hexane to saturate
the bed. DO NOT ALLOW THE COLUMN TO DRAIN
FAR ENOUGH TO EXPOSE THE BED OF SILICA.
11.1.5 Transfer the sample to the column using a
Pasteur pipette. Complete the transfer with
three 0.5-mL rinses of hexane. Collect the
eluent in a 6-dram vial.
11.1.6 Allow the sample extract to flow through the
column and add 5 mL of hexane into the vial.
11.1.7 Allow the column to run dry and rinse the tip
with about 1 mL of hexane into the vial.
11.1.8 Concentrate the eluate to about 0.5 mL with a
gentle stream of nitrogen. Cap with a Teflon-
lined lid.
11.2 Alumina Cleanup
11.2.1 Prepare the columns as described for the sulfuric
acid/silica columns (Section 11.1.1). Use 1.0 g
of basic alumina prepared as described in Section
6.1.1.
11.2.2 Wet the column with enough hexane to saturate the
bed. DO NOT ALLOW THE SOLVENT LEVEL TO FALL BELOW
THE TOP OF THE ALUMINA BED.
A-17
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11.2.3 When the solvent level has reached the bed, add
the sample extract with a Pasteur pipette.
11.2.4 Measure 10 mL of 1% (v/v) diethyl ether in hexane
into a graduated cylinder. Complete the transfer
of the sample extract to the column with three
rinses of the 1% ether in hexane mixture when
the sample extract has completely drained into
the alumina bed. Add the remaining 1% ether in
hexane. Collect the eluate in a 4-dram vial.
11.2.5 When the 1% ether in hexane has reached the top
of the bed, add 10 mL of 50% diethyl ether in
hexane to the column. Collect the eluate in a
fresh 4-dram vial. Discard the 1% ether eluate.
11.2.6 After the 50% ether in hexane fraction has
completely eluted and the column drained dry,
rinse the tip of the column with about 1 mL of
hexane and concentrate the sample to about 0.5
mL with a gentle stream of nitrogen.
11.2.7 Transfer the sample with a Pasteur pipette to a
2-mL conical reaction vessel (Supelco). Complete
the transfer with one rinse of hexane and two
rinses of acetone (about 0.5 mL each). Reduce
the sample to dryness with a gentle stream of
nitrogen.
11.2.8 Cap with a Teflon-lined lid and store for analysis
by mass spectrometry.
11.2.9 Prior to analysis, the analyst will add a 50 uL
(or other volume) aliquot of isooctane to the
sample and sonicate for 30 sec.
12. INSTRUMENTAL PROCEDURES
12.1 Once routine calibration criteria were met, the
instrument was ready for sample analysis. Prior to
the first sample, a blank injection of isooctane was
analyzed to document system cleanliness. If any evidence
of system contamination was found, corrective action
was taken and another isooctane blank analyzed.
12.2 The typical daily sequence of injections is shown in
Table A-4.
A-18
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Table A-4 Typical Daily Sequence for CP Analysis
1. Tune and calibrate mass spectrometer with FC-43.
2. Inject concentration calibration solution.
3. Inject isooctane blank.
4. Inject samples.
5. Inject concentration calibration solution.
A-19
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13. DATA REDUCTION
In this section, the procedures for data reduction are
outlined for the analysis of chlorinated paraffins in
environmental samples.
13.1 Quantitative Calculations
13.1.1 Calculation of Response Factors
Response factors for each mass range were
calculated from the data obtained during the
analysis of concentration calibration solutions
using Equation 13.1.
RF = Astd EQ. 13.1
Cstd x Vstd
Where:
Astd is computer generated area for a mass range
Cstd is the concentration of the standard (ng/uL)
Vstd is the volume of sample injected in (uL)
13.1.2 Calculation of Chlorinated Paraffin Concentrations
Chlorinated paraffin concentrations were calculated
for each mass range using Equation 13.2.
Concentration (ppb) = Aex x Vex EQ> 13>2
RF x Vinj x M
Where:
Aex is the computer generated area of the mass
range in the extract
RF is the response factor calculated in
Equation 13.1.
Vinj is the volume of extract injected (jjL)
Vex is the final volume of the extract (pL)
M is the mass of sample taken for analysis (g)
13.2 Estimated Method Detection Limit
Estimated method detection limits were calculated in
situations where (1) no response was noted for a
specific mass range and (2) where a response was
quantitated as a trace value, that is, where the
response is between 3 and 10 times the signal to
noise ratio. These two cases are discussed below.
A-20
-------
13.2.1 For samples in which no signal was detected
above the baseline, the estimated minimum
detectable concentration was calculated. The
background ((T) was determined by integrating the
ion abundances for the mass ranges in the
appropriate regions and relating the area to an
estimated concentration that would produce that
area. The formula is given in Equation 13.3.
EDL = 3 x Aex x Vex EQ> 13>3
RF x Vinj x M
Where:
EDL is the estimated detection limit (ppb)
Aex is the computer generated area of the mass
range in the extract
RF is the response factor calculated in
Equation 13.1
Vinj is the volume of extract injected (uL)
Vex is the final volume of extract (uL)
M is the mass of sample taken for analysis (g)
13.2.2 If a response for a specific mass range was
quantitated as a trace value [signal to noise is
greater than or equal to 3 (
-------
APPENDIX B
ANALYTICAL METHOD VALIDATION RESULTS
-------
TABLE OF CONTENTS
Section
Heading
Page
1
2
3
4
5
Summary B-4
Experimental Design B-6
Analytical Procedures B-6
Data Quality Assessment B-6
Method Development and Validation
Study Results B-8
Statistical Evaluation of the Method
Validation Data B-10
FIGURES
B-2
B-3
B-4
B-5
TABLES
B-l
B-2
B-3
95% Confidence Interval for Single Observation
of Y, C10-12 Sediment B-23
95% Confidence Interval for Single Observation
of Y, Ci4_i7 Sediment B-24
95% Confidence Interval for Single Observation
of Y, C2Q-30 Sediment B-25
95% Confidence Interval for Single Observation
of Y, CiQ-12 Water B-26
95% Confidence Interval for Single Observation
of Y, C!4_17 Water B-27
Experimental Design for the Method
Validation Study B-7
Reported CP Concentrations (pq/L) in
Unspiked Samples of Filtered Stream Water B-ll
Reported CP Concentrations (jjg/L) in spiked
Samples of Filtered Stream V7ater and
Recovery Percentages B-13
Reported CP Concentrations (jjg/kg) in
Unspiked Samples of Sediment B-15
B-2
-------
TABLE OF CONTENTS (CONT'D)
Section Heading
TABLES (CONT'D)
B-5 Reported CP Concentrations (jjg/kg) in
Spiked Samples of Stream Sediment and
Recovery Percentages B-16
B-6 CP Recovery Percentages for Spiked
Sediment Samples, Adjusted for
Pre-spiking, CP Concentrations Reported
for Sediment B-18
3-7 Reported CP Concentrations fyjg and ug/10 L)
in Stream Water Particulates B-20
B-8 Working Equations for Predicted Values and
95% Confidence Limits (C.L.) for Reported
($) and True (£) CP Concentrations in
Individual Sediment Samples B-29
3-9 Working Equations for Predicted Values
and 95% Confidence Limits (C.L.) for
Reported (Y) and True (X) CP Concentrations
in Individual Water Samples B-30
B-10 Chlorinated Paraffin Concentrations, by Carbon
Chain-length Group, Reported for Spiked and
Unspiked Sediment Samples and Method Blanks:
Method Validation Study B-32
3-11 Chlorinated Paraffin Concentrations, by Carbon
Chain Length Group, Reported for Spiked and
Unspiked Stream Water Samples and Distilled
Water Method Blanks: Method Validation Study..B-33
B-3
-------
1. Summary
The method validation phase of this work was designed to
assess the precision, accuracy, and recovery of the method
Matrix samples (except mussel tissue, which was obtained
commercially) for the validation were obtained from Sugar
Creek (Dover, Ohio) sampling stations A and B during the
reconnaissance trip conducted on August 12, 1986. Station
A is located downstream from the Dover Chemical Plant and
Station B is located upstream. Station B samples provided
the basis for method assessment, while station A samples
were run to obtain a preliminary indication of downstream
CP concentrations and were used to prepare the spiked
environmental samples.
Overall, the methodology for analysis of CPs in water and
sediment was well-behaved for quantification of the C^g-12
C-14-17 carbon chain-length groups, providing stable recovery
rates of predictable precision. The methodology provided generally
useable C2Q-30 quantification, but of somewhat lower predictability
than for the C^g-12 an<^ ^14-17 carbon chain-length groups.
A statistical summary of the validation phase follows:
o CPs were not identified in unspiked filtered stream water
although present in particulates and sediment from the
same sampling stations. Values reported for filtered
stream water (0.003-0.157 pg/L) were comparable to those
for distilled water (0.005-0.11 ^ug/L) and were indistinguish-
able from procedural noise.
o The numerical values reported for unspiked filtered stream
water and distilled water were statistically significantly
highest for C^o-12 an<^ lowest for C2Q-30' suggesting a
higher limit of detection for C^Q_^2 than for C2Q-30 f°r
CP analysis of water.
o Recovery percentages for CPs spiked in filtered stream
and distilled water were significantly higher statistically
for C10-12 (* = 100%) than for C14_}7~ (X = 75%). Recovery
of C20-30 was too variable for meaningful comparison.
o CP residues were reported in unspiked stream and sediment
both upstream of and downstream from the Dover Chemical Plant
outflow ditch, with downstream concentrations significantly
higher than upstream concentrations. Within stations, the
lowest residues were reported consistently for C^o-12 an<^
the highest for C2Q-30- There was no overlapping of values
among the three carbon chain-length sets.
o Evaluation of recovery data for spiked sediment is confounded,
to some extent, by the presence of CPs in the unspiked
sediment from Station A prior to spiking. An attempted
3-4
-------
o
arithmetic correction to estimate recovery of spiked CPs
alone was not fully effective.
o Contrary to recoveries reported for spiked water, those for
the Cio-12 and C14-17 were essentially equal among all three
spiking levels for sediment, the six recovery values ranging
from 56.3% to 63.5%. Recovery_of C2Q-30 from the 500 and
1,000 pq/kg sediment spikes (X unadjusted = 84.4%) was
significantly higher than was recovery of C^o-12 or C14-17
for those spikes. ( C2Q-30 recovery data for the 200 jug/kg
spike was too variable for meaningful comparison as the
result of two apparently false negative reports.)
o Concentrations reported for the single downstream particulate
sample were decidedly higher than for the single upstream
sample, being highest for C2Q-30 (4.2 ug/L water).
o Of the 45 water, sediment and method blank samples analyzed
(Tables 10 and 11), there were 14 samples that might have
resulted in false positive reports for C^o-12' C14-17' and
C20-30' and the remaining 31 samples that might have resulted
in false negative reports. Among these quantifications, there
was one apparent false positive report (13.89 ^g/kg of
C2Q-30 f°r an unspiked method blank for sediment) and two false
negative reports (0.048 and 0.052 /jg/L of C2Q-30 f°r stream
water spiked at 1 ug/L). There were no false positives or false
negatives for analyses of C^Q-12 or C^4_iy. The false
positive frequency for C2Q-30 was 1 i° -^ analyses, and the
false negative frequency 2 in 31 analyses (see Section 6.6).
Statistical analysis of the water and sediment spiking
recovery data provided least squares estimates of overall
method recovery and accuracy. Estimates for recovery and,
equivalently, accuracy for quantification of CPs in sediment
averaged 61%, ranging from 57% for C14-17 to 66% for C2Q-30-
Recovery and accuracy for CP quantification in water was
essentially 100% for C]_o-i2» 75% f°r C14-17 and not calculated
for C20_30.
o Precision estimates as coefficients of variation, or relative
standard deviation, for individual spiking levels are presented
in Tables B-3, B-4 and B-5. Coefficients of variation for
quantification of CPs in water averaged approximately 12%
for CiQ-12' 25% for C^4_j[7 and 73% for C2Q-30 (^ degrees
of freedom per average; derived from Table B-3). For
quantification of CPs spiked in stream sediment (excluding
method blanks), coefficients of variation averaged approx-
imately 26% for Cjo-12' 23% for C14-17 and 34% for C20-30
(6 degrees of freedom per average; derived from Table B-5).
o Regression equations to derive "best estimates" of true
CP concentrations in water and sediment samples for given
reported concentrations, and their statistical confidence
limits, were developed using methods of inverse prediction.
B-5
-------
2. Experimental Design
The experimental design for the method validation phase of this
study is outlined in Table B-l. The design is broken down into
two phases. The first phase was designed to measure background
(Lg) levels of CPs in the matrices and to provide a basis for
setting spiking levels (L^-I^) for phase II. The phase II analyses
were used to assess method accuracy, precision, and recovery. A
batch of samples consists of four validation samples and associated
quality control samples. A laboratory method blank and a spiked
control sample for water and a laboratory method blank for sediment
were incorporated. Since control sediment was not available,
spiked control sediments were not included in the design.
3. Analytical Procedures
The validation samples were analyzed according to the procedures
detailed in Appendix A. The Chlorinated Paraffin concentrations
measured in these samples and used in this statistical analysis
are given at the end of this Appendix as Tables B-10 and B-ll.
4. Data Quality Assessment
Precision, accuracy and recovery were determined for three spiking
levels for each of the three cells.
4.1 Precision
Precision was assessed as relative standard deviation, or
coefficient of variation, within each cell. Precision is
expressed as relative standard deviation as defined in Section
9.1 of the QAPP.
4.2 Accuracy
The accuracy of the method was assessed within each cell.
Accuracy is expressed as A% as defined in Section 9.2 of the
OAPP. Method overall accuracy was assessed using regression
estimates of recovery for known spiking levels.
4.3 Recovery
Recovery was assessed within each cell. The measure of
recovery is percent recovery as defined in section 9.3 of the
QAPP. Method overall recovery was assessed using the same
procedures as for method accuracy.
B-6
-------
TABLE B-l Experimental Design for the Method Validation Study
Upstream Downstream Method Spike
WATER MATRIX "B" Pool "A" Pool Blank Control
PHASE
I
II
II
II
Total t
SEDIMENT
PHASE
I
II
II
II
Total #
BATCH NO.
1
2
3
4
of Analyses
LQ LQ LI L2 L3 SQ S]_
2X 2X IX IX
IX IX IX IX IX IX
IX IX IX IX IX IX
- IX IX IX IX IX
24333 4 4
Upstream Downstream Method Blank
MATRIX "B" Pool "A" Pool (no sediment)
BATCH NO.
5
6
7
8
of Analyses
LQ LQ LI L2 L3 SQ
2X 2X - - - IX
IX IX IX IX IX
IX IX IX IX IX
- IX IX IX IX
2 4333 4
Mote 1: IX = single analysis; 2X = replicate analysis
Note 2: Each sample in the above table went through the extraction
process.
Note 3: One solvent blank and one calibration check at the 1^2
spiking level was run per day for instrument check.
Note 4: Spiking level ?>\ for the distilled water spike check
was 10 times the estimated LOQ (i.e., 5 ppb for water).
B-7
-------
Method Development and Validation Study Results
5.1 Spiked Recoveries
5.1.1 Sediment Blank Spike Recoveries
The method development and validation studies indicate
that acceptable recoveries from spiked sediments are
obtained using the analytical method. However, spiked
method blanks analyzed with the sample sets did not
yield recoverable CPs. It is thought that the loss
of analyte from these samples is the result of lack
of matrix. The method development and validation
studies were performed with Missouri River sediment
and Sugar Creek sediment, respectively. These sediments
were spiked and dried by mixing with egual portions of
sodium sulfate at moderate temperatures until free-
flowing mixtures were obtained. This was done to prevent
plugging of the Soxhlet apparatus during extraction.
The method spikes consisted of sodium sulfate only.
It would appear that CPs are bound to the sodium sulfate
tightly enough that Soxhlet extraction will not recover
them. It is recommended for future analyses that a
control sediment be identified and used for spiked
recovery determinations during sample analysis.
5.1.2 Water and Particulate Field Spikes
The environmental spike samples (field and lab) were
designed to show differences upon transport and storage
of the environmental samples. The analytical results
showed generally consistent results between the field
and lab spikes, indicating that sample degradation was
not a serious problem; however, low extraction
efficiencies were obtained for these samples. This is
not surprising considering the complex nature of these
samples and the difficulty in generating four samples
containing the same amount of particulates from a
single source at each QA station.
The trip spike and spiked DI water (both 50 ppb) also.
exhibited low recoveries, which were in general agree-
ment with the environmental water spikes. This was
expected since these spikes did not contain particulates,
which was thought to contribute heavily to the low
recoveries.
Several experiments, using the chlorinated paraffin
standards were carried out to isolate the cause of the
low recoveries. These included experiments to isolate
various possible aspects of the extraction procedure,
in particular, adsorption to glassware, losses during
transfers, and losses by filtration. Adsorption to
glassware or loss during transfers were not thought to be
B-8
-------
the cause of the low recoveries; these would have been
evident during the method validation study, which
incorporated these steps. The Sugar Creek validation
water was filtered prior to spiking to remove the
particulates; the environmental water samples were spiked,
then filtered; and the trip spike and lab spike DI water
were extracted unfiltered.
The results of these experiments indicate that losses to
adsorption and filtering are not significant. However,
the results obtained do indicate that the solubility
of chlorinated paraffins is less than 50 ppb, as evidenced
by recoveries from DI water spiked at 50 ppb, extracted
with hexane, and analyzed. The recoveries obtained were
consistent with those obtained for the trip and lab spikes.
This spiking level was chosen prior to the Sugar Creek
sampling effort without knowledge of the CP and particulate
levels which would be encountered. This level is an
order of magnitude higher than the highest validation
level and was chosen in an effort to provide a concentration
which could be measured above the existing environmental
levels. This spiking level was maintained for the Tinkers
Creek study as analytical data was not available from
the Sugar Creek study to form a basis for change.
The analytical results for the environmental samples
indicate that no significant concentration of chlorinated
paraffins is contained in the filtered water fractions,
even above sediments which contain relatively large
amounts of chlorinated paraffins, as in the Dover Chemical
lagoon. For future analyses, it is recommended that
spiking levels be reduced to 5 ppb or less.
5.2 Mussel data
It is noted in the QAPP and preliminary draft of the final
report that 10 mussels were to be considered a sample of
mussels. This estimate was based on the size of the mussels
purchased for the methods development and validation work.
It was found, however, that the mussels collected in Sugar
Creek were significantly larger, reguiring only one to two
mussels to generate 100 g of tissue for analysis.
As previously discussed, the first set of mussels presented
extraction problems, e.g plugging of the Soxhlet extractor,
followed by storage of the extracts at room temperature.
The analytical results of the spiked blank, which was
stored under the same conditions indicate that the -ambient
storage did not have an adverse effect on the chlorinated
paraffins in the field samples. The results obtained for
the upstream mussel samples indicated nondetectable
levels of CPs; measurable CP levels were found in the
downstream mussel samples. Additional mussel tissue was
available for the two upstream sites and the analysis
B-9
-------
was repeated with results consistent with the first
analysis. However, no tissue from the downstream site was
available to confirm the original analysis. Although
the quality assurance data would indicate that the original
analysis of the downstream sample is valid, the CP level
measured should probably be considered a minimum value,
due to possible incomplete extraction.
6. Statistical Evaluation of the Method Validation Data
To review, the chloroparaffin method validation study is
based on quantification data from analyses of spiked and unspiked
samples of sediment and filtered water from Sugar Creek, Ohio,
of unspiked particulates filtered from that water, and of spiked
and unspiked method blanks analyzed concurrently with those
samples. The water and sediment samples, collected during the
reconnaissance survey (August, 1986) were taken both upstream
(Station B) and downstream (Station A) of the outflow ditch
from the Dover Chemical Plant lagoon.
Three separate levels of spiking were used for water and
sediment samples. The spiked samples and their respective
method blanks were prepared in replicate: generally three
replicates for the spiked series and either two or four replicates
for the sets of unspiked samples and their method blanks.
Particulate material filtered from the stream water samples was
of insufficient quantity to provide replicate particulate samples.
Statistical analyses of the data were conducted to examine
and evaluate various aspects of the method as related to carbon
chain length groups and sampled media. Although intended to
provide an overall evaluation of the method, separate statistical
analyses were necessarily conducted of the water and sediment
data for spiked and unspiked samples. Specifically, the analyses
compare reported levels and precision among unspiked samples
and their method blanks to evaluate method sensitivity, and
they quantify and evaluate recovery characteristics among spiked
samples.
6.1 Statistical Evaluation of the Unspiked Water Data
The unspiked water samples were derived from the filtered
composite water samples collected at upstream station B and
downstream station A. Two replicate samples were taken from
the station B composite and four replicates from the station A
composite. The four method blank replicates comprised
distilled water.
'leans and standard deviations for the replicated unspiked
water samples are presented, by stations and carbon chain length
groups, in Table B-2. Analysis of variance (split-plot) of' the
total set of data failed to demonstrate statistical differences
among stations (considering method blanks as a station)
(F2'7df ~ 0.978). The result indicates that the reported values
B-10
-------
Table B-2. Reported CP Concentrations (;ug/L) in Unspiked Samples of Filtered Stream Water
w
i
Sampling
Station Replicates Statistic
B X
(Upstream) 2 (s.d.)
A X
(Downstream) 4 (s.d.)
Method
Blank 4 X
(s.d.)
"x
Stations
Combined 10 s.d.
X + 3 s.d.
Carbon
Cio-12
0.110
(0.066)
0.042
(0.015)
0.053
(0.043)
0.060
(0.044)
0.192
Chain-length Group
C14-17
0.006
(0.008)
0.014
(0.012)
0.039
(0.042)
0.022
(0.029)
0.109
"?n-30
0.004
(0.006)
0.009
(0.007)
0.002
(0.004)
0.005
(0.006)
0.023
Total CPS
0.120
(0.052)
0.065
(0.034)
0.094
(0.055)
0.087
0.047
-------
are apparently not distinguishable from "noise" in the
methodology and are therefore not properly attributable to CPs.
There were statistically significant differences among carbon
chain-length groups in those reported values, being highest for
the CiQ-i2 group (x = 0.060 pg/L) and lowest for the C2Q-30 group
(x = 0.005 jjg/L) , suggesting a higher noise level for the former
than for the latter group.
Table D-2 presents values for the mean plus three standard
deviations for each of the C-groups as estimates of minimum
levels of CP detection in water.
6.2 Statistical Evaluation of Reported CP Concentrations
in Spiked VJater Samples
Subsamples from the composite water sample collected from
station A were used to prepare the spiked samples of filtered
stream water. Three spiking levels were used: 1, 2.5, and 5
pg/L for each of the carbon chain-length groups. Thus a
sample spiked at "1 pq/L" contained 1 }iq/L each of C^g-12'
^14-17' an<^ ^20-30 "standard", for a total of 3 ^g of CPs/L
of water. Method blanks of distilled water spiked at 5 ^g/L
were also included. All samples were prepared and analyzed
in triplicate.
Table B-3 presents the replicate means and standard
deviations of the reported CP concentrations, by carbon
chain-length group and spiking level, and the means and
standard deviations of the respective recovery percentages.
The coefficients of variation for reported concentrations
and recovery percentages are algebraically identical and
thus are presented once in the table to represent both
variables.
Analyses of variance of recovery percentages for the C^o-12
and Ci4_i7 groups indicated that within each group, numerical
differences among spiking levels were not statistically
significant (F3 8df ~ 1.09 and 1.63 respectively.) Analyses
were conducted only after Bartlett's test for homogeneity
of variances indicated that variances of the C}Q_}2 an<3
o
^14-17 sets were not heterogeneous (X j^f - 8.769; P>0.25).
Sartlett's test indicated statistically significant
heterogeneity for replicate variances when the C20-30'
1 ug/L cell was included (reported recoveries of 5.2%,
309.2%, and 4.8%); that cell was therefore excluded from
further statistical comparisons as being anomalous.
Recovery rates among the remaining C2Q-3Q cells, as within
the C]_o-i2' and C14-17 groups, did not differ statistically.
Analysis of variance indicated that overall differences in
recovery percentages between the C^Q-12 groups (X = 102.6%)
and the C14_17 group (Y = 76.9%) were statistically
B-12
-------
Table B-3.
Reported CP Concentrations (ug/L) in Spiked Samples of Filtered Stream Water, and
Recovery Percentages
Sampling Spike
Station (pg/L) Replicates Statistic
/
A 1.0 3 IT
(s.d.)
A 2.5 3 X
(s.d.)
C.V.(%)
A 5.0 3 Y
(s.d.)
c.v.(%)
MR 5.0 3 X"
(s.d.)
C.V.I.)
Ci n-i •>
ug/L
0.996
(0.104)
2.293
(0.162)
5.605
(1.286)
5.343
(0.357)
%Recov.
99.6
(10.45)
10.4
91.7
(6.47)
7.1
112.1
(25.73)
22.9
106.9
(7.15)
6.7
C14-17
ygA
0.701
(0.093)
13.
1.555
(0.521)
33.
4.806
(1.736)
36.
3.952
(0.605)
15.
%Recov.
70.1
(9.32)
3
62.2
(20.83)
5
96.1
(34.71)
1
79.0
(12.08)
3
C?n-^0
ug/L
i
1.064
(1.756)
165
1.330
(0.498)
37.
5.983
(3.203)
53.
2.342
(0.814)
34.
%Recov.
106.4
(175.63)
.0*
53.2
(19.97)
4
119.7
(64.07)
5
46.8
(16.25)
8
to
Variability is significantly greater(P <0.025) than that of remaining cells.
-------
highly significant (F^ 3df =61.8). A tendency for the
recovery percentage for the C2Q-30 9r°up to be lower than
the CjQ-j2 an<3 possibly the C^4_^7 groups could not be
substantiated because of high recovery values in two
of the three C2o-30' 5 ^jg/L replicates (178%, 130%, 51%).
Comparison of coefficients of variation (CVs) across carbon
chain-length groups reveals that within each spiking level
(viewing MB as a separate level), CVs were always lowest
for the Cio_^2 group and highest for the C2Q-30 9r°up
(see Table B-3). The probability of this being a chance
event is approximately 0.0008 (1 in 1,296 chances),
indicating an inverse relationship between analytical
precision and carbon chain-length group for CP analysis
in water. This relationship was not evident for sediment
analysis (see Table B-5).
6.3 Statistical Evaluation of Unspiked Sediment Samples
The unspiked sediment samples were derived from the composite
sediment sample collected at upstream station B and that
collected at downstream station A. Two replicate samples
(subsamples ) were derived from the station B composite sample
and four replicates from the station A composite sample.
The method blanks consisted of a mixture of all the reagents
used in the sediment extraction process, but did not include
sediment per se.
Replicate means, standard deviations, and coefficients of
variation are presented in Table B-4. The table also includes
values for the method blank "mean-nlus-three standard deviations"
for each of the carbon chain-length groups, as estimates of
minimum detection levels.
Chemical analysis indicated levels of CPs in the sediment
samples collected at both stations that were well in excess of
"noise" present in the method blank analyses. Analysis of
variance (split-plot using log-transformed data to stabilize
variances) of the A and B replicates showed differences in
reported levels between the two stations to be statistically
highly significant (F^ 4df= 52.84), the higher levels occurring
at downstream station A, as might be expected. The reported
"levels" in the method blanks were obviously lower than
those for stream sediment and were excluded from the analysis
of variance so as not to obfuscate results.
Analysis of variance showed statistically significant
differences among carbon chain-length groups, the lowest levels
being reported for the C^g-12 group and the highest levels
for the C20-30
B-14
-------
Table B-4. Reported CP Concentrations (jag/kg) in Unspiked Samples of Sediment
Sampling
Station Replicates Statistic
n o \7~
o £ A n
(Upstream) (s.d.)
Carbon Chain-length Group
Ci n-i 9.
4.56
(2.737)
60.1
Cia 17 C?n ™
13.39 65.08
(3.033) (21.99)
22.7 33.8
Total CPS
83.02
(16.22)
20.0
C.V.,*,
A 4 TA
(Downstream) (s.d.)
C.V.
Method 4 Xp1B
Blank
(s.d.)
C.V.
~XJ..1B + 3 s.d.
60.1
30.55
(11.724)
38.4
0.18
(0.281)
158.1
1.02
22.7
58.14
(10.155)
20.2
0.22
(0.440)
200.0
1.54
33.8
162.93
(32.539)
20.0
3.47
(6.945)
200.0
24.31
20.0
251.62
(50.620)
20.1
3.37
(7.352)
190.0
-
tt)
M
LTI
-------
Table B-5. Reported CP Concentrations (ug/kg) in Spiked Samples of Stream Sediment, and Recovery
Percentages
Sampling Spike
n-i 7
Station (ugAg) Replicates Statistic
A 200 3 T
(s.d.)
C.V.(%)
A 500 3 T
(s.d.)
C.V.
A 1,000 3 X
(s.d.)
C.V.
MB 50 1 ~X~
MB 1.000 3 X"
(s.d.)
C.V.
ugAg
113.02
(40.285)
35
301.17
(63.930)
21
635.27
(141.881)
22
37.53
645.39
(111.028)
17
%Recov.
56.5
(20.14)
.6
60.2
(12.75)
.2
63.5
(14.17)
.3
75.1
64.5
(11.07)
.2
ugAq
/
124.01
(42.304)
34.1
304.36
(52.874)
17.4
587.69
(96.268)
16.4
24.49
507.53
(37.303)
7.3
%Recov.
62.0
(21.15)
60.9
(10.57)
58.8
(9.62)
49.0
50.7
(3.73)
pgAg
253.34
(154.795)**
61.
415.29
(72.443)
17.
855.89
(199.881)
23.
15.44
371.92
(68.593)
18.
%Recov.
126.7
(77.4)**
1
83.1
(14.50)
4
85.6
(19.81)
1
30.9
37.2
(6.86)
4
tfl
I
** Bartlett's test for homogeniety of variances is highly significant (p<0.01) when cell 200: C2Q-30
is included, but not so (p<0.50) when it is excluded.
-------
The outcomes of higher reported CP levels in sediment
downstream from the lagoon ditch outfall and of a low to high
progression of levels from the C^g-12 9rouP to the C2Q-30 <3roup
are consistent with results of the Sugar Creek field study.
6.4 Statistical Evaluation of Reported Concentrations in
Spiked Sediment Samples
Subsamples of the composite sediment sample from station A
were used to prepare the spiked sediment samples. Three
spiking levels were used for each of the carbon chain-length
groups: 200, 500 and 1,000 pg/kg of sediment. Thus samples
spiked, say, at 200 ug/kg were spiked so as to contain that
concentration of each of the carbon chain-length "standards."
All spiked sediment samples were prepared and analyzed in
triplicate. Method blanks spiked with an equivalent of 1,000
jag/kg were also prepared and analyzed in triplicate, and a
single method blank spiked at an equivalent of 50 ug/kg was
included.
Table B-5 presents the replicate means and standard
deviations of the reported CP concentrations in spiked sediment,
by chain-length group and spiking level and the means and standard
deviations of the respective recovery percentages. Also, the
coefficient of variation is presented for each replicate cell.
Evaluation of the recovery data for spiked sediment is
complicated somewhat by the reported levels of CPs in the
unspiked sediment from station A. Adjustment of average
reported concentrations and recovery percentages for spiked
samples has been attempted by subtracting average reported
concentrations in unspiked samples from those for spiked samples
and recalculating average recovery percentages based on the
adjusted concentrations values. The adjusted concentrations
and recovery percentages are presented in Table B-6.
The adjusted recovery values are presented for review and
consideration only. Comparison of the adjusted recovery
percentages with those for the method blanks indicates that
adjustment is warranted for the C2Q-30 averages and possibly
for the Ci4_i7 averages. Adjustment of the C^Q_^2 averages,
however, is aoparently not warranted and may well be counter-
productive. Because of apparent inconsistencies in the
adjustment results, statistical evaluation presented here is
restricted to the unadjusted data. This decision should not
affect estimates of method precision, since the adjustment
procedure merely multiplied each value in a replicate set
by a constant.
Contrary to results for spiked water samples, averag'e
recovery percentages among the three Cio-12 spiking sets for
sediment were virtually equal to those among C^.-^-y sets
(X = 60.3%, range 56.3% to 63.5%; unadjusted values). Recovery
B-17
-------
Table B-6. CP Recovery Percentages for Spiked Sediment Samples, Adjusted for Pre-spiking
CP Concentrations Renorted for Sediment
Station
A
A
A
MB
MB
Mean
Spike
(jugAq ) Values
/
Spike
200 Pre-Spk
(Adj.)
Spike
500 Pre-Spk
(Adj.)
Spike
1,000 Pre-Spk
(Adj.)
50
1,000
Ci n-1 9
pgAg
113.02
-30.55
(82.47)
301.17
-30.55
(270.62)
635.27
-30.55
(604.72)
37.53
545.39
%Recov.
56.5
(41.2)
60.2
(54.1)
63.5
(60.5)
75.1
64.5
Ci
pqAg
1
124.01
-58.14
(65.87)
304.36
-58.14
246.22
587.69
-58.14
529.55
24.49
507.53
4-17
%Recov.
62.0
(32.9)
60.9
(49.2)
58.8
(53.0)
49.0
50.8
c™-™
ugAq %Recov.
253.34
-162.93
(90.41)
415.29
-162.93
(252.36)
855.89
-162.93
(693.0)
15.44
371.92
126.7
(45.2)
83.1
(50.5)
85.6
(69.3)
30.9
37.2
tu
I
M
00
-------
for the 500 and 1,000 ;ug/kg spikes was significantly higher
for the C2Q-30 9r°up (x = 84.4), contrary to results for spiked
water samples. (The £29-30' 200 ug/kg data were excluded
because of variance heterogeniety.) It should be noted that
adjustment of the recovery data (Table B-6) tended to diminish
these differences, reducing especially the CoQ-BO recovery
values after subtraction of the relatively high pre-spiking
levels of that chain-length group.
Recovery among the method blanks followed a pattern similar
to that of the method blanks for water, showing highest recovery
values for the CiQ-12 group (67.2%), intermediate for Ci4_i7
(50.3%) and lowest for~C2o-30 (35-7%)- The differences are
statistically significant (p<0.05).
6.5 Evaluation of Unspiked Particulate Data
Because the quantity of particulate material filtered
from the single composite water sample from either station
A or B was insufficient to construct replicate samples or
undertake spiking tests, a single analysis of each sample's
particulates was conducted. The Station B particulates of
0.23874 g were filtered from 10.02 L of stream water, and
those from Station A of 0.60645 g were from 19.25 L. Quanti-
tation levels are reported as ug CP and as ^jg/10 L, by
carbon chain-length groups (Table B-7).
CP extraction was performed on the particulates-plus-filter
to avoid the problem of completely removing and extracting
only the particulates. Thus an "unspiked blank" was created by
extracting and quantifying a filter only, and recovery efficiency
was measured by spiking a filter with 5 ug of each chain-length
standard, followed by extraction of the filter and quantification
of the extract. Method blank results are also presented in
Table B-7. Presented also in the table are residue and recovery
data adjusted For "noise" present in the unspiked method
blank analysis.
While these results are based only on four analyses, there
is consistency in the results in that the highest levels appear
in the downstream sample (A) and, in particular, in the C2Q-30
group as is consistent with field study results. In contrast,
the levels reported for the three remaining samples (B, MB and
^5) show the highest values for the C^g-12 9rouP an<3 the lowest
values for the C2Q-30 gr°up, which is consistent with noise
level estimates for filtered stream water (Table B-2) and, in
general, with recovery from spiked filtered water.
B-19
-------
Table B-7. Reported CP Concentrations (ug and ug/10 L) in Stream Water Particulates
tu
i
Station
B
A
MT3Q
Filtered
Water
(L)
10.02
19.25
(filter
only)
(filter
+ 5ug CPs)
Total
Particulates
(g)
0.23874
0.60645
—
Particulates
(q) Per 10 L
0.2383
0.3150
-
—
ADJUSTED DATA
B - MBo
A - MBQ
MB5 - MBQ
Unadjusted % recovery (MB5)
i
Adjusted % recovery (MB5 - MBQ)
pg CPs
GI n-i ?.
0.778
1.626
0.254
3.345
0.524
1.372
3.091
66.9
61.8
C14-17 C20-30
0.091 0.005
1.495 4.172
0.073 0.011
2.193 0.749
0.018 nd
1.422 4.161
2.120 0.738
43.9 15.0
42.4 14.8
jjg CPs/10 L H?0
Ci'n-l? C14_17 C9n-
0.776 0.091 0.005
0.845 0.777 2.167
0.523 0.018 nd
0.712 0.739 2.162
-------
6.6 Frequency of Classification Errors
There was a possibility for false positive reports to occur
for C;[Q-12' Ci4_i7, and/or C2Q-30 Quantifications among
14 samples: 4 unspiked method blanks for water, 6 unspiked
samples of stream water and 4 unspiked method blanks for
sediment (Tables 10 and 11). There was only one report
that could be considered a false positive, that of 13.89
jjg/kg of C2Q-30 i-n a sediment method blank. Otherwise,
reports were either "n.d." or trivial values attributable to
"noise". Thus, there were no false positive reports among
14 analyses each for CjQ-12 an<3 ^14-lT- The observed false
positive frequency for C2Q-30 was ^ i-n -^ analyses.
There was a possibility for false negative reports to occur
for C]_Q-12' Cl4-17f and/or C2Q-30 ^n a total of 12 spiked water
samples (9 stream water and 3 distilled water, Table 11),
and in a total of 19 sediment samples (9 spiked stream
sediment, 4 method blanks for sediment and 6 unspiked but
contaminated stream sediment samples, Table 10). There were
only two apparent false negative reports: those of 0.048
and 0.052 pg/L of C2Q-30 i° two of the three stream water
samples spiked at 1 jug/L, reported values that could be
attributed to procedure noise. Thus, there were no false
negative reports among 31 analyses each for C^o-12 an<3
C14-17- Tne false negative frequency for C2Q-30 was 2 in
31 analyses, essentially the same frequency as that for
false positive reports.
6.7 Regression Analysis of CP "Concentrations Reported" on
"Concentrations Added"
Regression analyses of CP "concentrations reported" (Y) on
"concentrations added" (X) were performed for each carbon
chain-length set of sediment and water method validation
data. The analyses generated least squares regression
statistics for measuring overall method accuracy and
precision and for developing predictive equations, and
95% confidence limits, for estimation of Y for known
X values and, in particular, for estimation of X for known
Y values by means of inverse prediction.
Because of apparent direct proportionality between the means
and standard deviations of reported recoveries as spiking
levels increased (i.e., coefficients of variation did not
vary significantly within carbon chain-length groups), both
water and sediment data were transformed to logarithms
(natural logarithms) for regression analysis. The resulting
log-linear model, In Y^ = In a + b In X + In e^, proved to be
satisfactory, stabilizing standard deviations and p'roviding
correlation coefficients (r) that ranged from 0.95 to 0.99
for all but the C2Q-30 sets, which were 0.85 for sediment
B-21
-------
and 0-73 for water. The model for Y (untransformed) is
Yj_ = aX e^, the random error component e^ being multiplicative
rather than additive. Plots of Y on X, with 95% confidence
bounds for individual measurements, are shown for Cig-12'
C14-17 and C20-30 in sediment in Figures B-l, B-2 and B-3,
respectively, and for C]_g-i2 and C14-17 i° water in Figures B-4
and B-5. (The plot for C2Q-30 i-n water is not presented
because of erratic data for the 1 ug/L spiking level.)
Working equations for calculating the predicted value of a
reported concentration (Y) for a given spiked concentration
(X) and of a true concentration (X) for a given reported
concentration (Y), with respective 95% confidence limits,
are presented for sediment in Table B-8 and for water in
Table B-9, for each carbon chain-length group. (Confidence
limits incorporate the 2-tail, 0.05 value of t with n - 2
degrees of freedom.) The equations are used in the
following manner:
o To determine Y for a given value of X, first solve for
IrfY by inserting the value of In X in the right side
of the InY equation. The antilog of In Y, or exp IrT^Y,
is Y, the best estimate of the concentration Y that will
be reported for a single analysis of a sample spiked
at concentration X.
o To determine upper and lower 95% confidence limits
for Y, first determine those limits for In Y by inserting
the values for In X and the now-determined In Y in the
respective equation and solving first for the upper ( + )
and then for the lower (-) confidence limit. The
antilogs of those values are the upper and lower 95%
confidence limits for Y.
A
o To determine values for X, the best estimate of the true
CP concentration in a sample whose reported concentration
from a single analysis is Y, and the 95% confidence limits
for X (the true concentration), the procedure is as
above in solving for Y and the confidence limits for Y,
except that the values of In Y and, once solved, of lfT~X
are inserted as required. The antilog of In X is X,
and the antilogs of the upper and lower confidence limits
for In^X are those limits for X.
Approximate values for the above calculations may be derived
directly from Figures B-l through B-5. Values for predicted
Y (Y and 95% confidence limits for Y) for a given value of X
are read conventionally on the Y-axis by extending
horizontal lines to that axis from the points at which a
line extended vertically from a selected value on the X-axis
intersects the regression line for Y on X and the lines for
the upper and lower confidence limits for individual measure-
ments. Values for predicted X (X and the 95% confidence
limits for X) are read on the X-axis by extending vertical
B-22
-------
C SEDIMENT (UG/KGI
10-12
>
Y = EXP LN Y = .6145 X
.9984
1100 •
1000
900
BOO
700
E 600-^
0
V 500-1
R
U <00
E
1 300
200
100
0
100
200 300 400 500 600 700 BOO 900 1000
SPIKE. X
FIGURE B- 1. 95% CONFIDENCE INTERVAL FOR
SINGLE OBSERVATION OF Y
B-23
-------
C SEOlnENT (UC/KC)
14-17
1000
900
500
200
100
0-1
Y = EXP LN Y = .5596 X
1.0013
—i—
200
—i—
800
100
300 400 500 600
SPIKE. X
700
900
1000
FIGURE B-2. 95% CONFIDENCE INTERVAL FOR
SINGLE OBSERVATION OF Y
B-24
-------
C SEDIMENT (UC/KCI
20-30
3000-]
2000
1000 J
Y = EXP LN f = .8275 X
.9682
100 200 300 400 500 600
SPIKE. X
700
800
900 1000
FIGURE B-3. 95% CONFIDENCE INTERVAL FOR
SINGLE OBSERVATION OF Y
B-25
-------
C URTER IUC/L)
Y = EXP LN Y r .9SH X
1.0642
p
R 6
E
0
24
-------
C MHTER (UC/LI
10-12
R 6
E
0
T
E
°4
V
n
li3
E
A ^"--^ I.MtS
Y = EXP LN Y = .6386 X
2 3
SPIKE. X
FIGURE B-5 95% CONFIDENCE INTERVAL FOR
SINGLE OBSERVATION OF Y
B-27
-------
lines to that axis from the points at which a line extended
horizontally from a selected point on the Y-axis intersects
the regression line for Y on X and the lines for the
individual confidence bounds. (Note that in reading from
a plot, the line that provides the upper 95% bound for
predicted Y provides the lower 95% bound for predicted X,
and vice versa. )
6.8 Estimation of True CP levels (X) in Individual Samples,
Using Inverse Prediction from Regression Analysis
From the working equations for X and the 95% confidence limits
for X presented for sediment in Table B-8 and for water in
Table B-9, a "best estimate" of the true level of each CP
group in a sample, and the 95% confidence limits for that
estimate, can be derived from the reported concentration (Y)
for that sample. Estimation of X by inverse prediction is
similar to th_e use of a correction factor for recovery
except that X is based on least squares regression procedures
that utilize recovery data from all spiking levels and
provide valid statistical confidence limits for estimates
of X. (Procedures for using the equations are given in
Section 6.7.)
It should be noted that confidence limits for inverse
prediction are typically not symmetrical, being somewhat
greater above than below predicted values of X. This lack
of symmetry is increased for CP confidence limits because
the CP model for X is multiplicative rather than additive.
Because the equations are necessarily based on recoveries
for spiked samples, their validity for use in environmental
studies requires the assumption that extraction of CPs
from unspiked environmental samples will be of efficiency
comparable to that for spiked CPs.
6.9 Estimation of Method Recovery, Accuracy, and Precision
Measures of overall method recovery and accuracy (both expressed
as percentages) can be derived directly from the regression of
Y on X, recovery being measured as Y/X x 100 and accuracy as
(1 - | Y" - X|/X) x 100, which is equivalent to recovery for
values of Y" less than X. The regression values Y and its
respective X provide the necessary input values, "Y* being a
function of recoveries for all spiking levels rather than a
single level.
Regression estimates for accuracy and, equivalently, for
recovery for analysis of CPs in sediment averaged 61%,
ranging from 57% for the C^4_^y group to 66% for the C2Q-3Q
group. (Estimates are comparable to those for arithmetic
averages of recovery data in Table B-5.) Accuracy and
B-28
-------
Table B-3. Working Equations1/ for Predicted Values, and 95% Confidence Limits (C.L.), for Reported (Y) and
True (X) CP Concentrations in Individual Sediment Samples
Log-Linear
A
In Y =
C.L. In
In X =
C.L In
0.
Y
1.
X
Predictive
9984 In X
= In Y ±
0016 (In
= 1.0259
_
Equation
0
/>
Y +
In X
.4869
.2888 +
0.4869)
(Natural
Logarithms)
Cin-i
0.0252 (In X -
- 0.1594 ±\/0.
2974 +
9
6.1459)2
0.0266 (
Predicted Concentration2/ (ugAg)
exp
exp
exp
A 0
In X - 6.1459)2 exp
A
In Y
C.L.
In X
C.L.
....... ; . — _ _
In Y
In X
I xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx I
td
I
In Y = 1.0013 In X - 0.5805
i / 0.2C
C.L. In Y = In Y £ / 0.2079 + 0.0181 (In X - 6.1459)2
In X = 0.9987 (In Y + 0.5805)
C.L. In X = 1.0184 In X - 0.1133
i/o.
2112 + 0.0188 (In X - 6.1459)2
A
exp In Y
exp C.L. In Y
exp In X
exp C.L. In X
A
In Y = 0.9682 In X - 0.1893
A
C.L. In Y = In Y ± /1.8243 + 0.1592 (In X - 6.1459)2
In X = 1.0329 (In Y + 0.1893)
C.L. In X = 1.2046 IrTx - 1.2573
±/2.
A
exp In Y
exp C.L. In Y
A
exp In X
3445 + 0.2464 (In X - 6.1459)2 exp C.L. In X
I ^ . _ _ . ..._ _
IKXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXX
V Derived from regression analysis of In spiked sample recovery data, method validation study. Equations
for IriY are logarithmic transformations of the respective multiplicative regression equations (Y=aXb)
shown in Figures B1-B3. Logarithmic confidence limits incorporate "t" values for <*. = 0.05,
n - 2 = 11 degrees of freedom.
2/ exp In Y reads eln Y or the antilog of In Y, where e = 2.71828
-------
Table B-9. Working Equations1/ for Predicted Values and 95% Confidence Limits (C.L.) for Reported (Y) and
True (X) CP Concentrations in Individual Water Samples
tu
i
u>
O
Log-Linear Predictive Equation (Natural Logarithms) Predicted Concentration (jaq/L)
C.L.
In X
C.L.
= 1.0642 In X - 0.
In Y = In Y ±V/0.
= 0.9396 (In Y + 0
In X = 1.0148 IrTk
C10-12
0498 exp In Y
0937 + 0.0165 (In X - 1.0338)2 exp In C.L.Y
.0498) exp In X
- 0.0153 + V/0.0840 + 0.0150 (IrTk - 1.0338)2 exp In C.L. X
xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx
1
C.L.
Irfx
C.L.
= 1.1429 In X - 0.
In Y = IfTV +V 0.
= 0.8749 (In Y + 0
In X = 1.0615 Irfx
C14-17
4485 exp ln*Y
4290 + 0.0756 (In X - 1.0338)2 exp In C.L. Y
.4485) exp IrTx
4. / ^ 7
- 0.0635 ±\/ 0.3486 + 0.06523 (In X - 1.0338)^ exp In C.L. X
xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx
I/ Derived from regression analysis of In spiked sample recovery data, method validation study.
Equations for InY are logarithmic transformations of the respective multiplicative regression
equations ( ^=aXb) shown in Figures B-4 and B-5. Logarithmic confidence limits incorporate
111" values forc(= 0.05, n - 2 = 10 d.f.
NOTE: Recovery of C2Q-3Q spikes in water samples was too variable to provide useful predictive
equations.
-------
recovery for water analysis were essentially 100% for the
C10-12 group and 75% for the Ci^-n group. The percentages are
comparable to the arithmetic averages of the respective
replicate recoveries presented in Table B-3. (As mentioned,
regression analysis of the C20-30 water data was not utilized
because of anomalous results at the 1 yug/L spiking level.)
Precision was assessed for each set of replicated samples as
the standard deviation expressed as the percentage of their
mean, i.e., as the "coefficient of variation" (CV) or,
equivalently, as the "relative standard deviation" (Tables B-3,
B-4 and B-5). For replicated spiked water samples (Table B-3),
CVs ranged from 6.7% to 53.5% (excluding an aberrant 165%),
with a median CV of approximately 28% (2 degrees of freedom
(d.f.) per CV). Precision was consistently higher for
quantification of C^o-12 than for C2Q-30' C^s ranging from
6.7% to 22.9% for the former and from 34.8% to 165% for the
latter. CVs for C^4_^7 quantification were of intermediate
values.
For replicated unspiked and spiked sediment samples (excluding
method blanks as potentially atypical because they could
not be prepared from sediment), CVs ranged from 16% to 61%,
with a median CV of approximately 23% ( 1 and 3 d.f. per CV for
unspiked replicates and 2 d.f. per CV for spiked replicates).
There were no discernible differences in analytical precision
between unspiked and spiked samples or among carbon chain-
length groups.
B-31
-------
Table B-10
Chlorinated Paraffin Concentrations, by Carbon
Chain-length Group, Reported for Spiked and Unspiked
Sediment Samples-^/and Method Blanks: Method
Validation Study
Sample
Source
Station B
Station A
Method Blank
Station A
Station A
Station A
Method Blank
Method Blank
Spike
(ug/kg)
/
0
0
0
200
500
1,000
50
1,000
Replicate
1
2
(mean)
1
2
3
4
(mean)
1
2
3
4
(mean)
1
2
3
(mean)
1
2
3
(mean)
1
2
3
(mean)
1
1
2
3
(mean)
Reported
Cin-1 7.
2.62
6.49
(4,56)
16.21
36.93
26.32
42.71
(30.55)
0.12
0.59
nd^/
nd
(0.18)
157.86
101.35
79.87
(113.02)
365.23
300.92
237.37
(301.17)
709.44
724.70
471.68
(635.27)
37.53
730.41
685.99
619.78
(645.39)
Concentr
(jig/kg)
Cl 4-17
11.24
15.53
(13.39)
52.67
73.02
50.81
56.06
(58.14)
0.88
nd
nd
nd
(0.22)
169.54
116.56
85.92
(124.01)
364.05
285.59
263.42
(304.36)
621.58
662.43
479.06
(587.69)
24.49
502.14
547.23
473.21
(507.53)
•ations
80.63
49.53
(65.08)
126.19
184.48
145.55
195.49
(162.93)
13.89
nd
nd
nd
(3.47)
415.95
236.30
107.77
(253.34
496.91
390.36
358.61
(415.29)
850.22
1056.55
660.91
(855.89)
15.44
293.27
403.17
419.33
(371.92)
/ Sediments from Sugar Creek, Stations
Ohio: Reconnaissance Survey, August
/ nd = not detected; assigned value of
A and B near Dover,
12, 1986
0
B-32
-------
Table B-ll
Chlorinated Paraffin Concentrations, by Carbon
Chain-length Group, Reported for Spiked and
Unspiked Stream Water1/ Samples and Distilled
Water Method Blanks: Method Validation Study
Reported
Sample Spike
Source (ug/kg) Replicate C] o-i 2
Station B
Station A
Method Blank
Station A
Station A
Station A
Method Blank
'
0
0
0
1
2
(mean)
1
2
3
4
(mean)
1
2
3
4
0.064
0.157
(0.110)
0.039
0.047
0.060
0.023
(0.042)
0.014
0.110
0.062
0.026
(mean) | (0.053)
1.0 1
2
3
(mean)
2.5
5.0
5.0
1
2
3
(mean)
1
2
3
(mean)
1
2
1 3
(mean)
0.928
0.943
1.116
(0.996)
2.277
2.139
2.462
(2.293)
7.089
4.823
4.902
(5.605)
5.749
5.080
5.199
(5.343)
Concentrations
(jug/kg)
Ci4_i7 C20-30
0.011
nd2/
(0.006)
n.oil
0.010
0.031
0.003
(0.014)
0.096
0.044
0.010
0.005
(0.039)
0.694
0.797
0.611
(0.701)
1.947
0.964
1.754
(1.555)
6.810
3.769
3.840
(4.806)
4.641
3.510
3.704
(3.952)
0.008
nd
(0.004)
0.010
0.009
0.017
nd
(0.009)
nd
0.007
nd
nd
(0.002)
0.052
3.092
0.048
(1.064)
1.221
1.874
0.896
(1.330)
8.900
6.493
2.556
(5.983)
3.282
1.859
1.885
(2.342)
1
Water from Sugar Creek, Stations A and B near Dover, Ohio:
Reconnaissance Survey, August 12, 1986
2/ nd = not detected; assigned value of 0
B-33
-------
APPENDIX C
SAMPLE COLLECTION PROTOCOL
-------
TABLE OF CONTENTS
Section Heading Page
1. Parameter Coverage C-2
2. Sample Collection C-2
3. Field Quality Control C-5
FIGURES
C-l Demonstration of Technique
Used in Grab Sampling of
Waters and Wastewaters C-4
C-2 Water and Sediment Samplers
Used in the Study Sites C-6
C-3 Field Study Observation Sheet C-8
C-4 Sample Data Sheet C-9
TALBES
C-l Correlation of Sample Identity with
Barcode Numbers, Sugar Creek C-10
C-2 Correlation of Sample Identity with
Barcode Numbers, Tinkers Creek C-12
C-l
-------
The sample collection protocol for the field studies for
Sugar Creek near Dover, Ohio, and Tinkers Creek near Bedford, Ohio,
is given below.
1. Parameter Coverage
In addition to Chlorinated Paraffin determinations, temperature
(°C), flow (cfs) and depth in feet (ft) were recorded at each
sampling station.
2. Sample Collection
All samples v/ere collected and handled using procedures that
are fully approved by EPA. A duplicate set of samples (except
mussels) from the Sugar Creek site was provided to the Dover
Chemical Corporation for their independent analysis. A duplicate
sample of the process water from the S.K. Wellman Company in the
Tinkers Creek site was provided to that facility's management.
All samples from both sites, with the exception of the lagoon
samples collected from the Sugar Creek site, were collected
by wading in the stream. For the lagoon, two canoes were lashed
together with three 2 in x 3 in x 0 ft studs to form a stable
catamaran platform. All lagoon samples were collected from this
platform.
Sampling in Sugar Creek was done in a downstream to upstream
direction in order to avoid unnatural disturbances and thereby
minimize contamination of the samples.
2.1 Sample Preparation
All water column and sediment samples were collected in
glassware that had undergone the following cleaning steps:
o Surface residuals were removed.
o A hot, soapy soak was used to loosen and flotate most of
the residue.
o A hot water rinse was used to flush away floating residue.
o A soak with deep penetrant or oxidizing agent was used
to destroy traces of organic residue.
o A hot water rinse was used to flush away materials
loosened by deep penetrant soak.
o A rinse with deionized water was used to remove metallic
deposits from the tap water.
C-2
-------
o The glassware was then rinsed with high purity methanol
followed by high purity methylene chloride.
Glassware was handled using polyethylene gloves to avoid contact
with hands.
2.2 Water Column Samples
Each water column sample collected at stations A1, B, B1, D
and K in Sugar Creek and stations A, B and C in Tinkers Creek was
a composite of single grab samples collected from at least three
eguidistant points along a stream transect. A 0.5 gallon glass
jar was triple rinsed with stream water at the location the
sample was to be collected. The jar was then submerged in the
stream until all air was replaced by a water sample (Figure C-l).
The water sample depth was half way between the surface and the
bottom of the stream. The samples collected along the stream
transect were then composited to form a single sample.
Water samples collected at stations D, E, F, and G at Tinkers
Creek were collected as a single grab in 0.5 gallon glass jars.
Water samples collected at stations LJ , L2 , and 11.3 at the
Sugar Creek site were depth-integrated with discrete samples
collected from three depths per station: near the bottom (17-20
ft), at mid-depth (10 ft) and near the surface (2 ft). To avoid
outside contamination, a stainless steel Kemmerer sampler (Figure
C-2) with non-rubber stoppers was used.
All jars were capped with Teflon-lined lids. The water
samples reguired no preservatives.
Each sample jar was labeled with a barcode label.
2.3 Sediment Samples
All sediment samples were collected in 500 mL glass jars.
At stations A', B, B1, D, and K at Sugar Creek and stations A, B,
and C at Tinkers Creek, a stainless steel scoop was used to remove
sediment from the same eguidistant points along the same stream
transect that the water column samples were collected. These
discrete samples were then composited to form a single sample.
At stations D, E, and F at Tinkers Creek, the sample was
a single grab using a stainless steel scoop.
C-3
-------
FIG. C-l Demonstration of Technique Used in the Grab
Sampling of Waters and Wastewaters
04
-------
At stations LI, L2, and 1.3 in Sugar Creek, sediment samples
were collected using an Ekman dredge (Figure C-2).
Large rocks were removed before placing the samples in the
jars. All jars were capped with Teflon-lined lids. Sediment
samples reguired no preservatives. Each sample jar was labeled
with the same information as described above. The stainless
steel scoop and the Ekman dredge were triple rinsed with distilled
water prior to filling a sample collection jar.
2.4 Tissue Samples
Mussel samples (where available) were collected from the
Sugar Creek stations by hand and placed on ice in the coolers.
In accordance with the permit obtained by the field crew
from the Ohio Department of Natural Resources, no more than 10
mussel specimens were collected from any of the stations in Sugar
Creek.
At the Tinkers Creek study site, attempts were made to
collect biological organisms from the stream bottom at each of
the field stations. Sediment scoops were sieved using a standard
No. 30 sieve in search of invertebrate larvel forms, especially
chironomid larvae. None were found after several hours of sampling.
All sample jars were kept in coolers out of direct sunlight
and transported in ice-filled coolers with sufficient packaging
material to reduce the possibility of breakage. The mussels
collected during the Sugar Creek study were also placed in an ice-
filled cooler. This kept the mussels alive during transport to
the laboratory in Kansas City. All water, sediment, and mussel
samples were shipped via overnight delivery service to MRI's
Kansas City laboratory.
3. Field Quality Control
Monitoring for chlorinated paraffins reguires demanding
guality control procedures because of the potential for contamination,
During this study, special precautions were made to avoid any
contamination. These included using polyethylene gloves in the
field and in the laboratory to avoid possible contamination by
hands, avoiding seals and paints that may contain CPs, and avoiding
PVC and plastic and rubber materials which may contain CPs.
C-5
-------
(a)
(b)
FIG. C-2 Water and Sediment Samplers Used in the Study Sites
(a) Ekman Dredge (b) Kemmerer Sampler
C-6
-------
A Field Study Site Observation Sheet (Figure C-3) was completed
for each sampling station deployed in the field. The field study
crew used this sheet to describe each sampling station site,
weather conditions at the time of sampling, and the like. Also,
for each sample collected at a station, the field crew completed
Sample Data Sheets (Figure C-4). The field crew used these sheets
to record sample information such as the time of collection, depth
of sample collection, and the like.
3.1 Sample Traceability
All samples were uniquely identified with preprinted barcode
labels. These labels (printed as a set of six) were used to
physically track samples for this project. One of the labels was
affixed to the sample container and a second to a Sample Data
Sheet. The remaining labels were affixed in the laboratory.
The MRI sample traceability protocol was followed for sample
tracking for this project. Traceability records started with
sample collection and the completion of the lower portion of the
Sample Data Sheets. Upon receipt at MRI, the samples were
inventoried by the project sample custodian (See Tables C-l and
C-2). The water and sediment samples were stored in a locked cold
room. This room is accessible only through the cold room custodian,
who maintains records of room temperature and staff accessing the
room. The mussel samples were individually wrapped in aluminum
foil and stored in a freezer. Further transfer of samples was
documented by the sample custodian.
3.2 Quality Control Checks
Spiked water samples were prepared at two stations in the
Sugar Creek site (stations B and L^) and two stations at the
Tinkers Creek site (stations A and D). Water samples collected
at these stations were spiked at 50 ppb. The water sample
collected from station Lj at the Sugar Creek site was taken at
mid-depth for spiking.
The OC field samples were collected in three 4-L glass jugs
and transferred to 0.5 gallon glass jugs for spiking. Separate
sets of 4-L jugs were provided for stations B and LI. Homogenization
and spiking was done according to the following procedures.
C-l
-------
FIELD STUDY OBSERVATION SHEET
Site ID:
Signature:
Date:
Title:
Time:
Sampling Station Description:
Weather Conditions:
Personal Observations:
Dover CP production during Field Study:
Ibs
FIG. C-3 Field Study Observation Sheet
C-8
-------
SAMPLE DATA SHEET
SUGAR CREEK
Field Study: DOVER, OHIO
Station ID:
Field:
Flow (cf s) :
Calculated :
Sample No.
Type of Sample
1 = water
2 = sediment
3 = mussel
Contract Number Date (Mo/Da/Yr)
68-02-4252
Work Assignment No. Substance Monitored:
Chlorinated Paraffin
Samples collected by:
Comp.
or
Grab
Temp.
Cc
Time
Depth
(ft)
Remarks
Samples relinquished to:
to:
by:
by:
on:
on:
Date )
( Date )
FIG. C-4 Sample Data Sheet
C-9
-------
Table C-l Correlation of Sample Identity with Barcode Numbers,
Sugar Creek (Midwest Research Institute)
STATION
ID
B'
B (OC)
MATRIX
Water
Water
Water
Water
Sediment
Sediment
Sediment
Sediment
Mussel
Water
Water
Water
Water
Sediment
Sediment
Sediment
Sediment
Mussel
Water
Water
Water
Water
Sediment
Sediment
Sediment
Sediment
Mussel
Water
Water
Water
Water
Water
Water
Water
Water
Water
Water
Water
Sediment
Sediment
Sediment
Sediment
SAMPLE
TYPE
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Comoosite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Field Spike
Field Spike
Lab Spike
Lab Spike
Trip Spike
Trip Spike
Trip Blank
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
BARCODE
LABEL
01681
01682
01683
01684
01685
01686
01687
01688
01704
01647
01648
01649
01650
01675
01676
01677
01678
01703
01669
01670
01679
01680
01729
01730
01701
01702
01718
01711
01712
01713
01714
01715
01716
01717
01631
01632
01633
01634
01635
01636
01637
01638
* *
*
* *
*
**
* *
*
* *
*
* *
* *
*
*
**
* *
* *
* *
*
* *
*
* *
*
010
-------
Table C-l (continued)
STATION
ID
LI (OC)
MATRIX
Water
Water
Water
Water
Sediment
Sediment
Sediment
Sediment
Water
Water
Water
Water
Sediment
Sediment
Sediment
Sediment
Water
Water
Water
Water
Water
Water
Water
Water
Water
Water
Sediment
Sediment
Sediment
Sediment
Water
Water
Water
Water
Sediment
Sediment
Sediment
Sediment
SAMPLE
TYPE
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Trip Spike
Field Spike
Field Spike
Trip Blank
Field Blank
Field Blank
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
BARCODE
LABEL
01657
01658
01659
01660
01661
01662
01663
01664
01639
01640
01651
01652
01653
01654
01655
01656
01641
01642
01643
01644
01645
01646
01665
01666
01667
01668
01671
01672
01673
01674
01721
01722
01723
01724
01725
01726
01727
01728
**
*
*•*
*
*
**
* *
*
* *
* *
* *
* *
* *
*
*
* *
* *
*
* *
* Split samples for the Dover Chemical Corporation
** Analyzed at MRI
C-ll
-------
Table C-2 Correlation of Sample Identity with Barcode Numbers,
Tinkers Creek (Midwest Research Institute)
STATION
ID
B
MATRIX
Sediment
Sediment
Sediment
Water
Water
Water
Fish
Sediment
Sediment
Sediment
Water
Water
Water
Sediment
Sediment
Sediment
Water
Water
Water
Fish
Sediment
Sediment
Sediment
Water
Water
Water
Sediment
Sediment
Sediment
Water
Water
Water
Water
Water
Water
Sediment
Sediment
Sediment
SAMPLE
TYPE
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composi te
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Composite
Grab
Grab
Grab
Grab
Grab
Grab
Grab
Grab
Grab
Grab
Grab
Grab
Grab
Grab
Grab
Grab
Grab
Grab
BARCODE
LABEL
01787 **
01788
01789
01790 **
01791
01792
01834
01793
01794
01795
01796
01797
01798
01799
01800
01801
01802
01803
01804
01833
01805
01806
01807
01808
01809
01810
01811
01812
01813
01814
01815
01816
01817
01818
01819
01820
01821
01822
* *
**
* *
**
**
* *
C-12
-------
Table C-2 (continued)
STATION
n>
A (OC)
D (OC)
MATRIX
Water
Water
Water
Water
Water
Water
Water
Water
Water
Water
Water
Water
Water
Water
Water
Water
Water
SAMPLE
TYPE
Lab Spike
Lab Spike
Field Spike
Field Spike
Trip Spike
Trip Blank
Field Spike
Bad Blank
Lab Spike
Field Spike
Field Blank
Trip Spike
Grab
Composite
Composite
Grab
Composite
BARCODE
LABEL
01781
01782
01783
01784
01785
01786
01771
01772
01773
01774
01775
01776
01826
01827
01828
01831
01832
**
* *
**
**
**
* Split samples for the S.K,
** Analyzed at MRI
Wellman Company
C-13
-------
The 4-L glass jugs were etched in the laboratory at the 3-L
level. The 0.5-gallon jugs were etched in the lab at the 475,
950, and 1,425 raL levels. In the field, the 4-L jugs were filled
to the 3-L marks with the water sample. The first jug was shaken
thoroughly and the contents poured into the 0.5 gallon jugs to
the first mark (475 mL). The second and third 4-L jugs were used
to fill the 0.5-gallon jugs to the second and third marks
respectively. Two of the four samples for each station were
spiked at the 50 ppb level. This was done by adding 1.0 mL of a
chloroparaffin standard (approximately 70 pg/mL each cell) in
methanol. The remaining field QC samples were spiked at the
same level immediately before extraction in the laboratory.
Extraction and analysis of the eight QC samples (four
samples from each of the two stations), constituting 16 analyses
(8 filtrate and 8 suspended solids fractions) was done at the
same time the field samples were analyzed.
In addition to these field QC samples, trip QC samples were
prepared as follows:
Two samples of laboratory deionized water (volume =
1,425 mL) were prepared for each of the four QC stations, i.e.
stations B and L^ (Sugar Creek) and stations A and D (Tinkers
Creek). These samples were then transported to the field. At
each of the designated QC stations a set of two of these samples
were removed from the cooler and one of these per QC station
selected, at random, and spiked at 50 ppb (a total of four
samples). The other sample from each set of two was not spiked
but was returned to the lab and analyzed along with its spiked
counterpart.
Just prior to analysis, an additional sample per QC station
(a total of four samples) was prepared, again using laboratory
deionized water and spiked at 50 ppb.
Because the rate of adsorption of CPs to suspended solids may
differ between environmental and spiked samples and between field-
spiked and laboratory-spiked samples, CP recovery is expressed in
a weight/volume basis (pg/L) after summing the weights of CP in
the filtered water sample and its respective solids. (It is
similarly meaningful to express CP residues in water samples in
the same way, especially when comparing residues in samples
containing different amounts of suspended solids. For example,
residue levels in the solids of two samples might be quite
similar on weight CP/weight solids basis, whereas total weight of
CP would be considerably greater in the water sample having the
higher concentrations of suspended solids.)
-------
50277-101
REPORT DOCUMENTATION
PAGE
l._HCTOKT HO.
"560/5-87-012
J. •*cip»«nrs Acc*»ion No
4. TMt *«d SuMitlc
Chlorinated Paraffins: A report on the Findings
From Two Field Studies, Sugar Creek, Ohio and
Tinkers Creek, Ohio
1. ••pert O>tt
January 22, 1988
7.
Murray, Tom and Mary Frankenberry
Steele, David H. ; Heath, Robert G
•. Perferminc Orgciuiation ««pt. No.
10. Piui»U/T»a/Wof1i Unit No.
a) Exposure Evaluation Division. OTS
b) Midwest Research Institute, 425 Volker Blvd.,
Kansas City, Missouri 64110
c) Battelle Columbus Division, 2030 M St. N.W.
Washington. D.C. 20036
11.
«:> EPA 68-02-4252
£> EPA 68-02-4243
It. Saonieong Orc*niut>on
Environmental Protection Agency
Office of Toxic Substances
Exposure Evaluation Division
401 M St. S.W., Washington D.C. 20460
11. Type ef Report 4 Pvriod Covered
Final Report
1986 - 1987
14.
IS. Supplementary Notrt
Joseph J. Breen, Project Officer - MRI contract 68-02-4252
Cindy Stroup, Project Officer - Battelle contract 68-02-4243
1C. AMrvct (Limit: 200 word*)
This report presents the results of two field studies conducted in
1986 by the Environmental Protection Agency's Office of Toxic Substances
(EPA/OTS) under the existing chemicals program to screen selected
waterbodies for the presence of chlorinated paraffins. Chlorinated
paraffins are saturated straight-chain hydrocarbons ranging from 10 to
30 carbons in length and containing 20 to 70% chlorine by weight. The
information gained from these field studies will be coupled with that
from other environmental hazard and environmental exposure studies
and collectively contribute to an EPA risk assessment for this chemical.
The report also develops an analytical method for chlorinated paraffins
in Different environmental matrices and includes a rigorous statistical
analysis of the data used to validate the method.
17.
Chlorinated Paraffins, lubricating oils, survey design,
HRGC/NCIMS/SIM analytic method, statistical assessment of
method validation studies.
Chromatography
Cleanup
Statistical analysis
Literature review
Extraction
Mass spectrometry
c. COIATI Ftotd/Group
1ft. AvclUbillty St*t«fn*fit
Release Unlimited
It. Security CU» fTr.il H«p*1>
Unclassified
21. No. of
55 plus App.
20. Security Cln\ (Thit *t
Unclassified
22. Pnct
------- |