&EPA
United States
Environmental Protection
Agency
Great Lakes National Program Office
77 West Jackson Boulevard
Chicago, Illinois 60604
September 1996
Assessment and
Remediation
of Contaminated Sediments
(ARCS) Program
FIELD AND LABORATORY AND
SUPPORT RESULTS
BUFFALO RIVER MASS BALANCE
PROJECT
® United States Areas of Concern
• ARCS Priority Areas of Concern
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FIELD AND LABORATORY AND SUPPORT RESULTS
BUFFALO RIVER MASS BALANCE PROJECT
Submitted to:
U.S. Environmental Protection Agency
Great Lakes National Program Office
Grant #X995280-01
Submitted by:
Great Lakes Center for Environmental Research and Education
State University of New York College at Buffalo
1300 Elmwood Ave.
Buffalo, NY 14222
Principal Investigator:
Harish C. Sikka
September 1995
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Ftaif
CTwcago.lL 60604-3590
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CONTENTS
1. Introduction 1
1.1.Background 1
2. Objectives 7
3. Sampling approach 9
3.1. Buffalo River water samples 9
3.1.1. Sample location and times 9
3.1.2. Sample methodology 15
3.2. Combined sewer sampling 17
3.2.1. Sample locations and times 17
3.2.2. Sample methodology 18
3.3. Fish samples 22
3.3.1. Collection time, location, and methodology 22
3.3.2. Preliminary processing of fish samples 22
3.3.3. Fish sample preparation for organic analysis 25
3.3.4. Determination of fish age for scale growth 26
3.4. Hydrometeorologic sampling 26
3.4.1. Water levels and discharge 26
3.4.2. Rainfall data 28
4. Sample Processing 29
4.1. Sample identification nomenclature 29
4.2. Blank water preparation 29
4.3. Pentaplate system filtration 31
4.4. XAD-2 resin columns 35
4.5. Water sample pre-concentration 35
4.6. Quality control 35
5. Materials used for chemical analysis 38
5.1. High purity standards 38
5.2. High purity solvents 38
5.3. High purity gases 38
5.4. Glassware and chemicals 38
5.5. GC and HPLC supplies 38
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6. Analytical procedures 39
6.1. Extraction 39
6.1.1. Suspended sediments 39
6.1.2. Water samples (XAD-2 resin) 40
6.2. Analysis of PAHs 41
6.2.1 HPLC parameters used for the analysis of PAHs 41
6.3. Analysis of PCBs and chlorinated hydrocarbon pesticides 41
6.3.1. Sample cleanup and separation of PCBs and chlorinated
hydrocarbon pesticides 41
6.3.2. Analysis of PCBs and chlorinated hydrocarbon pesticides 42
7. Quality assurance and quality control (QA/QC) procedures for organic analysis 60
8. Results 62
8.1. Field measurements 63
8.1.1. River discharge and flow characteristics 63
8.1.2. Conventional parameter determined using the SeaBird Sealogger 65
8.1.3. Carp measurements 65
8.2. Results of organic analysis 81
8.2.1. Total PCBs (Dissolved Phase) Fall, 1990 81
8.2.2. Total PCBs (Dissolved Phase) Spring, 1992 90
8.2.3. Total PCBs (Paniculate Phase) Fall, 1990 95
8.2.4. Total PCBs (Paniculate Phase) Spring, 1992 112
8.2.5. Pesticides (Dissolved Phase) Fall, 1990 117
8.2.6. Pesticides (Dissolved Phase) Spring, 1992 133
8.2.7. Pesticides (Paniculate Phase) Fall, 1990 141
8.2.8. Pesticides (Paniculate Phase) Spring, 1992 159
8.2.9. PAHs (Dissolved Phase) Fall, 1990 166
8.2.10. PAHs (Dissolved Phase) Spring, 1992 185
8.2.11. PAHs (Paniculate Phase) Fall, 1990 190
8.2.12. PAHs (Paniculate Phase) Spring, 1992 209
8.2.13. Comparison of levels of organics in the Buffalo River samples
collected during Fall, 1990 and Spring, 1992 215
9. Metals levels in the Buffalo River water and suspended sediments 232
10. Results of conventional parameter analysis and metals QA/QC 243
10.1. Fall, 1990 sampling 244
10.2. Spring, 1992 sampling 262
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11. Combined sewer quantity analysis 273
11.1. December 5, 1990 sampling 273
11.2. August 9, 1991 sampling 273
11.3. Additional overflow observations 274
11.4. Babcock St. automated station 276
12. Combined sewer quality analysis 279
12.1. Additional quality data for Babcock St. sewershed 279
12.2. Additional quality data for Bailey Ave. outfall (site 10) 285
13. Results 286
13.1. Total PCBs Buffalo River Water Fall 1990 286
13.1.1. Total PCBs Buffalo River Water Spring 1992 286
13.1.2. Total PCBs Buffalo River Sediments Fall 1990 286
13.1.2.1. Total PCBs Buffalo River Sediments Spring 1992 286
13.2. Pesticide Concentration Buffalo River Water 1990 286
13.2.1 Pesticide Concentrations Buffalo River Spring 287
13.2.2. Pesticide Concentrations Buffalo River Sediments Fall 1990 287
13.2.2.1. Pesticide Concentrations Buffalo River Sediments spring 1992 287
13.3 PAHs Buffalo River Sediment Fall 1990 288
13.3.1. PAHs Buffalo River Water 288
13.3.1.1. Benzo[a]anthracene 288
13.3.1.2. Chrysene 288
13.3.1.3. Benzo[b]fluoranthene 288
13.3.1.4. Benzo[k]fluoranthene 289
13.3.1.5. Benzo[a]pyrene 289
13.3.2. PAHs Buffalo River Sediment Fall 1990, Spring 1992 289
13.3.2.1. Benzo[a]anthracene Concentrations in Sediments 289
13.3.2.2. Chrysene Concentrations in Sediments 289
13.3.3.3. Benzo[b]fluoranthene Concentrations in Sediments 289
13.3.3.4. Benzo[k]fluoranthene Concentrations in Sediments 290
13.3.3.5. Benzo[a]pyrene Concentrations in Sediments 290
14. Summary 290
14.1. Total PCBs 290
14.2. Pesticides 291
14.3. PAHs 291
14.4. Metals 292
15. References 293
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1. INTRODUCTION
1.1 Background
The Buffalo river is located in western New York State and drains an area of 1244 km2,
primarily to the south and east of the city of Buffalo (Figure 1). The lower portion of the Buffalo
River has been designated an "Area of Concern" by the International Joint Commission (IJC) due
to a variety of environmental impairments. The impairments identified in a Level I Remedial
Action Plan submitted to the IJC (New York State Department of Environmental Conservation
(NYSDEC), 1989) included: restrictions on fish and wildlife consumption; fish tumors and other
deformities; degradation of benthos; restrictions on disposal of dredged sediment; and loss of fish
and wildlife habitat. In addition, the Remedial Action Plan noted that degradation of fish and
wildlife populations and bird or animal deformities/reproduction problems were likely.
Most of the Buffalo River watershed lies within Erie County, with the exception of the
uppermost reaches. The county is in two physiographic regions. The northern half and western
edge of the county are within the Erie=-Ontario Lake Plain Province, while the southern half of
the county is within the Allegheny Plateau Province. The Erie-Ontario Province formerly was a
glacial lakebed and therefore has limited relief except in the areas of the major drainage ways.
The southern and eastern boundaries of the Erie=Ontario Province are formed primarily by glacial
lake beaches. The Allegheny Plateau has characteristic wide ridge tops and flat-toped hills. The
soils in the watershed primarily are medium-textured, with some areas of moderately-fine texture
(Soil Conservation Service, 1986). Except for a few kilometers above their confluence with the
Buffalo River, the tributaries are fast-flowing with many rapids and waterfalls. Average slopes of
the tributaries typically range between 0.001 and 0.007. In contrast, the Buffalo River has an
average slope of less than 0.0002 (Sargent, 1975). Land use within the watershed varies. The
upper portion of the watershed is characterized primarily by woods and farmland. However,
tributaries to the river also pass through several communities, receiving both industrial and
municipal discharges.
The Buffalo River Area of Concern (AOC) spatially extends from the mouth o the Buffalo
River to the point upstream at which backwater effects during Lake Erie's highest monthly average
level do not impact river flow (Figure 1). Historically, the AOC was heavily industrialized, with
activities including: steel production; coking operations; oil refining; chemical and dye production;
and flour milling (Sauer, 1979; Rossi et al. 1993; Bingham, 1931; Kassel, 1923; Rundell and Stern
1962; Buffalo Evening News, 1900). Industrial activity has declined along the river in the last
decade and steel production, coking operations and oil refining have ceased. Land use along the
river currently is a mix of industry, open space, commercial and residential. The AOC is
designated a navigable channel from approximately 450 meters downstream of the Cazenovia Cr.
confluence to the river mouth at Lake Erie (Figure 1). Accordingly, the river depth is maintained
at approximately 7 meters through dredging operations supervised by the Buffalo District Corps of
Engineers.
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Figure 1 Buffalo River Area of Concern and Buffalo River Watershed (from Irvine and
Pettibone, 1993).
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Historical (1940-1985) monthly mean inflows into the upper end of the river range between
45 mV1 in March and 3.3 mV1 in July (Meredith and Rumer, 1987). The river can exhibit
esturine-like characteristics during low flow periods when levels at the eastern end of Lake Erie
increase due to higher velocity, south-westerly winds. Flow reversals and thermal stratification
between lake and river water have been observed for several kilometers upstream during these
times of wind setup (e.g. Sargent, 1975; Irvine et al. 1992).
The Buffalo River Improvement Corporation (BRIC) augments flows within the river
through pumping operations that transfer water from Lake Erie to industries along the river. The
industries discharge the lake water to the river after using it for cooling and other processing
purposes. The BRIC flow augmentation has diluted pollutant concentrations within the river and
decreased residence times (Sauer, 1979). Prior to the industrial decline, the BRIC often
contributed 90% of the total river flow during the summer months (Sauer, 1979). Pumping rates
from the lake have declined along with industrial activity, averaging around 0.7m3s"1 hi recent
times (J. Dietz, BRIC, pers. comm.). A more detailed discussion of the physical, industrial and
cultural characteristics within the Buffalo River AOC is provided by Irvine et al. (1992) and
NYSDEC (1989).
The NYSDEC (1989) identified potential pollutant sources to the Buffalo River, including:
combined sewer overflows (CSOs); direct industrial discharges; leaching from inactive hazardous
waste sites; water column interaction with historically contaminated bed sediment; and upstream
point and nonpoint sources such as municipal wastewater treatment plants and agricultural runoff
(Figures 2 through 4). This report summarizes recent field and analytical efforts applied hi
support of a mass balance evaluation of pollutant level dynamics and loadings in the Buffalo River
AOC. One of the objectives of this mass balance evaluation was to quantify relative poolutant
inputs from the sources identified in the Remedial Action Plan.
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Figure 3 Inactive hazardous waste sites within the AOC (from NYSDEC, 1989).
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COMBINED SEWER
OUTFALLS
Figure 4 Combined sewer outfalls and sample locations. Site names used in the text are as
follows: 1 - Indiana St.; 2 - Dead Man's Cr.; 3 - Hamburg St.; 4 - St. Stephans PL; 5 -
Babcock St.; 6 - Boone St.; 7 - Tamarack St.; 8 - Cazenovia Park; 9 - Hillery Park; 10 -
Bailey Ave. Note that sample site 4 is one of several overflows that discharge into the Smith
St. outfall.
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2. OBJECTIVES
The Buffalo River AOC (Figure 1) is one of five demonstration sites for the U.S.
Environmental Protection Agency's ARCS (Assessment and Remediation of Contaminated
Sediments) program. Toxic organics and heavy metals, which historically have impaired the
ecosystem of the lower river, are the pollutants of concern (Table 1). As a part of the ARCS
program a mass balance evaluation of pollutant level dynamics and loadings within the Buffalo
River AOC was developed. The mass balance approach implemented hydrodynamic, sediment
transport and chemical fate models to estimate pollutant movement through the lower Buffalo River
(Atkinson et al., 1993). The modeling results will be used to guide the selection of remediation
strategies for this river.
Model calibration requires data both on the levels and dynamics of the target pollutants in
the River and the governing environmental parameters (e.g. water levels and flows, precipitation,
solar radiation, air and water temperature). The objectives of this study have (1) to determine the
levels of chemical contaminants (polychlorinated biphenyls [PCBs], chlorinated hydrocarbon
pesticides, polynuclear aromatic hydrocarbons [PAHs], and metals) and selected conventional
parameters hi water and suspended sediment samples collected from Buffalo River and (2) to
determine the levels of above-listed chemical contaminants in combined sewer flow. Samples
collected hi this study included Buffalo River water during event and interevent periods; combined
sewer flow at different locations hi South Buffalo; and carp of different ages from the river. This
report: i) summarizes the field and analytical methods used in the determination of target pollutant
levels; ii) presents and summarizes pollutant levels for collected river and combined sewer
samples; and iii) provides preliminary interpretation of data, including identification of trends.
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Table 1 List of Chemical contaminants and Conventional Parameters Determined in the
Buffalo River Water and Suspended Sediments
1. Chlorinated Aromatic Hydrocarbons (CAHs)
Total PCBs
Gamma-Chlordane
Alpha-Chlordane
Dieldrin
p,p'-DDT
2. Polynuclear Aromatic Hydrocarbons (PAHs)
Benz(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
3. Metals
Lead
Copper
Iron
4. conventional Parameters
Sulphide
Chloride
Alkalinity
Hardness
Total Suspended Solids
Total and Dissolved Organic Carbon (TOC and DOC)
Calcium
Magnesium
Water Temperature *
Dissolved Oxygen*
Conductivity*
Fluorescene*
Transmissivity*
5. PCB congeners, Pesticides and PAHs in fish (carp)
Analysis for categories 1 and 2 was done at the Great Lakes Center for Environmental Research and
Education, SUNY College at Buffalo. Analysis for categories 3, and 4 was done at the Alfred Analytical
Laboratory, Alfred State College, Alfred, NY 14802, except those marked by *, determined by Dr. J.K.
Singer, SUNY College at Buffalo with a Seabird Sealogger. Analysis for category 5 was done by Battelle,
Pacific Northwest Division, Marine Sciences Laboratory, Sequim, WA 98383 and U.S. Fish and Wildlife,
National Fisheries Contaminant Research Center, Columbia, MO.
8
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3. SAMPLING APPROACH
The primary objective of our study was to determine the levels of the various water quality
parameters listed hi Table 1 for Buffalo River water under event and non-event conditions. In
addition, samples of combined sewer flow and carp (from within the AOC) were collected for
chemical analysis. Preliminary processing of the carp samples also was done by SUNY College at
Buffalo personnel, but all analytical work was done by Batelle Pacific Northwest (Sequim, WA)
and the National Fisheries Contaminant Research Center (Columbia, MO). This section of the
report describes locations, timings and methodologies used in the collection of the various sample
types (i.e. Buffalo River water, combined sewer flows, carp).
3.1 BUFFALO RTVER WATER SAMPLES
3.1.1. Sample Locations and Times
Samples for water quality analysis were collected at six sites within the AOC between
October 16, 1990 and November 13, 1990. The locations of the sample sites are presented in
Figure 5 and a more precise description of the locations is provided in Table 2. Samples for the
analytes of interest (Table 1) were collected at all sites on 6 days during the fall, 1990 period and
the actual sample dates are summarized in Table 3. In addition, samples were collected at sites 1
and 2 on October 18, 1990, but sampling was stopped due to high winds and waves. Water
column profiling and flow velocity measurements were done on the day prior to the sampling or
the metals and organics listed in Table 1. The water column profiling was done using a Seabird
SEE 25 Sealogger CTD that provided data on water temperature, dissolved oxygen, conductivity,
fluorescence and transmissivity. because of the potential for the migration of lake water up the
Buffalo River due to wind setup (Irvine et al. 1992), the profiles of temperature and dissolved
oxygen were reviewed prior to additional sapling. The flow velocity measurements were taken
throughout the sample vertical using a Montedoro-Whitney PVM-2A directional flow meter (i.e. a
negative measurement indicated upstream water movement). These data were reviewed at SUNY
College at Buffalo to determine if lake-river water stratification was present and this information
helped guide the selection of a sample depth on the following day.
Major storm events were not observed during the fall, 1990 sampling period and as a result
sampling also was done in the spring of 1992. Samples were collected on April 17 (Survey 1).
April 18 (Survey 2) and April 22 (Survey 3) at sites 1,3, and 6. Samples were collected at fewer
sites because of budget constraints and the limited availability of the pentaplate systems for
filtration of samples. Because of the reduced number of sample sites, it was possible to do the
water column profiling and flow velocity measurements on the same day that the samples for other
parameters (Table 1) were collected Storm even sample dates and the field comments are
summarized in Table 4.
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Rgure 5 Sample transect locations in the Buffalo River Area of Concern.
10
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Table 2 Sample Locations within the AOC
Sample Site Number
1
2
3
4
5
6
Site Location
27 m upstream of the dual Boone St.
combined sewer overflow (sample site 6,
Figure 4)
Corps of Engineers dredging survey transect
739
immediately upstream of Corps of Engineers
dredging survey transect 685 (upstream of
Conrail bridge)
Corps of Engineers dredging survey transect
577
Corps of Engineers dredging survey transect
517
Corps of Engineers dredging survey transect
489
11
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Table 3 Field Sample Summary; Fall, 1990 Sampling*
Sample Date
10/16/90
10/17/90
10/18/90
10/21/90
10/22/90
10/26/90
10/27/90
10/30/90
10/31/90
Parameters
DO. temp., conductivity,
fluorescence,
transmissivity; velocity
DO, temp., conductivity,
fluorescence,
transmissivity; velocity
all remaining metals,
organics and
conventional
DO., temp, conductivity,
fluorescence,
transmissivity, velocity
all remaining metals,
organics and
conventional
DO, temp., conductivity,
fluorescence,
transmissivity;
all remaining metals,
organics and
conventional
DO, temp., conductivity,
fluorescence,
transmissivity; velocity
all remaining metals,
organics and
conventional
Method
SeaBird
Sealogger
Montedoro-
Whitney
PVM-2A
SeaBird
Sealogger
Montedoro-
Whitaey
PVM-2A
pump samples
SeaBird
Sealogger
Montedoro-
Whitney
PVMO-2A
pump samples
SeaBird
Sealogger
pump samples
SeaBird
Sealogger
Montedoro-
Whitney
PVM-2A
pump samples
Comments
Sites 1 and 2 sampled
only; sampling stopped
due to high wind and
waves
light rain through the
night of 10/21, lasting
until noon, 10/22.
Duplicate TOC bottle
broke (Site 3), duplicate
not available for analysis
no velocity measurements
were taken
Site 4 was moved from
transect 577 to 590
because lake vessels
docked at 577
12
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11/4/90
11/5/90
11/8/90
11/9/90
11/12/90
11/13/90
11/30/90
DO, temp., conductivity,
fluorescence,
transmissivity; velocity
all remaining metals,
organics and
conventional
DO, temp., conductivity,
fluorescence,
transmissivity; velocity
all remaining metals,
organics and
conventional
DO, temp., conductivity,
fluorescence,
transmissivity; velocity
DO, temp., conductivity;
fluorescence,
transmissivity
organics
SeaBird
Sealogger
Montedoro-
Whitney
PVM-2A
pump samples
SeaBird
Sealogger
Montedoro-
Whitney
PVM-2A
pump samples
SeaBird
Sealogger
Montedoro-
Whitney
PVM-2A
SeaBird
Sealogger
pump samples
Velocity measured at
Sites 4 and 5 only
Lake vessel docked at
transect 577 (Site 4) -
sampling done at transect
588: considerable wave
action observed early in
the week - may produce
higher TSS
concentrations at lower
sites
Samples taken at sites 1-5
only; winch broke down
at last site
Sites 5 and 6 only
60 liters of water
sampled at site 5 for
spike recovery
Through this report, the individual sample periods have been termed "surveys" and the fall, 1990 sample
dates and survey numbers are as follows:
10/21/90;
10/26/90;
10/30/90;
11/04/90;
11/08/90;
11/12/90;
10/22/90
10/27/90
10/31/90
11/05/90
11/09/90
11/13/90
Survey 1
Survey 2
Survey 3
Survey 4
Survey 5
Survey 6
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Table 4 Field Sample Summary; Spring, 1992 Sampling
Sample Data
4/17/92
4/18/92
4/22/92
Parameters
DO. temp., conductivity,
fluorescence,
transmissivity;
velocity;
metals, organics and
conventional
DO, temp., conductivity,
fluorescence,
transmissivity;
velocity;
metals, organics and
conventional
DO, temp., conductivity,
fluorescence,
transmissivity;
velocity;
metals, organics and
conventional
Method
Seabird Sealogger
Montedoro-
Whitney
PVM-2A
Pump samples
Seabird Sealogger
Montedoro-
Whitney
PVM-2A
pump samples
Seabird Sealogger
Montedoro-
Whitney
PVM-2A
pump samples
Comments
water column profiling and
mil sampling were
performed on the same day
at sites 1,3, and 6
water column profiling and
full sampling were
performed on the same day
at sites 1, 3 and 6
Water column profiling
and full sampling were
performed on the same day
at sites 1,3 and 6
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3.1.2. Sample Methodology
Water column profiling was done at a vertical in the middle of the river channel at each
site. The SeaBird SEE 25 Sealogger CTC was lowered at a constant rate through the water
column by an electric-powered winch system operated from a 16 foot (4.9m) Boston Whaler. The
parameters recorded by the Sealogger included depth (m), water temperature (°C), conductivity (S
m'1), pH, dissolved oxygen (mg I"1), % light transmission (transmissivity), and fluorescence (mg
m"3). The Sealogger sampled each of these parameters at a rate of 8 times per second. The
profiles of temperature and dissolved oxygen were reviewed prior to additional water quality
profiles of temperature and dissolved oxygen were reviewed prior to additional water quality
sampling to determine if there was fluvial-lacustrine stratification as well as the depth of the
stratification. After review of the profiles, samples were taken for organics, metals and other
conventional parameter analyses from a depth at which river water was observed.
Flow velocity measurements were taken at the same vertical in which the water column
profiling was done. Velocity measurements typically were taken immediately prior to the water
column profiling. By taking the velocity measurements before the water column profiling, the
motor of the Boston Whaler was off for at least 5 minutes and this helped reduce the possibility of
any oil contamination. Velocity measurements were made with a Montedoro-Whitney PVM-2A
electronic current meter. The Montedoro-Whitney meter has the capability of registering
directional flow velocities. A positive reading represents normal downstream flow, while a
negative velocity represents an upstream or reverse flow. The velocity measurements were taken
at various depths below the water surface. A total of five instantaneous velocity measurements
were taken at each depth and these readings subsequently were averaged to provide single
representative readings for the individual depths.
Water samples for analysis of organics, metals and conventional parameters were obtained
using American Sigma Streamline Model 700 pump samplers. Teflon-lined tubing was used for
the intake leading to the pump and silicon tubing was used within the pump housing. Clean teflon-
lined and silicon tubing were installed prior to the sample collection at each site. The tubing was
cleaned hi the laboratory using a sequential rinses of soap and water, distilled water, and acetone.
The ends of the tubes were capped with acetone and hexane washed aluminum foil and this foil
was removed immediately prior to use of the tubing.
The water samples were collected from a single depth, but at some sites were width-
integrated. The samples were collected from a depth half way between the bed and the fluvial-
lacustrine interface int he case of stratification (often hi the fall, 1990 period) or at approximately
half of the entire river depth when there was no stratification. Samples were collected at the
following locations across the river channel:
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Site 1: mid=channel (1 sample location)
Site 2: 1/3 and 2/3 across the channel (2 sample locations)
Site 3: 1/3 and 2/3 across the channel (2 sample locations)
Site 4: mid-channel (1 sample location)
Site 5: 1/3 and 2/3 across the channel (2 sample locations)
Site 6: 1/3, 1/2, 2/3 across the channel (3 sample locations)
The number of sample locations across the channel was dependent on the total width of the channel
at the particular transect. The motor on the Boston Whaler was turned off and the sample team
remained anchored for five minutes prior to the collection of samples. This procedure was
designed to eliminate possible sample contamination from motor oils.
Samples for metals and conventional parameters were collected in pre-cleaned I=Chem
plastic or amber glass bottles (having teflon cap liners), depending on the analyte, as follows:
chlorides - 0.5 L plastic
sulfides - 1 L amber glass
TOC - 1 L amber glass
DOC - 1 L amber glass
TSS - 1 L plastic
metals - 1 L plastic
alkalinity -0.5 L plastic
The pump sampler was operated for five minutes at each site prior to sample collection and the
pumped water was returned to the river. Each sample bottle was rinsed once with river water at
the collection site prior to filling the bottle. In addition, the following procedures were used for
collection of metals and conventional parameter samples. Samples for sulfides and alkalinity were
collected at each sample vertical (e.g. three separate samples were collected at site 6). A single
sample bottle was used at each site for the remaining parameters. However, hi the case of two
sample verticals at one site, the bottles were filled half way at one vertical and then completely
filled at the second vertical. In the case of three sample verticals the bottles were filled 1/3 at
each vertical. The intake pump tube was placed at the bottom of the bottle when collecting
samples for alkalinity and the bottles were filled so that there was no head space. For the
remaining samples, the intake pump tube was placed along the side of the bottle and the bottle was
tilted slightly. This procedure limited the amount of turbulence within the bottle. The only
chemical preservation procedure required in the field was the addition of 2 ml of zinc acetate to
the sulfides bottle prior to the collection of the sample. All metals and conventional parameter
samples were placed on ice for transportation to the laboratory.
A total of 60 L* of river water was pumped at each site for organics analyses. The water
was placed into three 20 L pre-cleaned clear glass bottles. The sample bottles were cleaned using
successive rinses of hydrochloric acid, detergent and water (scrub), distilled water, acetone and
hexane. The bottles were allowed to air dry and were capped with aluminum foil that had been
rinsed with acetone and hexane. For the sites having two sample verticals, 11/2 sample bottles
16
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were filled at the first vertical and 1 1/2 sample bottles were filled at the second vertical. For the
site having three sample verticals a single sample bottle was filled at each vertical.
*-It originally was planned to collect 100L of water from each of the sampling sites of the
Buffalo River. When the actual sampling started (on the October 17, 1990) with 100L water, it
was not possible to maintain the holding times of the sample, due to longer filtration time and
passing the sample through XAD-2 resin columns. According to the SOP (standard operating
procedure section 8.8.4 the holding time should be kept to the bare minimum, less than an hour if
possible). Based on the observed operations both in the field and the laboratory (it was taking
approximately 45 min. at each sampling location, transportation time from field to the laboratory,
sample filtration time 1.75 to 2.0 hours (1 L/min.) and IL/min. through the XAD-2 column will
take an additional 1.75 to 2.0 hours) consideration was given to reduce the volume of the collected
sample to 60 L. Marc Tuchman, Bill Sabato (U.S. EPA) and R.H. Plumb (Lockheed Engineering
Sciences Co.,) made afield and laboratory inspection during the week of October 15, 1990. It
was confirmed by M. Tuchman and B. Sabato that the EPA requested the number of sample
transects to be reduced from 7 to 6 n addition to the reduced sample volume.
All samples (organics, metals, conventionals) promptly were transferred to the laboratory at
SUNY College at Buffalo after collection at each site in order to limit holding tune in the field.
Duplicate samples for all parameters (except those collected by the Sealogger) were taken at one
randomly selected site on each sample day.
3.2 COMBINED SEWER SAMPLING
3.2.1. Sample Locations and Times
It had been proposed that samples of one overflow event would be collected at 10 different
combined sewer outfall sites (Figure 4). Due to laboratory time constraints samples could not be
collected and analyzed during the fall, 1990 period. It was decided that "wet weather" samples
would be collected at a subset of the 10 sites after the fall sample period hi order to check the
analytical procedures for sewer samples. To limit costs, these samples were not analyzed for
conventional parameters or metals. "Wet weather samples" are defined as samples collected from
the combined sewer system during a period of stormwater runoff. The magnitude of runoff may
not be great enough to generate an over flow, but the samples would represent a mixing of sanitary
and storm flow.
A first set of wet weather samples were collected at four sites (Babcock, Hamburg, St.
Stephans and Cazenovia) on December 5, 1990 (Figure 4). The times of sample collection on
December 5, 1990 were as follows:
17
-------
Babcock St. (Site 5) - 10:30
Cazenovia Park (Site 8) - 11:30
St. Stephans PI. (Site 4) - 13:00
Hamburg St. (Site 3) 13:30
Subsequently, it was arranged with the EPA that the pentaplate system used for sample filtration
could remain at SUNY College at Buffalo with the hope that a full overflow sampling could be
done during the summer of 1991. Unfortunately, the summer of 1991 was dry and only three
overflow periods were observed (Irvine et al. 1993). These overflows occurred on the holiday of
July 4 and at 6:30 a.m. on July 7 and 1:30 a.m. on July 8. Samples therefore were not collected
during these overflows except at the automated sampling station located at the Babcock overflow
(see next section). A second set of wet weather samples finally was collected at the St. Stephans
PI. and Hamburg St. sites on August 9, 1991. The St. Stephans PI. sample was collected at 8:15
a.m. and the Hamburg St. sample was collected at 9:10 a.m.
3.2.2. Sample Methodology
All sewer samples analyzed in this study represent single grab samples collected using an
American Sigma Streamline Model 700 pump sampler. Teflon-lined tubing was used for the intake
leading to the pump and silicon tubing was used within the pump housing. Clean teflon-lined and
silicon tubing were installed prior to the sample collection at each site. The tubing was cleaned in
the laboratory following the procedures discussed in Section 3.1.2 and the ends of the tubes were
capped with aluminum foil. The aluminum foil was pre-cleaned with acetone and hexane rinses, as
discussed in Section 3.1.2.
A total of 20 L of sample for organic compound analysis was collected at each site in
precleaned clear glass bottles. The bottles were the same as those used for the river sampling and
were cieaned using the same procedures, as discussed in Section 3.1.2. The general sample
methodology and the volume of sample collected for metals and conventionals analysis followed
that described in Section 3.1.2 for the river sampling.
In addition to the grab sampling done within the study framework, an automated combined
sewer sampling station was installed at site 5 (Babcock St.) for the periods June 25, 1990 to
December 4, 1990 and April 12, 1991 to November 4, 1991. The automated system consisted of
a Montedoro-Whitney System Q flow device connected to an American Sigma Stremline Model
700 pump sampler. The System Q had a datalogger connected to a probe that measured average
(directional) flow velocity and flow depth. The flow probe was fixed to the top of the side weir
within the overflow chamber (e.g. Irvine and Torok, 1991). The system was programmed to
record velocity and depth at five minute intervals and these data were used to calculate overflow
rates. The data were uploaded to a laptop computer at approximately weekly intervals and
hardcopies and disk backups of the data are maintained at SUNY College at Buffalo. The System
Q also was programmed to communicate with the Sigma 700 ump sampler to provide 250 ml
18
-------
samples at 250 m3 overflow intervals. This combination of sample volume per volume of overflow
was determined, through field experience, to provide both enough sample for analysis and full
coverage of an event (i.e. when the sample bottle within the Sigma 700 is full, sampling
automatically ceases). The intake for the pump sampler was fixed at a level several centimeters in
front of, and below, the crest of the weir. Water quality parameters determined from this flow-
proportioned sewer sampling represent an event mean concentration.
Prior to installing the flow meter and pump sampler in the Babcock overflow chamber, the
sampling system was calibrated in a 6.1m long recirculating flume at SUNY College at Buffalo.
The flume is not capable of producing high velocity flows, but calibration runs were done at
velocities of 10, 20 and 30 cm s'1. The average flow velocities recorded by the System Q were
compared to velocities measured using a Marsh=McBirney Model 201D flow meter. The Marsh-
McBirney flow meter measures flow velocity at a particular point in the vertical profile rather than
average flow velocity. The probe of the Marsh=McBirney meter therefore was installed in the
center of the flume at 0.4 of the total depth up from the bed, to approximate average flow
velocity. The Montedoro-Whitney velocities, on average, were 3% less than the
Marsh=McBirney velocities. The small difference could, hi part, be due to the slightly non-
logarithmic profile observed in the flume. As a result of the non-logarithmic profile, velocities at
the 0.4 depth would be slightly different than the average flow velocity. The flow depths
measured by the System Q, on average, were within 2 cm of the observed average flow depth of
24 cm.
The Babcock St. sewershed was selected for more detailed evaluation using automated
sampling equipment because of several factors. First, the sewershed is large (contributing area of
approximately 256 ha) and the outfall represents one of the major overflow points from the entire
city (Calocerinos and Spina, 1989). The sewershed is industrialized and represents a high potential
source of various types of pollutants. The sewer system for the sewershed was easily defined
(Figure 6) and the overflow was easily instrumented hi a secure location. Finally, rainfall data
for this area were available from the Buffalo Sewer Authority (BSA).
Land use within the Babcock St. sewershed primarily is industrial (20% heavy and 67%
light industry) with smaller percentages of residential (11%) and commercial (2%) zones. There
are a variety of industries located hi the sewershed, including those related to food processing,
automobiles and automobile recycling, metal workings, china and chemical production. The
industrial properties often include large, open pervious area. The Erie-Lackawanna rail lines
occupy the central portion of the sewershed. The BSA estimates that the average industria waste
flow hit he Babcock St. sewershed is 2,419,152 liters per day (0.028 mV1). Residential structures
are a mix of primarily double and multi-family dwellings of a relatively high density. High=rise
apartment structures are not present. The BSA estimates that the average residential waste flow hi
the Babcock St. sewershed is 1,355,682 liters per day (0.016 mY1).
As shown hi the schematic (Figure 6) a 1.8m diameter brick conduit carries flow from the
sewershed into the primary overflow chamber. The overflow weir is 4.9m long and 1.7m in
height. Interevent sanitary flow enters the chamber and is deflected to the right by the weir
19
-------
0 268 536 804 meters
Inlet
Overflow
O Outfall
Sewer Pipe
6 Sutacatchment
Figure 6 Schematic of the Babcock St. sewershed (from Irvine et al., 1993).
20
-------
72" DIAMETER BRICK PIPE
TO
24" DIAMETER
TREATMENT
PLANT
PLAN VIEW
SIDE WEIR
FLOW PROBE
NORMAL FLOW
— OVERFLOW
72" DIAMETER
BUFFALO RIVER
Figure 7 Schematic of the Babcock St. overflow chamber.
21
-------
(Figure 7). The flow leaves the chamber by a 0.61m diameter pipe. Excess combined flow
during storms is routed over the weir and through a 1.8m diameter pipe to the Buffalo River.
3.3 FISH SAMPLES
3.3.1. Collection Time, Location and Methodology
Carp were the fish species of interest for this study. The carp were collected using the
SUNY College at Buffalo electroshocking boat in which an onboard generator connected to an
electrode boom in the water produces an electrical shock that temporarily stuns the fish. All
stunned fish surface and the carp were brought onboard with nets. The carp were placed directly
from the nets into ice-filled coolers. The coolers available to the field personnel were plastic and
therefore were lined with IN HCl-washed aluminum foil. The ice bed within the coolers also was
covered with IN HCl-washed aluminum foil. Carp that came into contact with the field personnel
and other objects were released back to the river in an effort to limit contamination problems. A
total of 48 carp were collected from the river in an area between Corps of Engineers transects 626
and 686 (just downstream of site #3, Figure 5) on July 24, 1991.
3.3.2. Preliminary Processing of Fish Samples
All carp samples were taken from the field to the SUNY College at Buffalo Field Station
and preliminary sample processing was done on the day of sample collection (July 24, 1991). The
carp were sorted into three broad age classes, young, middle-aged and old, according to length and
girth. It was not possible to determine the exact age of individual fish in the preliminary sample
processing, but five scales from each fish were taken to determine age by scale counting at a later
date. There were 15 fish in each age class and these were divided into three subsamples of five
fish each, according to the approved QAPP (Figure 8). The fish at all times were carried on a bed
of IN HCl-rinsed aluminum foil, and personnel handled the fish with gloves.
22
-------
Electro-shock Fish
Divide Fish into
3 Age Classes
15 Fish in Each
Age Class
Keep Stomach Content
& Whole Fish Composites
Separate and Tagged
Composite (grind)
5 Whole Fish Giving
3 Subsamples in Each
Age Class
Take 15 g from Each
of the 9 Whole Fish
Composites and Combine
(i.e. 1,135 g Sample)*
15 Fish in Each
Class Divided into
3 Groups of 5
Each Group of 5
Get Stomach Content
and also Keep Rest
of the Fish (Whole Fish)
Composite (grind)
5 Stomach Content
giving 3 Subsamples
in Each Age Class
Send the 90 g Whole
Fish Sample to Fish
& Wildlife
Send 9, 75 g Whole Fish
Composites & 1 Stomach
Composite to Battelle
Total wet weight actually was 130 g
**
All stomach contents composited in
1 jar because of the small mass (see text)
Figure 8 Flow chart of preliminary sample processing, Buffalo River carp
23
-------
The following procedure was used int he preliminary processing of each fish:
1. The fish was assigned an I.D. label with the following (general) nomenclature:
BRF Y W - 1 5
where: BRF = Buffalo River Fish
Y = age class of the fish and: Y is young; M is
middle-aged; O is old
W = sample type; W for whole fish; S for stomach
contents
15= the subsample number (1 to 3) and the fish
number within the subsample (1 to 5)
The fish number within the subsample subsequently is dropped when the five fish are
homogenized.
2. The wet weight, standard length (fish snout to caudal peduncle) and total length (fish snout
to tip of caudal fin) were recorded.
3. An incision was made along the mid-ventral part of the fish using a stainless steel fillet
knife.
4. The stomach contents of the fish were removed by cutting the anterior end of the stomach
with stainless steel scissors, pinching off the posterior end and squeezing the contents into an
amber glass sample jar. The sample jars had previously been cleaned using hexane and acetone
(pesticide grade) rinses and the empty weight of the bottle was recorded. The stomach contents
from the five fish in each subsample were placed in the same bottle for a total of nine (three
subsamples x three age classes) stomach content jars.
The I.D. nomenclature corresponds to that of the whole fish with the exception that the fish
number within the subsample (1 to 5) was not used because the stomach contents of the five fish
were placed in one bottle. Therefore:
BRF O S- 1
would represent the stomach contents for subsample 1 of the old age class.
5. The sex of the fish was determined, if possible, through an examination of the internal
sexual organs (ovaries and testes).
6. The stomach lining was placed back into the fish and the fish (hereafter referred to as the
"whole fish") was double-wrapped in IN HCl-washed aluminum foil.
24
-------
7. The "whole fish" I.D. label was taped to the outside of the wrapped fish and the fish was
placed in a freezer.
8. The stomach contents jar containing the contents of the five fish hi each subsample was
weighed and the weight was recorded. The jar subsequently was placed hi the freezer.
9. The stainless steel fillet knife and scissors were cleaned with distilled water and rinsed with
acetone and hexane (pesticide grade) after each subsample to avoid cross-contamination.
3.3.3. Fish Sample Preparation for Organic Analyses
Whole Fish Preparation
It was established by the U.S. EPA that all whole fish samples would be ground at SUNY
College at Buffalo prior to transferal to the analytical laboratories. The grinding of the whole fish
samples took place at the college Field Station according to the following procedure:
1. A subsample of five frozen whole fish was taken from the freezer and placed on aluminum
foil-covered tables. The aluminum foil covering the tables was pre-rinsed with IN HC1. The
aluminum foil wrap hi which the fish had been frozen was removed and the data tags were
collected.
2. The fish were cut into approximately 4 cm diameter sections using a band saw. The band
saw had a hardened steel blade (stainless steel blades could not be obtained) and the cutting board
on the saw was covered with a pre-rinsed (IN HC1) aluminum foil platter.
3. The fish sections were fed into a Hobart stainless steel meat grinder. All grindings were
caught on a pre-rinsed (IN HC1) aluminum foil tray. Subsequent to grinding, the subsample of
five fish was mixed manually.
4. The ground sample was wrapped hi pre-rinsed (IN HC1) aluminum foil and re-frozen until
all samples were processed and ready for transferal to the analytical laboratories.
5. After each subsample of five fish was cut and ground, the band saw and the meat grinder
were thoroughly cleaned by scrubbing and washing with tap water, rinsing with distilled water
(DI), followed by an acetone (pesticide grade) rinse.
6. The ground, manually-mixed (i.e. composite) subsamples of five fish were removed from
the freezers and were allowed to thaw. Approximately 15g of sample was removed from each
whole fish composite and was placed hi the sample bottle provided by Mr. Ted Schwartz of U.S.
Fish and Wildlife (National Fisheries Contaminant Research Center). Samples were taken from
several randomly-selected locations hi the ground fish mass using a pre-cleaned (DI and pesticide
25
-------
grade acetone rinse) stainless steel spatula. The sample bottle was placed hi a cooler with ice and
shipped to Mr. Ted Schwartz. Samples from each of the nine whole fish composites were placed
in individual sample bottles provided by Mr. Eric Crecilius (Battelle) so that the sample bottles
were 3/4 full (approximately 75g of fish). Each sample was taken from several randomly-selected
locations in the ground fish mass using a pre-cleaned stainless steel spatula, as discussed above.
The samples were placed in a cooler with dry ice for shipping.
Stomach Contents Preparation
Although the stomach contents of each subsample of five fish were frozen and stored
separately, total mass was small and after discussions with Mr. Marc Tuchman and Mr. Eric
Crecilius it was decided that all stomach contents would be composited into one sample. The
samples therefore were allowed to thaw and all samples were mixed into one sample bottle. This
single sample bottle was placed in a cooler with dry ice for shipping to Mr. Eric Crecilius at
Batelle.
3.3.4. Determination of Fish Age from Scale Growth
The age of each fish was determined ~^y counting the number of annual growth rings on the
sampled scales after the methodology describ i by Everhart and Youngs (1981). It was necessary
to obtain a sample of five scales for each fisl. because the growth rings on individual scales may be
damaged or otherwise difficult to count. The counting was done by placing the individual scales hi
a microfiche reader for magnification.
3.4. HYDROMETEOROLOGIC SAMPLING
3.4.1 Water Levels and Discharge
The water surface elevation was measured at nine locations within the AOC by personnel
from the U.S. Army Corps of Engineers, SUNY college at Buffalo and the University at Buffalo.
The measurements were taken at various times throughout each sample day and the locations of the
elevation staffs are shown in Figure 9.
26
-------
COUPS of tm)inuft»
ho
j y KSfv
•*' N»t»f »M*«**tun
STAff
v
(?)
Mima
t MMM M MWOIMI Ml MIIIMMt II
Mttl* llrtlMIATf Mwlff
.,
it, 19 nraxtt »IHH o* so rur
»tt COMflltl* «W«IIM (Ml
.
lOUfl* «MWT I 1/4 Hull tft«U
•0 F>IMH|k» II IM I»•*«»')
to MOJICI MFIM or if ffir
co«**t,itco ov«»« inf
/•/?
>
BUFFALO HARBOR
YORK
USAMMY ENOINEEfl DISTRICT BUFFALO
JO SfPICMBtR nil
Figure 9 Buffalo River staff gauge locations.
-------
The U.S. Army Corps of Engineers had lead responsibility to determine discharge within
the AOC. Because of the low flows during the fall, 1990 sampling and equipment problems,
direct discharge measurement was not possible. Personnel from the Corps of Engineers did
monitor discharge at the three U.S. Geological Survey (USGS) recording gauges located on the
tributaries to the Buffalo River (Figure 1) and these data were summarized in a report submitted to
the U.S. EPA in February, 1991.
The U.S. Army Corps of Engineers directly measured discharge near the moth of
Cazenovia Cr. (at Cazenovia Parkway) and the top of the Buffalo River (at Harlem Rd.) during the
spring 1992 sampling effort. Corps of Engineers personnel also monitored discharge at the three
USGS recording gauges during the spring sampling. All discharge and water surface elevation
data were summarized in a report submitted to the U.S. EPA hi June, 1992.
All discharge measurements were made using an AA Price current meter attached to a B-56
or A-55 reel, mounted on a four-wheeled Type A crane. Each bridge was divided into
approximately 20 measurement stations at which the stream velocity, depth and angel of flow were
determined. For each station with a depth of at least 3 feet (0.91m), the mean velocity was
determined by averaging the velocity at 0.2 and 0.8 of the depth below the surface. For stations
that displaced depths of less than 3 feet (0.91m), the mean velocity was determined as the velocity
at 0.6 of the depth below the surface.
3.4.2. Rainfall Data
Precipitation data referenced in this report were obtained for two stations. First, the
Buffalo Sewer Authority (BSA) maintains a tipping bucket gauge at the South Buffalo Pump
Station on the north shore of the Buffalo River near the confluence of Cazenovia Creek. The
sensitivity of the gauge is 0.25 mm of rain and the data were determined for 5 minute time
intervals. Rainfall intensity has been measured at this location since 1985, although the gauge
normally is operated only during the months April through November. Second, a weather station
is maintained at the Buffalo Airport by the National Oceanic and Atmospheric Administration
(NOAA). Precipitation data are reported at three hour intervals and as daily totals.
28
-------
4. SAMPLE PROCESSING
4.1. Sample Identification Nomenclature
All samples were assigned an identification label immediately after arrival in the
laboratory from the field. The general nomenclature used in sample identification labeling was as
follows:
BR10101W1, W2,DP
Where: BR : Buffalo River
1-6
01
01-06
Wl
W2
P
For CSO samples:
CSO
HA
SM
CA
BA
D
P
Survey number
Composite
Site number
Water- regular
Water -duplicate
Particulate
Combined sewer overflow
Hamburg Street
St. Stephans PL (Smith Street)
Cazenovia Park
Babcock
Dissolved phase
Particulate phase
The above nomenclature was used for all the samples collected during Fall 1990 and
Spring 1992.
4.2. Blank Water Preparation
Blank water was prepared from commercial spring water (Harbor spring/ Mountain valley,
Michigan) which has been tested and found to be low in levels (trace) of chlorinated
hydrocarbons (CHs). The spring water was passed through a clean XAD-2 resin column (see
Figure 10 for blank water preparation assembly). The blank water was used to produce GF/F and
XAD-2 resin column blanks during the operation. This blank water was also used to rinse at the
end the precaliberated 20-L bottles and any part of the apparatus during cleaning.
29
-------
3XAD24
c Integra. I D.
Figure 10 Preparation of blank water.
Key for Figure 10:
1.
2.
3.
4.
a.
b.-e.
Spring water
Blank water receiving bottle
Stainless steel swage-lock fitted XAD-2 column cap
3/8 in. OD HDLPE nippled fitted XAD-2 column cap
See section 8.9.1.6 of pentaplate system SOP
See section 8.9.1.7 of pentaplate system SOP
30
-------
4.3. Pentaplate System Filtration
Two pentaplate filtration units (system "A" & "B") borrowed from the Great Lakes
National Program Office of U.S. EPA were used for filtration of water samples. The Samples
were filtered in order to determine the levels of organic compounds associated with the
particulate phase (i.e. compounds attached to particles retained on the filters) and those in the
dissolved phase (i.e. compounds passing through the filter in the water). Please refer to the QAPP
(quality assurance project plan) for the details and standard operating procedures for filtration.
Figure 11 shows a schematic diagram of the final assembly of the pentaplate system and the
sample run through various steps.
Whatman Glass Fibre Filters (GF/F) of size 293 mm (part # 1825293 Whatman
International Ltd. Maidstone, England) were used on the pentaplates to filter the samples. These
filters were enveloped in IN HC1 washed aluminum foil and ashed in a muffle furnace at 450 °C
prior to use.
The procedure for operating the pentaplate system is described in the following
paragraphs. The system was assembled as described in the SOP for running the samples. Upon
receipt of the samples from the field, the temperature of the water was noted, and water was
drawn through a peristaltic pump at a rate of 4.0 L/minute or less depending on the amount of
suspended matter in the sample (always above 2.0 L/min. during start up) from a sample
reservoir (bottle). The sample was allowed to run through a flow integrator in order to suppress
the pulsating action of the pump. The water was then allowed to flow through pressure
monitoring manifold and then through pentaplate apparatus equipped with parallel 293 mm
filtering system. The number of filter chambers used in each case in the pentaplate apparatus
depended upon the turbidity of the water samples. Periodically the air valve was opened to
release trapped air in the system. Whenever pressure built up, the flow rate on the pump was
lowered to release the back pressure shown on the pressure gauge. Filters hi the pentaplate
system were considered full when the pressure reached 5.0 psi at a flow rate of less than 1.0
L/min. The filtered sample was then collected in a calibrated bottle. Since our sample bottle
volume was 19 L, and as the filtered water level reached the 19 L mark, a new bottle was
interchanged. The filtered sample was immediately transferred to the XAD-2 resin column
system for passing through the resins. Holding time was kept less than an hour.
The pentaplate system was vacuumed using a Schuco vacuum collection pump, by
releasing the air bleeder and tilting the pentaplates toward exit-port. All water that had passed
into the GF/F chamber was collected in a measuring cylinder, before unloading the filters. The
particulate volume was noted. The filters containing suspended sediments were folded using
tweezers into a pie shape, keeping the particulate matter enveloped hi the folding. All the filters
of the sample were kept in the original aluminum foil, labeled and stored in a freezer at -80 °C.
Suspended particulate matter retained on the GF/F was treated as suspended sediment sample and
processed separately for organic analysis. The list of suspended sediment samples collected is
given in Table 5. The filtrate (filtered water) was considered as dissolved phase and this filtered
31
-------
h.
Pump
Head
Row
Integra. 3.
Pressure Gau
b.
4.
a.
Pre-FJIter 6.
f.
e.
Pump Motor 2.
U
Switch
h.
n
f.
Bleeder Valve
Counter
II.
Roor
Shelf
III.
Submersible Pumping
System; Sec. 8.4 - 8.7
II.
I. Discharge from nylon 11 manifold; min. 20L/min.
II. Nylon 11 hose from submersible sampling pump.
HI. Stainless steel Sumersible pump; sampling pump
IV. Sampling Manifold; 3 liter/min. draw
1. Calibrated Carboy; 19 liters, acetone washed, blank water rinse
2. Peristaltic pump, pump head, on/off switch
3. Flow Integrator; with 3/8" HDLPE nipples
4. Pressure Gauge Manifold; 15 psi.; section 8.8.1.4 of pentaplate SOP
5. Penta-plate System
6. Pre-filter; in-line, 1mm pore size teflon filter
Figure 11 Final assembly of Pentaplate System
32
-------
Table 5 List of articulate Phase Including CSO Samples
Collected During Fall, 1990
Survey
1
Survey
2
Survey
3
Survey
4
Sample ID List
Sediment
Site # Date Sample ID Pentapiate
1
2
1
2
3
3D
4
5
6
1
2
3
3D
4
5
6
1
2
3
4
4D
5
6
1
1D
2
3
4
5
6
10/17/90
10/17/90
10/18/90
10/18/90
10/19/90
10/19/90
10/22/90
10/22/90
10/22/90
10/22, '90
10/22/90
10/22/90
10/22/90
10/23/90
10/23/90
10/27/90
10/27/90
10/27/90
10/27/90
10/27/90
10/27/90
10/27/90
10/29/90
10/29/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
11/5/90
BLANK 1 01 7A
BLANK1017B
BR10101W1P
BR10102W1P
BLANK1019A
BLANK1019B
BR10101W1P
BR10102W1P
BR10103W1P
BR10103W2P
BR10104W1P
BR10105W1P
BR10106W1P
BLANK1023A
BLANK1023B
BR20101W1P
BR20102W1P
BR20103W1P
BR10203W2P
BR20104W1P
BR20105W1P
BR20106W1P
BLANK1029A
BLANK! 029B
TRIP-BLANK
BR30101W1P
BR30102W1P
BR30103W1P
BR30104W1P
BR30104W2P
BR30105W1P
BR30106W1P
BLANK1031A
BLANK1031B
BR40101W1P
11/5/90 IBR40101W2P
11/5/90
BR40102W1P
11/5/90 IBR40103W1P
11/5/90
BR40104W1P
11/5/90 BR40105W1P
11/5/90 IBR40106W1P
System A
System B
System A
System B
System A
System B
System A
System B
System A
System B
System A
System B
System A ,
System A
System B
System A
System B
System A
System A
System A
System B
System A
System A
System B
System A
System B
System A
System B
System B
System A
System B
System A
System B
System A
Remarks
Test
Test
'::". - .'.'. •'•"'.
Trip Blank
System B|
System A
System B
System B
System B
System A|
33
-------
Table 5 (Continued)
Survey
5
Survey
6
CSO
Samples
Sample 10 List Sediment
She #
6
5
4
3
2
2D
1
1
2
3
4
5
5D
6
Date
11/6/90
11/6/90
11/9/90
11/9/90
11/9, '90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
Sample ID IPentaplate
BLANK1106A
BLANK1106B
BR50106W1P
BR50105W1P
Trip Blank
BR50104W2P
BR50103W1P
BR50102W1P
BR50102W2P
BR50101W1P
BLANK1109A
BLANK1109B
BR60101W1P
BR60102W1P
BR60103W1P
BR60104W1P
BR60105W1P
BR60105W2P
BR60106W1P
I
11/13/90
11/14/90
11/14/90
12/5/90
12/5/90
12/5/90
12/5/90
12/5/90
12/5/90
12/6/90
12/6/90
7/30/91
8/9/91
8/9/91
TRIP-BLANK
BLANK1114A
BLANK1114B
BLANK1205A
BLANK1205B
CSO-1W1P{Ba)
CSO-2W1P(Ca)
CSO-3W1 P{Sm)
CSO-4W1P{Ha)
BLANK1206A
BLANK1206B
BLANK910730A
CSO-SM0809
CSO-HM-0809
8/16/91 BLANKS 1 08 16A
System A
System B
System B
System A
System A
System B
System A
System A
System B
System A
System B
System A
System B
System A
System B
System A
System A
System B
System A
System B
- System. A
System B
System .A
System A
System A
System .A
System A
SystemTJ
System A
System A
System A
System A
Remarks
34
-------
water was then passed through XAD-2 resin column. Pentaplate system units, GF/Fs and XAD-2
resin columns were handled and used according to the procedures described in the SOP.
4.4. XAD-2 Resin Columns
XAD-2 resin (mesh size 20 -60) columns obtained from the University of Wisconsin,
Superior, Wisconsin were used for Buffalo River fall 1990 water samples. The XAD-2 resin
(part #: 20279 purified: mesh size 16-50;) used for the spring, 1992 samples was purchased from
SUPELCO Inc. and the columns were prepared at the Great Lakes Laboratory, SUNY College at
Buffalo. The resin columns were stored hi a refrigerator (4°C) prior to use. Care was taken to
avoid air being pumped into or trapped inside the resin column.
4.5. Water Sample Pre-concentration
Although the set up for XAD-2 preconcentration system is similar to that used during the
blank water preparation, there is one main difference. Filtered sample water in the calibrated
glass bottles (therefore volume of the water sample is known) was drawn directly into the XAD-2
resin before entering the peristaltic pump head. Flow rate is then determined through the
discharge system, which contains a flow meter preceded by a flow integrator. The flow rate was
always maintained at 800 mL to 1000 mL/minute during the sample run. Temperature of the
water coming out of the XAD-2 resin column system was noted. All tubings were changed
before each sample run. The water which was passed through the resin column was then
discharged into the sink. The resin column was filled with blank water and closed with
appropriate caps. All pertinent information such as sample I.D., date, volume of the water run in
the column and the initial of the person who carried out these steps were labeled on the column.
The resin column was then stored in a refrigerator at 4 +1-2 °C until further analysis. The list of
water samples collected is given in Table 6.
4.6. Quality Control
Water blanks were run to check the performance of each system (system "A" and "B")
and the quality of both the systems. Each water blank created a filter blank and an XAD-2 resin
column blank. These blanks were run on each system at the beginning and end of every
completed cycle. The volume of blank water was 60 L per blank, except on the October 18,
1990 sampling which used about 100 L.
Trip blanks: Trip blanks otherwise are known as placement blanks. GF/F and XAD-2 resin
columns were installed hi the filtration and preconcentration system and then removed without
water having been run through them. These blanks served to check on filter preparation, XAD-2
resin column preparation, the handling/cleanup of the field systems and general procedures in the
analytical laboratory.
Duplicate samples: Water from a single station was processed hi parallel through the two field
systems. The number of pentaplates and filters and the volume of sample water were kept the
same for each system. These samples were run to check on the variability of pollutant levels in
the field, the reproducibility of the filtration and preconcentration process and that of the
analytical laboratory. One set of duplicates was run for each survey.
35
-------
Table 6 List of j__ssolved Phase Including CSO Samples
(Water), Sample List Fall, 1990
Survey
1
Survey
2
Survey
3
Survey
4
Sample ID list Water
Site #
1
2
1
2
3
3D
4
5
6
1
2
3
3D
4
5
6
*
1
2
3
4
4D
5
6
1
1D
2
3
4
Date Sample ID
10/17/90
10/17/90
10/18/90
10/18/90
10/19/90
10/19/90
10/22/90
10/22/90
10/22/90
10/22/90
10/22/90
10/22/90
10/22/90
10/23/90
10/23/90
10/27/90
10/27/90
10/27/90
10/27/90
10/27/90
10/27/90
10/27/90
BLANK 1 01 7A
BLANK1017B**
BR10101W1D
BR10102W1D
BLANK1019A
BLANK1019B
BR10101W1D
BR10102W1D
BR10103W1D
BR10103W2D
BR10104W1D
BR10105W1D
BR10106W1D
BLANK1023A
BLANK1023B
BR20101W1D
BR20102W1D
BR20103W1D
BR20103W2D
BR20104W1D
BR20105W1D
BR201 06W1 D
10/29/90) BLANK1029A
10/29/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
11/5/90
11/5/90
11/5/90
11/5/90
BLANK1029B
TRIP-BLANK
BR30101W1D
BR30102W1D
BR30103W1D
BR30104W1D
BR30104W2D
BR30105W1D
BR30106W1D
BLANK1031A
BLANK1031B
BR40101W1D
BR40101W2D
BR40102W1D
BR40103W1D
11/5/90 | BR40104W1D
5 11/5,'90
6
11/5/90
BR40105W1D
BR40106W1D
Pentaplate | Remarks
System A
System B
System A
System B
System A
System B
System A
System B
System A
System B
System A
System B
System A
System A
System B
System A
System B
System A
System A
System A
System B
System A
System A
System B
System A
System B
System A
System B
System B
System A
System B
System A
System B
System A
System B
System A
System B
System B
System B
System A
Test
Test
36
-------
Table 6 (Continued)
Survey
5
Survey
6
CSO
Samples
Sample ID List Water
She # | Date Sample ID |Pentaplate
6
5
4
3
2
2D
1
1
2
3
4
5
5D
6
11/6/90
H/6,'90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
11/14/90
11/14/90
12/5/90
12/5/90
12/5/90
12/5.'90
12/5.'90
12/5/90
12/6/90
12/6/90
7/30/91
8/9/91
8/9/91
8/16/91
BLANK1106A
BLANK1106B
BR50106W1D
BR50105W1D
TRIP BLANK
BR50104W1D
BR50103W1D
BR50102W1D
BR50102W2D
BR50101W1D
BLANK1109A
BLANK1109B
BR60101W1D
BR60102W1D
BR60103W1D
BR60104W1D
BR60105W1D
BR60105W2D
BR60106W1D
TRIP-BLANK
BLANK1114A***
BLANK1114B
BLANK1205A
BLANK1205B
CSO-1W1D(Ba)
CSO-2W1 D(Ca)
CSO-3W1 D(Sm)
CSO-4W1 D(Ha)
BLANK1206A
BLANK1206B
BLANK910730A
CSO-SM0809
CSO-HM-0809
BLANK910816A
System A
System B
System B
System A
System A
System B
System A
System A
System B
System A
System B
System A
System B
System A
System B
System A
System A
System B
System A
System A
System A
System A
System A
System A
System A
System A
System A
System A
System A
System A
System A
System A
Remarks
37
-------
5. MATERIALS USED FOR CHEMICAL ANALYSIS
Trace analysis of organics required highest purity grade chemicals, solvent and gases. The
list of the materials and the sources are given in the following subsections.
5.1 HIGH PURITY STANDARDS
Benzo[a]pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene,
benzo[ghi]perylene and d10-anthracene of high purity as standard solutions were purchased from
Supelco, Inc. (Bellefonte, PA).
2,2',3,4,4',5,6,6'-Octachlorobiphenyl, 2,2\3,3',4,4',5,5',6,6'-decachlorobiphenyI, aroclor-
1242, aroclor-1248, aroclor-1254 and aroclor 1260 were obtained from Supelco, Inc. (Bellefonte,
PA) or EM Science (Gibbstown, NJ).
High purity pesticide standards i.e. gamma-chlordane, alfa-chlordane, dieldrin, and 4,4'-
DDT were purchased from Supelco, Inc. (Bellefonte, PA) or EM Science (Gibbstown, NJ).
5.2 HIGH PURITY SOLVENTS
Burdick and Jackson brand high purity acetone, hexane, acetonitrile (HPLC grade) and
methylene chloride were purchased from Baxter (Edison, NJ). Nanopure water for HPLC was
obtained by filtration through Branstead Nanopure II Four Module System.
5.3 HIGH PURITY GASES
High purity nitrogen and helium gases were purchased from Strate Welding, Inc. (Buffalo,
NY).
5.4 GLASSWARE AND CHEMICALS
Soxhlets, chromatography columns, and other specialty glassware were obtained from
VWR Scientific (Rochester, NY) or Ace Glass Company (Vineland, NJ). Anhydrous sodium
sulfate, silicagel, fluorisil, etc. were obtained from Supelco, Inc. (Bellefonte, PA). Custom-made
XAD-2 resin columns were purchased from the University of Wisconsin (Superior, WI).
5.5 GC AND HPLC SUPPLIES
GC columns DB-5, DB-1701 and DB-1 were purchased from J&W Scientific (Folson,
CA). HPLC column, Supelcosil LC-PAH, for PAH analysis was obtained from Supelco, Inc.
(Bellefonte, PA). Specialty GC and HPLC parts such as glass inserts, autosampler vials, septa,
needles, syringes, etc. were purchased from Hewlett-Packard Co. (Rochester, NY) or Varian
Associates (Sunnyvale, CA).
38
-------
6. ANALYTICAL PROCEDURES
6.1. EXTRACTION
6.1.1. Suspended Sediments
The GF/Fs containing suspended paniculate matter were transferred from the freezer (-80
°C) to a refrigerator (4 +1-2 °C) and kept overnight, then thawed at room temperature for at least
2 hrs. The folded GF/Fs were opened and spiked with the surrogate standards: 2,4,5,6-
Tetrachloro-m-xylene (TCMX) and 2,2',3,3',4,4',5,5',6,6'-decachlorobiphenyl(400 ng each) for
PCBs and anthracene d10 and/or benzo(ghi)perylene for PAHs. The GF/Fs were transferred to a
glass thimble (size 190 mm, 50 mm I.D.). Subsequently, the thimble with the sample was placed
in a Soxhlet extractor (custom made: total length 505 mm; bowl length 380 mm; bowl diameter 68
mm I.D. ; top bend of siphon tube to bowl bottom 215 mm; I.D. of siphon tube at least 6 mm;
Top ground glass joint 71/60 for 95 mm; bottom ground glass joint 34/45; (ACE glass part # for
Soxhlet extractor is: 6810-803; for boiling flask (1 L) is: 887-53; for condenser: 6810-04). The
sample was extracted with 900 ml of methylene chloride (Krahn et al. 1988) for 16 hrs. The
extract was concentrated on a steam-bath to a smaller volume. Nitrogen gas was used to further
reduce the volume of the concentrated extract to 4 mL. The outline of the procedures used for
the analysis of organics in water and suspended sediments is given in the form of a flow chart
(Figure 12).
The concentrated extract (4 ml), was divided into two aliquots. Aliquot 1 (2 ml) was used
for PAHs analysis, and aliquot 2 (2 ml) was used for the analysis of PCBs and chlorinated
hydrocarbon Pesticides.
GC analysis of the suspended sediments revealed that the PCB levels were very low
(detection limit to < 10 ppt). This prompted us to check the efficiency of the extraction
procedure. The suspended sediments samples were reextracted using solvent system of different
polarity. A mixture of acetone and hexane (1:1) was preferred for this extraction. Due to problems
in the Soxhlet extraction (improper cycling) the ratio of the solvent system was modified to
acetone:hexane 1.5:1 (570 mL of acetone and 380 mL of hexane). The solvent mixture was
refluxed through the GF/F for 16 hrs. The sample extract was then concentrated on a steam bath in
round bottom flasks and 3-bulb Snyder columns. The volume of the concentrated extract was
more than 100-200 ml due to the presence of water. This extraction method (acetone/hexane)
brought water from the GF/F and caused further problems hi processing. Therefore, the extract
was transferred to 2-L separately funnel with the aid of about 800 mL of organic free water and
150 mL of hexane. The separatory funnel was shaken for 10 min, and the hexane layer transferred
to a clean Erhlenmeyer flask. The aqueous layer was extracted with an additional 100 mL of
hexane by shaking the funnel for 10 min. The water layer was discarded. The combined hexane
extracts (250 mL) were washed 3 times with an equal volume of hexane washed organic free
water. The hexane extract was then dried by passing through anhydrous sodium sulfate, and then
concentrated using a Kuderna-Danish (KD) apparatus to 6 mL. This volume was split into two
39
-------
equal portions for PAH analysis (Section 5.2), and for the analysis of PCBs and chlorinated
hydrocarbon pesticides (Section 5.3).
The data obtained from the first (methylene chloride) and second extraction
(acetone/hexane) was added to determine levels of PAHs, PCBs, and chlorinated hydrocarbon
pesticides quantitations in the samples. Surrogate standard recovery data for the first and second
extractions were also recorded.
6.1.2. Water Samples (XAD-2 Resin)
XAD-2 resin samples with overlying water and glasswool plugs (Section 4.5)were
transferred from the columns to bottles and clean acetone was added until all the resins were
immersed. The bottles were then stored in the refrigerator until analysis. Presence of water in the
samples poses problems in Soxhlet extraction of the samples. Therefore, the resins and water
acetone mixture has to be separated in order to get proper Soxhlet extraction of the resin. To
perform this, the resin with glasswool plugs was transferred to the Soxhlets and rinsed twice with
acetone to remove as much water as possible. This acetone-water "rinsate" (700-800 ml) was
collected in a separate Erlenmeyer flask. The XAD-2 resin was Soxhlet extracted using a 1:1
mixture of acetone and hexane.
The acetone-water rinsate was concentrated on a steam bath. This extract combined with
the concentrated extract obtained from the extraction of XAD-2 resin formed more than 150 ml of
liquid and we tried to concentrate this to a lower volume. At this point we encountered problems
in concentrating the sample to a lower volume and further analysis could not be performed (due to
the very low levels of analyte concentration and the large quantity of extract). This problem was
addressed to the EPA, GLNPO. Further, testing of the extract using GC-MS revealed the
presence of diacetone alcohol (Figure 13), boiling point 166 °C. The formation of diacetone
alcohol occurred most likely during the storage of the XAD-2 resin in acetone under refrigeration
for a period of time (approximately one year).
Since diacetone alcohol is soluble hi water, we separated PCBs and chlorinated hydrocarbon
pesticides from diacetone alcohol by partitioning the chemicals between hexane and water. About
700 mL of organic free nanopure water was taken hi a 2 L separatory funnel and 150 mL of
hexane was added. The sample extract (150-200 mL) was slowly poured on the hexane layer and
the separatory funnel was shaken vigorously for about 10 min. The hexane layer subsequently was
transferred to a Erlenmeyer flask. An additional 100 mL of hexane was added and the funnel was
shaken for 10 min (the water layer was transferred to a bottle) and stored until all the analysis
completed. The original 150 ml. of hexane extract was transferred to the separatory funnel
(containing 10 ml hexane extract) and the combined extract (150 + 100 mL) was washed 3 ties
with an equal volume of organic-free water. The hexane extract was then passed through
anhydrous sodium sulfate hi order to remove any trace of water. This extract was then
concentrated using a Kuderna-Danish (KD) apparatus to 8 mL. The 8 mL volume was split into
two portions for chlorinated aromatic hydrocarbons (CAHs) and polynuclear aromatic
40
-------
hydrocarbons (PAHs) respectively. The CAHs portion of the extract was then subjected to
sUicagel column chromatography for the separation of PCBs from chlorinated hydrocarbon
pesticides as described hi Section 5.3. The PAHs portions of the extracts were analyzed as
described in Section 5.2.
6.2. ANALYSIS OF PAHS
Appropriate aliquots for PAH analysis were further concentrated to dryness by evaporation
under a stream of nitrogen gas, and the residue was redissolved in acetonitrile (0.1-0.5 ml) for
PAH analysis. The analysis was performed at room temperature by HPLC on a reversed-phase
supelcosil LC-PAH column (size: 25 x 0.46 mm; part # 5-8229; vendor: Supelco, Inc.
Beliefonte, PA) using Varian 5000 high pressure liquid chromatograph equipped with varian
uv/vis (model #UV-100) or fluorescence detector (Varian model #9070). Varian autosampler
(model #9090) was used for sample injection. Chromatographic parameters were controlled by
Varian data system 401. Acetonitrile/water gradient was used as a mobile phase. In each case a 65
pi aliquot was injected with the autosampler in order to ensure complete and reproducible filling of
the 50 n\ sample loop. When necessary, the concentration of analytes in acetonitrile was modified
in order to detect and quantitate various PAHs above the instrument detection limit and within the
calibration curve range established for each PAH.
6.2.1. HPLC Parameters Used for PAH Analysis
HPLC parameters used to detect, separate, and quantitate the selected PAH are given in
Table 7. EPA method 610 was initially followed for quantitation of PAHs using a UV detector.
Initial analysis revealed that the levels of these chemicals were extremely low (< 10 ppt);
consequently the quantitation of PAHs present in trace levels was not possible by using UV
detector. Therefore, a fluorescence detector which is considerably more sensitive than UV
detector in detecting PAHs was used for the analysis of PAHs in most of the water and sediment
samples. The use of fluorescence detector allowed us to quantitate < 1 ppt of PAHs in Buffalo
River water and sediments. Fluorescence detector wavelength program was based on the procedure
described by Ogan et al. (1979).
A representative HPLC chromatogram of the PAHs of interest under conditions described
above is presented hi Figure 14.
6.3. ANALYSIS OF PCBs AND CHLORINATED HYDROCARBON PESTICIDES
6.3.1. Sample Cleanup, Separation of PCBs and Chlorinated Hydrocarbon Pesticides
In order to improve the separation and quantitation of PCBs and various chlorinated
hydrocarbon pesticides, initial experiments were performed to separate PCBs from pesticides by
41
-------
column chromatography. Silica gel columns were made by packing silica gel (1.5 g; Wakogel S-l,
Part # 230-00261, Wacogel, Virginia) activated for three hours at 130 °C into a column (10 mm
I.D., 30 mm length) using hexane. Preliminary experiments, using authentic standards, were
conducted to determine the elution pattern of PCBs and chlorinated hydrocarbon pesticides, and the
elution volume of the solvents used for achieving optimal separation of PCBs and pesticides.
Appropriate aliquots for PCB and chlorinated hydrocarbon pesticide analysis were
transferred onto the silica gel column and eluted with 120 ml of hexane at the rate of 1.5 mL/min.
This fraction contained PCBs and 4,4'-DDE. The column was then eluted with 100 ml of 20%
methylene chloride in hexane. The second fraction eluted alpha-chlordane, gamma-chlordane,
dieldrin and 4,4'-DDT. Since the surrogate standards spiked before the soxhlet extractions were
eluted with the PCB fractions, TCMX and decachlorobiphenyl standards were spiked again in the
pesticide fraction after the column chromatography. This was decided in consultation with Richard
Fox of U.S. Environmental Protection Agency.
The PCB and pesticide fractions were K-D concentrated to 2 ml each. The PCB fraction
was further cleaned up by treating it with 5% fuming sulfuric acid in concentrated sulfuric acid.
Finally, traces of acids were removed by washing with hexane washed water. After this treatment,
the sample was injected into the GC. However, due to the low concentrations of PCBs in the
sample, the sample was further microconcentrated to 100 iiL to raise the PCBs concentration to a
detectable level. The sample extract was microconcentrated using nitrogen gas and transferred to
GC- microvials.
6.3.2. Analysis of PCBs and Chlorinated Hydrocarbon Pesticides
A Varian model 3400 gas chromatograph (GC) and Varian model 8100 autosampler were
calibrated for total PCBs analysis. One microliter (jjl) of the sample was injected (splitless) into the
GC equipped with a 63Ni electron capture detector (BCD) using the autosampler. A DB-5 (5%
phenyl- 95% methyl) capillary column with dimensions of 30 m, 0.25 mm I.D. 0.25 micron film
thickness was used. Nitrogen was used as both carrier and makeup gas. The carrier gas flow rate
was at 2 ml/min and makeup gas was at 28 ml/min. Injector and detector temperatures were kept
at 250 and 300 °C, respectively. The GC was interfaced with Zenith Z386/20 data systems and a
Varian workstation (A04688939) equipped with an ADCB (anolog to digital converter board)
module 16. The GC parameters used to quantitate PCBs are given in Table 8.
Initial analysis for total PCBs in the suspended sediments revealed that the PCB levels were
extremely low (parts per trillion) and identification of specific Aroclors was not possible.
Therefore, total PCBs quantitation was done using 1:1:1:1 mixture of Aroclors 1242, 1248, 1254
and 1260. At least five PCB peaks within the Gaussian distribution were chosen and the total PCB
concentration was calculated using the response factor obtained for those peaks in the standard.
This method of calculation was used as a result of discussions with Brian Schumacher and Richard
Fox of U.S. Environmental Protection Agency.
42
-------
The pesticide fraction (2 mL), was split into two aliquots. A 1-mL aliquot was used for
quantitation of dieldrin and the other aliquot was used for other chlorinated hydrocarbon pesticides.
The aliquot for dieldrin quantitation was transferred to a GC-injection vial and 1 microliter
was injected into a Hewlett Packard 5890 Series II gas chromatograph equipped with eNi electron
capture detector using a Hewlett Packard 7673 autoinjector. A DB-1701 (14%
Cyanopropylphenyl-86% methyl) megabore column (30 m, 0.53 mm I.D. 1 micron film thickness)
was used for separation. The GC operating conditions for the detection of the pesticides were as
follows: The column oven temperature was programmed from 120 °C to 240 °C at a rate of 10
°C/ min up to 200 °C and at then at a rate of 2 °C/min to 240 °C and final hold time was 6 min.
Injector temperature was 250 °C and the detector temperature was 350 °C. Helium and nitrogen
were used as a carrier and makeup gases, respectively. The GC was interfaced with Zenith 386/20
data systems with a Varian workstation. An ADCB module 18 was used for quantitation of the
analyte. Quantitation of dieldrin was calculated using the response factor generated from the
calibration curve. (Note: Sulfuric acid cleanup was not performed for this aliquot of the sample
since dieldrin is known to be destroyed by the acid. The dieldrin fraction contained other
contaminants which caused problems in the GC-ECD analysis. Therefore, this portion of the
sample was not microconcentrated to lower volume).
The other aliquot (1 mL) for the analysis of chlorinated hydrocarbon pesticides (gamma-
chlordane, alpha-chlordane, 4,4'-DDT) was subjected to sulfuric acid cleanup. This fraction was
then microconcentrated to 100 uL and injected into the GC-ECD. The GC conditions and
detector and column used were the same as for dieldrin analysis.
The other aliquot (1 mL) for the analysis of chlorinated hydrocarbon pesticides (gamma-
chlordane, alpha-chlordane, 4,4'-DDT) was subjected to sulfuric acid cleanup (Section 5.3.1).
This fraction was then microconcentrated to 100 /*L and injected into the GC-ECD. The CG
conditions and detector and column used were the same as for dieldrin analysis.
Representative standard chromatograms of PCB mixtures and chlorinated hydrocarbon
pesticides under the chromatographic conditions described above are presented in Figure 14.
43
-------
ANALYTICAL PROCEDURE
BUFFALO RIVER WATER
Passed through pentaplates
containing Whatmann 293 mm
glass fiber filters
SUSPENDED SEDIMENTS
Soxhlet extraction
and concentration
CONCENTRATED EXTRACTS
(PAHs/CAHs)
FILTRATE
I
Passed through XAD-2
resin column
I
PAHs/CAHs IN RESIN
Soxhlet extraction
and concentration
4
CONCENTRATED EXTRACT
(PAHs/CAHs)
Figure 12 Flow chart of the analytical procedures for CAHs and PAHs in the
dissolved and paniculate phase
44
-------
CONCENTRATED EXTRACT
(PAHs/CAHs)
Fraction 1
HPLC-UV/
Fluorescence
Fraction 2
(PCB & Pesticides)
Silica gel column chromatography
I
Fraction 1 in hexane
(PCBs and DDE)
5% Fuming
sulfuric acid
clean-up
GC-ECD
Fraction 2 in
20% dichloro-
methane in hexane
(DDTs, Dieldrin &
Chlordane)
GC-ECD
Figure 12 (Continued)
45
-------
TABLET
HPLC Instrument Parameters Used for PAHs Analysis
Instrument:
Elapsed Time:
Composition:
Flow:
Reservoir:
Ext. Events:
Analog out:
Pressure:
PMax:
PMin:
VARIAN LC 5000
Page 1 or Program 3
0.0 min
35% A 65% C
2.0 ml/min Detector Disabled
AC
0
%B
0 Atm.
350
10
*A, Water; C, Acetonitrile
46
-------
Table 7 (Continued)
Paee 2 of Program 3
Time
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.1
28.0
28.0
28.0
32.0
32.0
32.0
Code
Flow
RSVR
% A
%C
EVNT
A/Z
RNG
EVNT
Flow
% A
%C
Flow
% A
% C
Value
2.0
AC
35
65
0
254
0
0.5
2
0
100
2.0
2.0
0
100
47
-------
Table 7 (Continued)
Page 3 of Program 3
35.0 Flow 0.5
35.0 % A 35
35.0 % C 65
38.0 Flow 2.0
48
-------
Table 7 (Continued)
FILE #0, RPS IN VARIAN FU 9070-1014 DETECTOR
*Ex. : 278 (for water samples) Em. : 376 (for water samples)
Lamp: Run CH 1: 20.00
Lamp Rate: 100 CH 2: 0.01
Rise Time: 2.0 PMT: 600
.^: 250 (for sediment samples)
Em.>.: 368 (for sediment samples)
49
-------
Table 7 (Continued)
WAVE LENGTH PROGRAM IN VARIAN FU 9070-1-14 DETECTOR
(for water samples)
Time
0.00
0.50
5.30
6.50
8.50
22.00
35.00
Ex.
278
278
278
278
256
278
278
Em.
376
376
376
376
420
376
376
Status
1 "' ' ~ '
start
zero
zero
zero
zero
zero
stop
50
-------
Table 7 (Continued)
WAVE LENGTH PROGRAM IN VARIAN FU 9070-1-14 DETECTOR
(for sediment samples)
Time
0.00
0.50
6.50
8.50
22.00
35.00
Ex.
250
250
278
256
250
250
Em.
368
368
376
420
368
368
Status
start
zero
zero
zero
zero
stop
51
-------
Table 7 (Continued)
SINGLE CHANNEL METHOD: RPS
SECTION 1: BASIC
PAGE1
ANALYSIS PARAMETERS
CHANNEL: 1
CALCULATION: A%
AREA/HT: A
STOP TIME: 35.00
NUMB EXPECTED PKS: 1024
EQUILBRATION TIME: 0
UNRETAINED PK TIME: 0.00
UNIDENT PK FACTOR: 0.000000
SLICE WIDTH: 10
PAGE 2
SAMPLE PARAMETERS
RUN TYPE: A
SMAPLEID: PAH
DIVISOR: 1.000000
AMTSTD: 1.000000
MLTPLR: 1.000000
PAGES
REPORT INSTRUCTIONS
WHERE TO REPORT: L
COPIES: 1
TITLE: PAG/BRRESIN/AUTO/FU
FORMAT: N
DECIMAL PLACE: 4
RESULT UNITES:
REPORT UNIDENT PKS: Y
REPORT INSTRUMENT CONDITIONS:
PAGE 4
PLOT INSTRUCTIONS
PLOT: Y
ZERO OFFSET: 10
ANNOTATION
RETENTION TIME: Y
PLOT CONTROL: Y
TIME TICKS: Y
TIME EVENTS: Y
PK START/END: Y
PAGES
CHART SPEED
52
-------
Table 7 (Continued)
PAGES OR CM/MIN: C
INIT VALUE: 0.0
LINE# TIME CHART SPEED
1 0.01 1.0
PAGE 6
PLOT ATTEN
INIT PLOT ATTEN: 128
SECTION 2:
PAGE1
LINE#
1
2
3
4
5
6
7
: TIME EVENTS
TIME
0.00
0.00
0.00
0.00
0.00
5.00
28.00
EVENT
PR
SN
T%
WI
II
II
II
VALUE
5000
10
5.0
10
2.50
5.80
35.00
SECTION 9: SAMPLE LIST + A/S CONTROL
PAGE1
AUTOSAMPLER CONTROL
INJECT/CALIBRATION: 1
INJECT/ANALYSIS: 8
SAMP VOLUME: 1
VISTA AUTOSAMPLER ONLY
A/S MODE: MR
PURGE PULSES: 2
INJECT TIME: 0.03
PAGE 2
SAMP = RACK/VIAL
AMT STD MLTPLR
1
TYPESAMPLE ID DIVISOR
PAH
53
-------
Gas Chromatograph:
Varian3400
ECD Detector
DB-5 Capillary Column
(30m. 0.25 mm i.d..
0.25 micron film)
for PCBs analysis and
confirmation of pesticides
Table 8
GC Parameters Used for Total PCBs Analysis
METHOD 1 1-2
TIME 16:34
REV 9303181633
18 MAR 93
INITIAL COLUMN TEMP 120°
INITIAL COL HOLD TIME 1.00
FINAL
PRGM TEMP RATE
1 180 10.0
2 250 3.0
3 270 4.0
INJECTOR TEMP 250-
INJ HOLD TIME 0.00
DETECTOR TEMP 300"
FID A ATTEN RANGE Art.
8 9 NO
EODB ATTEN RANGE A/Z
32 10 YES
PLOT SPEED 0.5 CM/MIN
ZERO OFFSET 15%
PLOT SIGNALS
TIME TICKS YES
INSTR EVENT CODES YES
USER NUMBER 1-2
PRINT USER NUMBER YES
PRINT REPORT YES
PRINT RUN LOG NO
PLOT
PRGM TIME SPEED SIG
1 2.00 1.0 B
AUTOSAMPLER MODE MULTI
SAMPLE VOLUME IN ul 1.0
SOLVENT PLUG SIZE IN ug 1.0
FAST INJECTION RATE YES
INJECTION TIME 0.02
WATT FOR READY YES
NUMBER INJ/CAUB VIAL 2
INJ PER ANALYSIS VIAL 1
INITIAL RELAYS-1
RELAYS
PRGM TIME STATE
1 0.01 1
2 0.75 -I
RUN MODE 1 - ANALYSIS
PEAK MEASUREMENT PARAMETER 1 - AREA
LONG REPORT FORMAT NO
RESULT CALCULATION TYPE 1 - AREA %
DIVISOR 1.0000000
AMOUNT STANDARD 1.0000000
MULTIPLIER 1.0000000
RESULT UNITS
REPORT UNIDENTIFIED PEAKS YES
UNIDENTIFIED PEAK FACTOR 0.0000000
SAMPLE ID EPA-BR
SUBTRACT BLANK BASELINE NO
PEAK REJECT VALUE 10000
SIGN ALTO NOISE RATIO 5
TANGENT PEAK HEIGHT 10
INITIAL PEAK WIDTH 2
HOLD TOTAL
TIME TIME
0.00 7.00
11.00 41.33
13.00 59.33
n
-s
co
rh
B)
ex
Q.
8.138
28.269
35.720
62.784 t/i
54
65.237
70.772
-------
CH3
CH3-COC-CH3
OH
Diacetone Alcohol
b.p.166°C
Figure 13 Structure of diacetone alcohol.
55
-------
VARIAN 3400 GAS CHROMATOGRAPH
METHOD 4 RUN 299
TIME 11:06 14 FEE 91
SAMPLE: EPA-BR-BL
RUN MODE: ANALYSIS
CALCULATION TYPE: PERCENT
PEAK TIME RESULT
NO. MIN
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
0.862
0.905
0.212
0.955
1.066
1.095
1.118
1.165
1.246
1.284
1.311
1.336
1.368
1.424
.444
.541
.568
.736
.842
.975
2.082
2.197
2.319
2.419
2.775
2.913
3.301
8.138
24.641
26.671
27.543
28.014
28.269
29.663
31.696
32.568
33.278
34.450
34.970
35.129
35.720
36.578
37.230
37.667
38.369
38.951
39.300
39.538
40.274
40.706
40.941
41.743
42.438
43.069
43.560
43.891
44.270
44.575
45.189
45.997
46.423
1.1056
8.7183
0.8319
3.1320
0.2190
0.3402
0.2014
0.1102
0.0762
0.0197
0.0116
0.0352
0.0107
0.0374
0.1190
0.0092
0.0328
0.0075
0.0052
0.0368
0.0253
0.0458
0.4048
0.0363
0.0100
0.0302
0.0381
2.7808
0.0351
0.8887
0.0978
0.4596
5.1990
0.0514
1.1197
0.1030
0.8117
0.0179
0.2166
0.1056
3.1475
1.2002
0.9396
0.2512
0.0946
1.2474
0.9276
0.8150
0.0204
1.5506
0.7956
2.0966
0.4199
0.0570
0.1037
1.1856
2.2196
3.2318
0.3065
2.2720
0.9210
AREA
COUNTS
261389
1776S29
2057528
7746132
541789
841630
498208
272578
188561
48952
2863
67062
26601
92511
294539
22986
01348
18639
12993
91134
62580
113390
110338
29859
24909
74871
94275
6877545
86284
219612
242889
1136757
12258224
127256
2763393
254835
2007671
44415
535910
261295
7784593
2970205
2321492
621460
234054
3085222
2294362
2015890
S0586
3835100
1967729
5185525
1038713
141283
256647
2232430
5489778
7993048
758203
5619313
2278054
PEAK NO
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
TIME
MIN
46.792
47.224
47.781
48.165
48.622
48.885
49.422
49.631
49.950
50.878
51.103
51.505
51.900
52.282
53.015
53.233
53.351
53.900
54.445
55.496
56.254
56.757
57.578
52.311
58.737
59.062
59.305
59.585
60.289
60.738
61.164
61.725
62.234
62.784
63.334
63.694
65.237
65.744
66.057
66.498
67.750
68.941
69.576
70.772
71.176
73.909
76.804
Totals:
RESULT
1.9903
0.7840
0.0366
0.1328
0.7198
1.6601
0.6631
0.2702
3.0149
0.4315
1.0396
0.7925
0.1964
4.7189
0.1948
0.1385
0.1276
0.6462
6.3088
2.0417
0.6376
5.7329
0.7119
2.4470
1.2911
0.8173
0.2142
0.4431
1.8806
1.1166
1.5330
0.3161
0.5304
6.1344
0.0718
0.1518
3.0908
0.0234
1.2204
1.4520
0.1054
0.6679
0.0467
1.4422
0.0432
0.3845
0.0400
100.0000
AREA
COUNTS
4922553
1939166
90522
328488
1788284
4105857
1640093
668354
7456756
1067342
2571324
1968236
485864
11670947
481822
342637
315606
1598214
15683083
5049586
1577066
14178784
1768762
6052833
3193193
2021403
529919
1095923
4651342
2761764
3791596
781933
1311819
15171743
177670
375571
7644273
58015
3018513
3591283
260842
1651889
115583
3566957
106960
950984
99062
243322141
Figure 14 Representative standard chromatograms, PCBS, 1:1:1:1 mixture of 1242, 1248, 1254 and
56
-------
DIBDTYL CHLORENDATE
46.167
VARIAN 3400 GAS CHROMATOGRAPH
METHOD 4
TIME 20:46
SAMPLE: SRM-PEST-MTX BL
RUN MODE: ANALYSIS
CALCULATION TYPE: PERCENT
p,p'-DDT
PEAK
39.931 -L - NO.
I 1
'I 2
i
DIELDRIN
31.641 -^
I 3
4
5
= 6
E 7
alpha-CHLORDANE j_ — g
28.969 -4! Q
gamma-CHLORDANE f- y
27.454 "t- 10
.
,
2,4,5, e-TETRACHLORO-m-XTLENE
11
- 12
13
14
15
- - 16
17
18
I 19
' - 20
21
22
23
j ^°
= 24
PEAK TIME
NAME MTN
0.993
1.001
1.110
1.246
1.515
2.890
3.331
4.055
6.386
8.596
9.966
15.861
28.163
27.454
28.969
30.791
31.641
31.995
35.825
37.231
38.871
41.878
44.469
46.167
TOTALS:
DETECTED PEAKS: 24
RESULT
0.3951
1.0476
2.1354
3.6281
0.5526
0.0619
0.0230
0.0471
17.7812
0.2407
0.0519
0.1690
0.1522
13.3871
13.3975
0.0670
12.2040
0.0967
0.0785
0.5328
78.5277
0.0561
0.0962
15.2697
100.0000
REJECTED
AREA
COUNTS
105662
280156
571678
970257
147796
16558
6155
12596
4755119
64386
13883
45207
40711
3580026
3582811
17930
25863
21005
142.486
4954762
75010
25742
4083486
26742332
PEAKS: 0
AMOUNT STANDARD: 1.0000000
MULTIPLIER: 1.0000000 DIVISOR: 1.0000000
NOISE: 351.7 OFFSET:-70
COLUMN: DB-1701- 30 m x 0.52 mm ID, 1
micron film
Figure 14 (Cont.) Representative standard chromatograms, pesticides
57
-------
CHART SPEED 0.0 CM/MHI
ATTEN: . ZERO: 10Z 1 MIH/TICK
STANDARD SOLUTION (10 ng/ul)
INJECTION VOLUME = 10 ul
ANTHRACENE-d
10
4.042
BENZ[a]ANTHRACENE
BENZO[b]FLUORANTHENE
11.648
BENZO[k]FLUORANTHENE
13.151
BENZO[a]FYREHE
14.288
TITLE: 11:10 15 OCT 91
CHANNEL NO: 1 SAMPLE: PAH/UV Detection METHOD: RPS
PEAK PEAK
NO. NAME
1
2
3
4
5
6
TOTALS: 100.000
MULTIPLIER: 1.00000
RESULT
34.7021
11.4511
18.8221
13.3207
9.1462
12.5579
TIME
(MIN)
4.042
7.981
8.560
11.648
13.151
14.288
AREA
COUNTS
364225
87190
143313
101425
69640
95617
SEP
CODE
BB
BV
VB
BB
BB
BB
761410
Figure 14 (Cont.) Representative standard chromatograms, PAHs (U-V detector)
58
-------
fTHART oPEED 9.9 CM/MIN
ATTENr 17« ^ERO: 10Z
1 MTU/TICK
STANDARD SOLUTION (0.025 ng/ul)
INJECTION VOLUME = 50 ul
4.096 ANTERACENE-d
10
8.101 BENZ [a] ANTHRACENE
8.683 CHEYSENE
11.832 BENZO[b]FLUORANTHENE
13.375 BENZO[k]FLTrORANTHENE
14.512 BENZO[a]FYRENE
TITLE: EPA/PAHS/BR SS SAMPLES/FLUOR/A
13:48 13 FEB 92
CHANNEL NO: 1 SAMPLE: PAH
PEAK PEAK
NO NAME
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
RESULT
TIME
(MIN)
0.2159
0.1955
17.1740
0.2782
2.7644
4.9364
0.1767
8.2440
45.8585
18.4431
0.4970
0.1914
0.3698
0.2412
0.2027
0.2113
3.413
3.808
4.096
4.592
8.101
8.683
10.185
11.832
13.375
14.512
15.089
15.281
15.344
15.532
15.798
16.378
METHOD: RPS
AREA SEP
COUNTS CODE
6587 W
5964 W
523945 W
8486 W
84337 BV
150600 W
5391 W
251509 BV
1399050 W
562665 W
15161 W
5839 W
11282 W
7359 W
6183 W
6446 W
Figure 14 (Cont.) Representative standard chromatograms, PAHs (HPLC-fluorescence detector).
59
-------
7. QUALITY ASSURANCE AND QUALITY CONTROL (QA/QC)
PROCEDURES FOR ORGANIC ANALYSIS
The quality control program for the analysis of organic compounds included the following
procedures: initial blank; final blank; trip blank; duplicate sample analysis; reagent blank;
surrogate recovery; matrix spike recovery; triplicate injections; and quality control charts for
instruments. The quality assurance objectives for the analysis of organic compounds are
summarized in Table 9.
60
-------
Table 9
Quality Assurance Objectives for the Analysis of Pesticides, PCBs and
PAHs in Water and Sediment Samples
Analyte
Chlordane
Dieldrin
B,B' -DDT
Total PCBs
Benz[a]anthracene
Benzo[b]fluoranthene
Benzo[k]fluoranthene
Benzo[a]pyrene
Chrysene
Detection
Limit*
ug/1
0.014
0.002
0.012
0.020
0.01
0.02
0.02
0.02
0.01
Accuracy
a
a
a
a
a
a
a
a
a
Precision
b
b
b
b
b
b
b
b
b
Reagent
Blank
c
c
c
c
c
c
c
c
c
Matrix
Spike
Recovery
d
d
d
d
d
d
d
d
d
Surrogate
Spike
Recovery
e
e
e
e
e
e
e
e
e
Cali
bration
f
f
f
f
f
f
f
f
f
a. Accuracy = ±20% of known Certified Reference Material (CRM) run at a minimum of one per sample set.
b. Precision = triplicate analysis with %RSD <20% run at one per sample set **, sample <_ 30% for the Field Duplicate (FD)
run at 1 per sample set. Only if one or more samples in the set has a detectable concentration.
c. Reagent blank = < detection limit run at one per batch (deionized distilled water).
d. Matrix spike recovery = ±30% of known run at one per batch of samples at 1-1.5 times expected concentration -- 4 hour
equilibrium time.
e. Surrogate spike recovery = ±30% of known added prior to extraction.
f. Calibration = a minimum of and a blank will be run three concentration point curve. Calibration will be checked at the
beginning, and every 12 samples, and at the end (±10% at a concentration of 1-1.5 times expected sample concentration.
*Detection limits will be determined prior to sample analysis and defined as 3SD of 20 blanks or samples with concentrations with a
factor of 10 of the detection limit.
**A sample set is defined as 20 routine samples, or every analytical run if the run contains less than 20 samples.
-------
8. RESULTS
62
-------
8.1. Field Measurements
8.1.1. River Discharge and Flow Characteristics
The approximate hourly discharge data (hi cfs) provided by the Corps of Engineers for the
three USGS gauge sites were used to caluculate mean discharges for the tune of sampling during
the fall, 1990 surveys. Simple summation of the discharges would underestimate flow entering the
AOC since the gauges do not represent the entire contributing area (Figure 1). A proportional-
area approximation has been used (Meredith and Rumer, 1987; Irvine and Pettibone, 1993) to
adjust the flow record for the upper end of the AOC and this approach was used here:
[7.1] Qt = Qg*(At/Ag)
where Qt is the flow from the tributary into the AOC (cfs), Qg is the flow at the gauge in the
tributary (cfs), At is the total drainage area at the mouth of the tributary (mi2), and Ag is the
drainage area upstream of the gauge (mi2, 94.9 mi2, and 134 mi2,, respectively. Buffalo, Cayuga
and Cazenovia creek gauges are 144 mi2, 124.4 mi2, and 135.4 mi2, respectively (Meredith and
Rumer, 1987). The values of Qt (equation 7.1) for each tributary subsequently were summed to
estimate the discharge to the top of the AOC.
The mean discharges during the time of sampling for the fall, 1990 surveys were as
follows:
10/22/90 - 317 cfs (9.0 mV1)
10/27/90 - 293 cfs (8.3 mV1)
10/30/90 - 203 cfs (5.7 nrV)
11/05/90 - 243 cfs (6.9 mV)
11/09/90- 504 cfs (14.3 mV)
11/13/90 - 544 cfs (15.4 nrV)
In general, fall, 1990 sampling occurred during baseflow, steady-state conditions with the
exception of very small events during the last two surveys.
The discharges associated with the spring, 1992 event sampling, as determined by the
Corps of Engineers, are summarized in Table 10. By comparison, a mean daily discharge of
2,700 cfs (76.4 nrV1) would have been exceeded approximately 8% of the time during the period
of record, 1940-1985, while a mean daily discharge of 1,200 cfs (34.0 mV1) would have to be
exceeded approximately 20% of the time (cf. Meredith and Rumer, 1987). The mean daily
discharge for January 1 to August 31, 1992 also are plotted in Figure 15 as an indication of the
relative sample event magnitude compared to those of the winter through summer seasons of 1992.
The flow velocity data for the fall, 1990 surveys previously were sent to Mr. K. Rygwelski
(8' 19/91) by Dr. K. Irvine. However, these data together with the velocity measurements for the
spring, 1992 surveys are summarized in Table 11. Flow velocities during the fall, 1990 surveys
typically were slow (1-3 cm s-1) and negative (i.e. upstream flow) velocities were observed.
Baseflow velocities in the range of 1-3 cm s-1 also were observed by Sargent (1975). Negative
flows periodically were observed as far upstream as site 1, but were less frequent than at site 6
63
-------
Table 10 Measured and Interpolated Discharges, Cazenovia Creek, Buffalo River at
Harlem Rd. and Buffalo River Downstream of Cazenovia Creek
Date
4/17/92
4/18/92
4/22/92
Time
10:35
11:30
11:45
14:00
14:15
15:20
15:35
17:40
08:10
08:50
09:00
10:05
10:55
11:05
12:20
13:45
14:35
11:35
11:45
12:30
13:10
13:55
14:35
14:40
Cazenovia Creek at
Cazenovia Parkway
cfs
1,040
1,000
990
1,000
1,000
980
980
910
470
480
480
430
450
450
450
460
470
640
630
600
580
560
550
550
mV
29.4
28.3
28.0
28.3
28.3
27.8
27.8
25.8
13.3
13.6
13.6
122
12.7
12.7
12.7
13.0
13.3
18.1
17.8
17.0
16.4
15.9
15.6
15.6
Buffalo River at Harlem
Rd.
cfs
1,830
1,800
1,780
1,710
1,700
1,680
1,680
1,620
800
770
760
740
720
700
680
700
700
1,200
UOO
1,190
1,180
1,150
1,110
1,110
mV
51.8
51.0
50.4
48.4
48.1
47.6
47.6
45.9
22.7
21.8
21.5
21.0
20.4
19.8
19.3
19.8
19.8
34.0
34.0
33.7
33.4
32.6
31.4
31.4
Total Estimated Inflow
to the Top of AOC
cfs
2,870
2,800
2,770
2,710
2,700
2,660
2,660
2,530
1,270
1,250
1,240
1,170
1,170
1,150
1,130
1,160
1,170
1,840
1,830
1,790
1,760
1,710
1,660
1,660
mV
81.3
79.3
78.4
76.7
76.5
75.3
75.3
71.6
36.0
35.4
35.1
33.1
33.1
32.6
32.0
32.8
33.1
52.1
51.8
50.7
49.8
48.4
47.0
47.0
64
-------
(near the river mouth). Both positive and negative velocities also occurred at a single sample
vertical (Table 11). Sargent (1975) similarly found that both positive and negative flows could
occur in a single sample vertical. Although the baseflow positive and negative flows could occur
in a single sample vertical (Table 11). Sargent (1975) similarly found that both positive and
negative flows could occur in a single sample vertical. Although the baseflow downstream
velocities often were in the range of 1-3 cm s-1, it is emphasized that there are distinct, local three-
dimensional currents superimposed on the downstream movement (see also Sargent, 1975).
Sediment transport dynamics within the AOC are being mathematically modelled (e.g. Lick et ah,
1992). however, as a first approximation to evaluating sediment movement in this repc ~, the
well-known Hjulstrom diagram can be used. The Hjulstrom diagram (not shown) relates the size
of sediment that can be eroded or transported to mean flow velocity (e.g. Knighton, 1987). the
Hjulstrom diagram indicates that velocities of 1-3 cm s-1 would be capable of transporting (but not
eroding) particle sizes ranging from clay to medium sand.
The flow velocities observed during the spring, 1992 event sampling were greater than
those observed for baseflow conditions and always were positive (i.e. downstream flow).
Measured velocities during the events were greatest at site 1 and decreased at the sites in the
downstream direction. This trend in velocity is related to channel geometry, as the river becomes
deeper and wider from sites 1 to 3 to 6. Again, using the Hjulstrom diagram, the measured
velocities at site 1 on 4/17/92 and 4/22/92 would be capable or eroding (and transporting) silt to
very coarse sand or granules (Wentworth scale). The velocities measured at site 3 would be
capable or eroding (and transporting) silt to very coarse sand, while the velocities measured at site
6 would be capable or eroding (and transporting) silt to coarse sand.
8.1.2. Conventional Parameters Determined Using the SeaBird Sealogger
Conventional parameter values determined using the SeaBird Sealogger for the fall, 1990
and spring, 1992 surveys were submitted to Mr. K. Rygwelski, CSC, by Dr. JillSinger, SUNY
College at Buffalo. These conventional parameters therefore are not summarized in this report.
8.1.3. Carp Measurements
The wet weights (prior to removal of stomach contents), lengths; ages and sex of the carp
in the young, middle and old age classes are summarized in Table 12. The separate wet weights
of the composited stomach contents for each subsample of each age class are summarized in Table
13.
65
-------
3 -1
m s
0
D)
x_
CO
O
CO
283 10000
226 8000
170 6000
113 4000
57 2000
0
Spring Sample Dates
I I I I I
^. ,_. . J M
1-1 1-29 2-26 3-25 4-22 5-20 6-17 7-15 8-12 9-9
Date
VO
Figure 15 Inflow to the top of the Buffalo River Area of Concern, January 1 through
August 31, 1992.
-------
TABLE 11 FLOW VELOCITY DATA, FLOW VELOCITY MEASUREMENTS (cm s'1)
BUFFALO RIVER, 10/16/90
Sample
Depth
(m)
0.2
0.34
0.84
1.34
1.94
2.44
4.28
6.12
time of
sample
Sample Station Number
1
2
2
run
nm
nm
nm
nm
nm
10:31
2
2
1
nm
nm
nm
nm
nm
nm
10:46
3
2
1
nm
nm
nm
nm
nm
nm
10:59
4
1
2
2
nm
nm
nm
nm
nm
11:11
5
1
1
3
1
1
nm
nm
nm
11:24
6
-13
-13
-11
-10
-9
-11
-9
-5
11:33
Notes: nm - no measurement taken; data for sites 1-5 are 10 second averages determined by the
Montedoro-Whitney PVM-2A current meter, data for site 6 are the average of 5 instantaneous
readings; a minus (-) indicates flow direction was reversed (i.e. upstream). All sample depths
represent a depth below the water surface.
67
-------
TABLE 11 (CONTINUED) FLOW VELOCITY MEASUREMENTS (cm s"1) BUFFALO
RIVER, 10/17/90
Sample
Depth
(m)
0.2
0.34
0.84
1.34
1.94
2.44
4.28
6.12
time of
sample
Sample Station Number
1
-5.2
-5.6
-6.8
-11.0
-8.4
-1.6
-1.6
nm
11:59
2
-3.8
-2.2
2.0
-1.6
-1.8
nm
nm
nm
12:17
3
6.2
4.2
8.2
5.0
8.0
3.4
nm
nm
12:38
4
-7.2
-9.4
-5.8
-4.8
-4.2
6.2
nm
nm
13:03
5
2.2
3.6
0.8
2.8
-1.6
nm
nm
nm
13:15
6
-16.7
-16.4
-19.2
-14.4
nm
-7.8
-8.6
-7.6
13:27
Note: all data are an average of 5 instantaneous readings.
68
-------
TABLE 11 (CONTINUED) FLOW VELOCITY MEASUREMENTS (cm s'1) BUFFALO
RIVER, 10/21/90
Sample
Depth
(m)
0.2
0.34
0.84
1.34
1.94
2.44
4.28
6.12
time of
sample
Sample Station Number
1
2.6
0.8
0.6
0.0
nm
nm
nm
nm
10:24
2
-0.8
0.4
-1.2
-2.4
nm
nm
nm
nm
10:38
3
-1.0
-0.6
-3.6
-6.0
nm
nm
nm
nm
10:49
4
2.4
4.0
7.8
-3.0
nm
nm
-7.8
nm
11:03
5
-4.0
-7.0
-4.4
-5.0
nm
nm
-2.6
3.6
11:17
6
1.8
-2.6
-5.0
-1.4
0.8
nm
3.0
3.6
11:29
Note: data are an average of 5 instantaneous readings
69
-------
TABLE 11 (CONTINUED) FLOW VELOCITY MEASUREMENTS (cm s'1) BUFFALO
RIVER, 10/26/90
No velocity measurements were obtained on 10/26/90
FLOW VELOCITY MEASUREMENTS (cm s'1) BUFFALO RIVER, 10/30/90
Sample
Depth
(m)
0.2
0.34
0.84
1.34
1.94
2.44
4.28
6.12
time of
sample
Sample Station Number
1
0.0
1.0
-3.2
-2.4
-1.6
nm
1.2
nm
9:02
2
-2.0
-2.8
-1.8
-3.0
-0.4
nm
3.0
nm
9:16
3
-0.8
1.6
2.0
4.6
1.2
nm
2.0
nm
9:25
4
7.0
3.8
1.2
3.4
3.6
nm
5.2
nm
9:38
5
4.2
9.4
5.6
15.2
10.0
nm
9.6
nm
9:50
6
-3.6
8.0
9.6
-15.6
-12.2
nm
7.8
5.2
10:00
Note - data are an average of 5 instantaneous readings
70
-------
TABLE 11 (CONTINUED) FLOW VELOCITY MEASUREMENTS (cm s'1) BUFFALO
RIVER, 11/04/90
Sample
Depth
(m)
0.2
0.34
0.84
1.34
1.94
2.44
4.28
6.12
time of
sample
Sample Station Number
1
3.0
-4.0
0.4
10.6
14.2
nm
11.8
nm
11:12
2
1.2
-1.4
1.6
0.4
2.0
nm
2.0
nm
11:28
3
1.2
2.6
4.4
1.6
-2.6
nm
-3.6
1.2
11:43
4
-1.6
-7.4
-8.2
-3.2
-6.4
nm
-7.6
-7.0
12:05
5
-12.6
-11.4
-7.2
-5.8
-6.6
nm
-10.8
nm
12:23
6
-16.6
-14.4
-16.0
-14.6
-13.0
nm
-12.6
-12.4
12:44
Note: data are an average of 5 instantaneous readings
71
-------
TABLE 11 (CONTINUED) FLOW VELOCITY MEASUREMENTS (cm s'1) BUFFALO
RIVER, 11/08/90
Sample
Depth
(m)
0.2
0.34
0.84
1.34
1.94
2.44
4.28
6.12
time of
sample
Sample Station Number
1
nm
nm
nm
nm
nm
nm
nm
nm
2
nm
nm
nm
nm
nm
nm
nm
nm
3
nm
nm
nm
nm
nm
nm
nm
nm
4
1.4
1.8
3.8
3.2
3.4
nm
2.0
nm
10:20
5
3.2
0.8
1.6
3.8
3.2
nm
6.6
nm
10:32
6
nm
nm
nm
nm
nm
nm
nm
nm
Note: data are an average of 5 instantaneous readings
72
-------
TABLE 11 (CONTINUED) FLOW VELOCITY MEASUREMENTS (cm s'1) BUFFALO
RIVER, 11/12/90
Sample
Depth
(m)
0.2
0.34
0.84
1.34
1.94
2.44
4.28
6.12
time of
sample
Sample Station Number
1
run
nm
33.6
30.0
32.6
nm
26.4
nm
10:22
2
nm
nm
2.0
-7.8
-5.6
nm
1.2
nm
10:35
3
nm
nm
1.2
-5.8
-10.4
nm
-5.8
nm
10:47
4
nm
nm
-23.2
-17.6
-16.0
nm
-17.0
nm
10:59
5
nm
nm
-20.0
-13.8
-14.2
nm
-10.6
nm
11:10
6
nm
nm
nm
nm
nm
nm
nm
nm
Note: data are an average of 5 instantaneous readings
73
-------
TABLE 11 (CONTINUED) FLOW VELOCITY MEASUREMENTS (cm s'1) BUFFALO
RIVER, 04/17/92
Sample Depth (m)
0.30
0.61
0.91
1.22
1.52
1.83
2.44
3.05
3.66
4.27
4.88
time of sample
Sample Station Number
1
38
41
32
32
45
31
32
32
33
33
37
11:45
3
21
21
18
17
17
18
16
15
14
17
14
16:00
6
12
10
9
9
8
8
8
12
11
11
11
18:10
data are an average of 5 instantaneous readings
74
-------
TABLE 11 (CONTINUED) FLOW VELOCITY MEASUREMENTS (cm s'1) BUFFALO
RIVER, 04/18/92
Sample Depth (m)
0.30
0.61
0.91
1.22
1.52
1.83
2.44
3.05
3.66
4.27
4.88
time of sample
Sample Station Number
1
14
15
16
15
16
17
16
15
17
15
14
8:30
3
9
10
13
12
15
12
12
11
10
10
11
10:55
6
11
12
12
9
10
10
9
8
7
8
9
13:40
data are an average of 5 instantaneous readings
75
-------
TABLE 11 (CONTINUED) FLOW VELOCITY MEASUREMENTS (cm s'1) BUFFALO
RIVER, 04/22/92
Sample Depth (m)
0.30
0.61
0.91
1.22
1.52
1.83
2.44
3.05
3.66
4.27
4.88
time of sample
Sample Station Number
1
26
26
29
29
28
27
26
24
nm
nm
nm
10:57
3
16
14
16
15
14
15
16
15
14
13
12
6
7
9
8
4
5
5
4
3
2
1
3
13:30
data are an average of 5 instantaneous readings
76
-------
TABLE 12 BUFFALO RIVER CARP, SAMPLING OF JULY 24, 1991, YOUNG AGE
CLASS"
Fish I.D.
BRF Y W - 1 1
BRF Y W - 1 2
BRF Y W - 1 3
BRF Y W - 1 4
BRF Y W - 1 5
BRF Y W - 2 1
BRF Y W - 2 2
BRF Y W - 2 3
BRF Y W - 2 4
BRF Y W - 2 5
BRF Y W - 3 1
BRF Y W - 3 2
BRF Y W - 3 3
BRF Y W - 3 4
BRF Y W - 3 5
Age,
Years
4
5
4
4
4
4
4
4
4
4
5
4
4
5
5
Sex
F
M
F
F
M
F
M
M
F
F
F
F
ND"
M
M
Wet Weight,
kg
1.218
0.569
1.049
0.936
0.950
1.218
0.936
0.765
0.921
1.020
0.751
1.218
0.569
1.049
1.049
Standard
Length, cm
35.7
27.1
33.3
31.6
34.5
35.4
32.4
29.0
33.4
33.0
30.7
37.0
25.6
34.2
33.8
Total
Length, cm
43.4
34.1
41.0
39.0
42.2
43.3
40.0
36.5
40.8
40.6
37.7
44.6
31.6
40.5
41.2
* wet weights and lengths were determined prior to removal of stomach contents
*' not possible to definitively determine sex by inspection at field station
77
-------
TABLE 12 (CONTINUED) BUFFALO RIVER CARP, SAMPLING OF JULY 24, 1991,
MIDDLE AGE CLASS
Fish I.D.
BRF M W - 1 1
BRF M W - 1 2
BRF M W - 1 3
BRF M W - 1 4
BRF M W - 1 5
BRF M W - 2 1
BRF M W - 2 2
BRF M W - 2 3
BRF M W - 2 4
BRF M W - 2 5
BRF M W - 3 1
BRF M W - 3 2
BRF M W - 3 3
BRF M W - 3 4
BRF M W - 3 5
Age,
Years
7
5
5
9
6
7
6
5
5
7
6
5
4
7
5
Sex
F
F
F
F
M
M
ND
F
F
M
M
M
ND
ND
M
Wet Weight,
kg
1.899
1.389
1.276
2.041
1.559
1.644
1.729
1.587
1.531
1.843
1.531
1.559
1.417
2.154
1.389
Standard
Length, cm
39.8
37.2
35.5
40.2
39.4
38.5
37.7
38.8
39.9
42.0
37.6
38.5
34.5
40.5
38.6
Total
Length, cm
49.4
44.9
43.6
49.5
47.0
46.2
46.4
48.0
48.4
51.7
46.5
47.0
42.6
49.6
47.0
78
-------
TABLE 12 (CONTINUED) BUFFALO RIVER CARP, SAMPLING OF JULY 24, 1991,
OLD AGE CLASS
Fish ID.
BRF O W - 1 1
BRF 0 W - 1 2
BRF 0 W - 1 3
BRF 0 W - 1 4
BRF 0 W - 1 5
BRF O W - 2 1
BRF O W - 2 2
BRF O W - 2 3
BRF 0 W - 2 4
BRF 0 W - 2 5
BRF O W - 3 1
BRF O W - 3 2
BRF O W - 3 3
BRF 0 W - 3 4
BRF O W - 3 5
Age,
Years
9
11
9
10
11
12
13
12
6
11
10
14
9
9
8
Sex
M
F
M
F
F
F
F
F
F
M
M
F
M
F
F
Wet Weight,
kg
2.296
5.980
2.438
6.547
5.499
5.442
4.337
5.159
2.919
3.430
2.551
8.220
6.264
2.692
2.523
Standard
Length, cm
44.1
58.9
45.0
61.8
61.3
57.0
56.0
58.3
49.2
51.3
44.5
66.2
59.0
45.3
46.2
Total
Length, cm
54.9
72.4
55.2
75.0
72.4
68.4
67.6
70.6
58.8
62.8
55.4
79.5
71.6
56.1
55.8
79
-------
TABLE 13 BUFFALO RIVER CARP, SAMPLING OF JULY 24, 1991, STOMACH
CONTENT WET WEIGHTS
Sample I.D.
BRF YS
BRF YS
BRF YS
- 1
-2
-3
BRF MS
BRFM S
BRF MS
- 1
-2
-3
BRF OS
BRF OS
BRF OS
- 1
-2
-3
Wet Weight, gm*
0.2
0.3
0.4
0.5
0.4
0.5
0.6
0.8
0.5
* weights should be taken for general information purposes only since the scale at the field
station was sensitive only to approximately 0.1 g.
80
-------
8.2. RESULTS OF ORGANIC ANALYSIS
(The results are not corrected for recovery)
8.2.1. TOTAL PCBs (DISSOLVED PHASE) FALL, 1990
81
-------
Table 14 Sample Abbreviations List
BR
1 through 6
01
01 -06
W,F
1
2
D
P
cso
CA
BA
SM
HM
Buffalo River
Survey Number
Composite
Station
Sample Type: W = Water; F = Fish
Regular
Duplicate
Dissolved
Particulate
Combined Sewer Overflow
Cazenovia Creek
Babcock Street
Smith Street (outfall; St. Stephans PI. chamber)
Hamburg Street
82
-------
Table 15
Total PCBs In Buffalo River Water Samples incliding CSO Samples, Fall 1990, Revised As Per Dr. Marc Tuchman
PCB Quantitation: Total PCBs in Buffalo River Water Samples
Sam.
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
15
16
17
18
19
20
(Revised)
IDLdnstrument detection limit) = 108 pg/injection in GC
LOQ(Limit of quantitation) = 161 pg/injection in GC
MDUMethod detection limit) = 125.1 ng/sample (3 x SD of background PCB levels)
BMDL(below method detection limit) =
-------
Table 15 (Continued)
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
52
50
51
49
48
46
45
47
53
54
55
10/27/90
10/2 7, '90
10/27/90
10/29/90
10/29.'90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
^ 11/5/90
11/5/90
11/5/90
11/5/90
!__1 1/5/90
11/5/90
11/5/90
11/6/90
11/6/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/13/90
BR20104W1D
BR20105W1D
BR20106W1D
BLANK 1029A
BLANK1029B
TRIP-BLANK
BR30101W1D
BR30102W1D
BR30103W1D
BR30104W1D
BR30104W2D
BR30105W1D
BR30106W1D
BLANK1031A
BLANK1031B
BR40101W1D
BR40101W2D
BR40102W1D
BR40103W1D
BR40104W1D
BR40105W1D
BR40106W1D
BLANK 1106A
BLANK 1106B
BR50101W1D
BR50102W1D
BR50102W2D
BR50103W1D
BR50104W1D
BR50105W1D
BR50106W1D
TRIP BLANK
BLANK 1109A
BLANK 1109B
BR60101W1D
100.4099
113.6264
127.2698
6.689773
49.43793
168.4128
172.8089
148.1895
130.0136
119.2442
114.7577
106.4876
217.5418
212.9242
109.6593
125.3597
80.97045
90.55266
89.9517
106.6749
61.25199
159.6254
113.6635
102.6797
104.3039
105.846
93.1307
98.7714
105.8033
109.155
116.0178
90.30557
71.33739
39.6306
104.4506
0.0000
8.72 + /-41.7
22.36 +/-41.7
0.0000
0.0000
63.50 +/-41.7
67.90 +/-41.7
43.28 +/-41.7
25.10 +/-41.7
14.33 +/-41.7
9.85 +/-41.7
1.58 +/-41.7
112.63 -f/-41.7
108.01 +/-41.7
4.75 +/-41.7
20.45 +/-41.7
0.0000
0.0000
0.0000
1.76 +/-41.7
0.0000
54.71 +/-41.7
8.75 -f/-41.7
0.0000
0.0000
0.94 +/-41.7
0.0000
0.0000
0.89 +/-41.7
4.24 +/-41.7
11.11 +/-41.7
0.0000
0.0000
0.0000
0.0000
BMDL
BMDL
BMDL
BMDL
BMDL
63.501999
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
-14.605222
BMDL
BMDL
BMDL
0
0.1529045
0.43415514
0
0
0
1.20600569
0.77283316
0.4482644
0.2550419
0.17583747
0.02866996
2.00232975
1.89497212
0.08330698
0.36581182
0
0
0
0.03097574
0
0.97530443
0.15629821
0
0
0.01700389
0
0
0.01703156
0.07955312
0.22348194
0
0
0
0
0
0
0
0
0
0
0.46529549
0.02815488
0
0
0
0
1.26096114
1.16335837
0
0
0
0
0
0
0
0.23195356
0
0
0
0
0
0
0
0
0
l_ °
0
0
0
0.66430536
0.88451811
1.24390224
0
0
0
1.94671574
1.5175113
1.19294254
0.99706995
0.92051561
0.78688771
2.74369821
2.62658574
0.81492059
1.11182212
0.31717198
0.51592147
0.48185377
0.76323168
0
1.71865516
0.90097635
0.70483672
0.73253209
0.77522164
0.53431923
0.635046
0.8128708
0.8612209
1.0625559
0
0.14260646
0
0.74510969
60.8499
122.9197
105.7433
76.1309
51.492
81.7017
99.4288
92.2452
42.0649
78.0154
90.7196
84.4192
83.7811
65.6996
69.172
90.8294
60.5041
70.6658
67.9832
88.1766
37.6036
97. 2#
75.464
85.822
103.2371
84.6836
81.4271
63.1093
65.8029
67.9122
70.2093
99.9101
47.2314
24.9676
96.13
-------
Table 15 (Continued)
56
57
58
59
60
61
62
63
64
68
69
70
71
72
73
74
75
76
78
79
80
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
11/14/90
11/14/90
12/5/90
12/5/90
12/5. '90
12/5/90
12/5/90
12/5/90
12/6/90
12/6/90
7/30/91
8/9/91
8/9/91
8/16/91
BR60102W1D
BR60103W1D
BR60104W1D
BR60105W1D
BR60105W2D
BR60106W1D
TRIP-BLANK
BLANK1114A***
BLANK1114B
BLANK 1205 A
BLANK1205B
CSO-1W1D(Ba)
CSO-2W1 D
-------
Table 15 (Continued)
***This blank's data was discarded due to abnormally high PCB levels. Further analysis of
this blank revealed that the PCB pattern resembled Aroclor 1 248 and 1 254 mixture.
Since our laboratory does not use this mixture, the contaminantion should have come
from other sources.
~ The low percentage recovery of the surrogate standards is due to the problem encountered
during the Soxhlet extraction of the XAD-2 resin. This problem was addressed to EPA
on the phone and Fax (Sept. 23, 91) to Richard G. Fox.
Background Total PCBs level calculations.
Sam.
No.
26
34
35
43
44
47
53
54
62
64
68
69
74
75
76
80
Date
10/31/90
10/31/90
10/31/90
11/6/90
11/6/90
11/9/90
11/9/90
11/9/90
11/13/90
11/14/90
12/5/90
12/5/90
12/6/90
12/6/90
7/30/91
8/16/91
Sample ID
TRIP-BLANK
BLANK1031A
BLANK1031B
BLANK 1106A
BLANK 1106B
TRIP BLANK
BLANK 1109A
BLANK 1109B
TRIP-BLANK
BLANK1114B
BLANK1205A
BLANK1205B
BLANK 1206A
BLANK 1206B
BLANK910730A
BLANK910816A
Average
S.D.
PCB
Amount-1
(ng/samp)
168.4128
212.9242
109.6593
113.6635
102.6797
90.3056
71.3374
39.6306*
89.2701
72.6123
148.0318
85.9184
108.3698
80.9513
104.0956
80.7104
104.9108
39.2248
*This value was obtained from data which was lower than the IDL (Instrument Detection Limit)
of the GC. All other values were obtained from data which was above the LOQ
(Limit of Quantitation).
-------
T;. .le 15 (Continued)
Test Analysis:
[
Soxhlet extraction of resin samples gave about 1 0-30ml liquid which is not
concentrated to lower volume. The boiling point of this liquid was > 1 00°C and is
soluble in methylene chloride , hexane and other organic solvents.
problem in analyzing trace organics. I
This caused
This problem was discussed with Richard G. Fox , GLNPO, US EPA (March 24, 25,
1 992) and other scientists engaged in similar kind of analysis and
also the
1 University of Wisconsin- Superior, who supplied XAD-2 resin. In the process
I of identifying the causative factor we extracted blanks (not the samples).
IGC-MS analysis of the extract revealed that the liquid is DIACETONE ALCOHOL
(boiling point 166rC). This diacetone alcohol might have formed due to
aldol condensation process that might have occurred during the storage
of resin samples in acetone under 4°C in refrigerator. We came to know
that Tom Markee's lab (Univ. Wisconsin-Superior) also encountered
similar problem in their samples.
Since diacetone alcohol (b.p 166°C)
is soluble in water, Wisconsin- Superior lab dissolved the diacetone alcohol
in excess amount of nanopure water and extracted the PCBs by hexane in
a separator/
funnel. Since we analyze not only PCBs and pesticides but also
PAHs, we tested whether the hexane -water partitioning method works for our
analytes of interest. We did recovery tests using PCB congener, pesticide and
PAHs. We repeated the test with four more blanks and the recovery of the analytes
were 100 + 7-30%. The results were discussed with Richard Fox.
using blanks, the samples were analyzed.
After the tests
87
-------
Table 16 Total PCBs in Buffalo River Water Samples, Triplicate Ini actions
PCB Quantitation-Total PCBs in Buffalo River Water Samples
Sam.
No.
12
22
33
42
45
58
73
Triplicate Injections
Date
10/22,90
10/27.'90
10/31/90
11/5/90
11/9/90
11/13,90
12/5/90
Sample ID
BR10105W1D
BR20105W1D
BR30106W1D
BR40106W1D
BR50106W1D
BR60104W1D
CSO-Hamburg
Injection
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
PCB
Amount*
(ng/samp.)
130.6146
114.8109
114.6676
116.2032
109.8165
114.8594
218.7149
216.3506
217.5601
162.5123
156.5291
159.8348
120.7524
114.0322
113.2689
140.6544
151.0190
1 60.0026
525.6308
532.2612
531.2222
'Total PCBs detected in samples. These values include background PCBs.
**Total PCBs amount after the background PCBs (104.9 +/- 41 .7 ng/sample)
have been subtracted.
Quantity
Detected**
(ng/L water)
(ppt)
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
23.0 + /-2.3
23.5 +/-2.S
23.4 +7-2.3
88
-------
Table 17 Matrix Spike Recovery of Total PCBs in Fall, 1990 Samples
PCB Quantitation-Total PCBs in Buffalo River Water Samples
Sample No.
22
42
45
73
Matrix Spike Recovery
Date
10/27. '90
11/5/90
11/9/90
12/5/90
*GC Injection Sample
Sample ID
BR20105W1D
BR40106W1D
BR50106W1D
CSO-4W1 D(Ha)
Actual
Amount
in Sample*
(ng)
28.40659
39.90634
29.00446
1 32.4262
Spiked
Amount
(ng)
40
60
40
180
Total
Amount
Recovered
(ng)
71.11313
102.8118
73.442
313.8498
Recovery
of Spiked
Amount
(%)
106.7663
104.8424
1 1 1 .0938
100.7909
89
-------
8.2.2 TOTAL PCBs (DISSOLVED PHASE) SPRING, 1992
90
-------
Table 18 Total PCBs In Buffalo River Water Samples (Spring, 1992)
PCB Quantitation: Total PCBs in Buffalo River Water Samples (Spring Event Samples)
Sam.
No.
1D
2D
3D
4D
5D
60
7D
8D
9D
10D
11D
12D
13D
14D
15D
16D
17D
18D
(XAD-2 Resin Samples, ng/L)
IDL(lnstrument detection limit) = 75 pg/injection in GC
LOQILimit of quantitation) = 112 pg/injection in GC
MDUMethod detection limit) = 94. 4ng/sample (3 x SD of background PCB levels)
BMDLIbelow method detection limit) =
-------
Table 18 (Continued)
These data were obtained using a Varian GC 3400 equipped with ECD detector and a DB-5 capillary
column-30m, 0.25 mm id, 0.25 micron film thickness.
'''Three levels calculated as per the suggestion by Dr. Marc Tuchman.
* Average value obtained from 5 Blanks. (Also, see below.)
(Sample No.: 1D, 6D, 1 1D, 16D, 17D)
Mean +/-S.D.= 95.116 +/-31.470
**This sample has TCMX recovery is 92.95%
Background Total PCBs level calculations.
Sam.
No.
1D
6D
11D
16D
17D
Date
April 16, '92
April 17, '92
April 18, '92
April 22, '92
April 22, '92
Sample ID
Blank (Initial)
BlanMafter SBR1)
Blank(after SBR2)
Blank (final)
Trip Blank
Average
S.D.
PCB
Amount- 1
(ng/samp)
130.25931
63.011
114.128
107.448
60.732
95.1157
31.4705
Page 2
-------
Table 19 Triplicate Injections For Total PCBs In Spring, 1992 Samples
PCB Quantitatlon • Total PCBs in Buffalo River Samples (Spring Event Samples)
Triplicate Injection
Sample
No.
5D
5D
5D
8P
8P
8P
13P
13P
13P
Date
17-Apr
1 7-Apr
1 7-Apr
1 8-Apr
1 8-Apr
1 8-Apr
22-Apr
22-Apr
22-Apr
Sample
ID
SBR10106W1D
SBR10106W1D
SBR10106W1D
SBR20103W1P
SBR20103W1P
SBR20103W1P
SBR30103W1P
SBR30103W1P
SBR30103W1P
PCB
Amount
in Sample
Ing)*
125.251416
118.749025
121.21937
94.6338355
90.7299441
95.8093872
306.677579
302.808617
309.583215
Water
Sample
Volume
(L)
52
52
52
54.94
54.94
54.94
55.09
55.09
55.09
PCB
Concentration
In Water
(ng/L)"«
T.S. Solids
(ppm)
0.580 +/- 0.605 (BMDL)
0.454 +/- 0.605 (BMDL)
0.502 4- /- 0.605 (BMDL)
0.541 + /- 0.163
0.470 +/-0.153
0.562 +/-0.153
4.389 +/-0.153
4.318 + /- 0.153
4.441 +/- 0.153
*Total PCBs detected in samples. These values included background PCBs
28
28
28
29
29
29
••Total PCBs amount after the background PCBs(95.12 + /-31.47 ng for Sample 50,
64.91 + /-8.42ng for Samples 8P and 13P) have been subtracted.
PCB
Concentration
in S.S.
(mg/kg)**
0.019 +1- 0.005
0.017 +/- 0.005
0.020 +/- 0.005
0.151 +/- 0.005
0.149 +/- 0.005
0.153 +/-0.005
CO
-------
Table 20 Matrix Spike Recovery of Total PCBs in Spring, 1992 Samples
Matrix Spike Recovery
Sample
No.
13D
5P
Date
22-Apr
17-Apr
Sample
ID
SBR30103W1D
SBR10106W1P
*GC Injection Sample
-•
Actual
Amount
in Sample*
(ng)
38.993275
128.7475
PCB
Spiked
Amount
(ng)
60
200
Total
Amount
Recovered
(ng)
102.6799808
303.3709185
PCB
Recovered
Amount
(ng)
63.6867058
174.623418
Recovery of
Spiked
Amount
(%)
106.1445096
87.31170923
VO
-------
8.2.3. TOTAL PCBs (PARTICULATE PHASE) FALL, 1990
95
-------
Table 21 Total PCBs fne/L) In Buffalo River Susoended Sediments Includine CSO Samples. Fall 1990
PCB Quantitation: Total PCBs in Buffalo River Water Suspended Sediment Samples
Sam.
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
(Glass fiber filter samples)
(Revised - ng/L)
IDUInstrument detection limit): first time extraction, 64 pg/injection; second time extraction, 58 pg/injection in GC
LOQ(Limit of quantitation): first time extraction, 107 pg/injection in GC; second time extraction, 131 pg/injection in GC
MDUMethod detection limit) = 69.1ng/sample (3 x SD of background PCB levels)
BMDLfbelow method detection limit) =
-------
Table 21
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
Continued)
10/27/90
10/27/90
10/27/90
10/27/90
10/29/90
10/29/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
1/5/90
1/5/90
1/5/90
1/5/90
1/5/90
1/5/90
1/5/90
1/6/90
1/6/90
1/9/90
1/9/90
1/9/90
1/9/90
1/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
BRT0203W2P
BR20104W1P
BR20105W1P
BR20106W1P
BLANK1029A
BLANK1029B
TRIP-BLANK
BR30101W1P
BR30102W1P
BR30103W1P
BR30104W1P
BR30104W2P
BR30105W1P
BR30106W1P
BLANK1031A
BLANK1031B
BR40101W1P
BR40101W2P
BR40102W1P
BR40103W1P
BR40104W1P
BR40105W1P
BR40106W1P
BLANK 1106A
BLANK 1106B
BR50106W1P
BR50105W1P
TRIP BLANK
BR50104W1P
BR50103W1P
BR50102W1P
BR50102W2P
BR50101W1P
BLANK 1109A
BLANK 1109B
291.8
223.1
235.4
220.7
91.4
78.8
117.4
120.6
86.1
147.6
218.8
192.7
153.9
146.5
60.2
77.8
135.8
276
225
316.8
238.6
205.9
156.9
202.41 +/- 23.05
133.71 +/- 23.05
146.01 +/- 23.05
131.31 +/- 23.05
2.01 +/- 23.05
0
28.01 +/- 23.05
31.21 + /- 23.05
0
58.21 +/- 23.05
129.41 + /- 23.05
103.31 +/- 23.05
64.51 +/- 23.05
57.11 +/- 23.05
0
0
46.41 +/- 23.05
186.61 +/- 23.05
135.61 + /- 23.05
227.41 +/- 23.05
149.21 +/- 23.05
116.51 +/- 23.05
67.51 +/- 23.05
Sample was lost during analysis.
108.3
354.6
210.6
84.8
225.5
137.2
136.7
123.2
62.6
69.6
128
18.91 +/- 23.05
265.21 +/- 23.05
121.21 +/- 23.05
0
136.11 +/- 23.05
47.81 +/- 23.05
47.31 +/- 23.05
33.81 +/- 23.05
0
0
38.61 + /- 23.05
3.58 +/-0.41
2.34 +/-0.40
2.52 +/-0.40
2.51 +/-0.44
BMDL
BMDL
BMDL
BMDL
BMDL
2.28 +/-0.41
1.83 +/-0.41
BMDL
BMDL
BMDL
BMDL
BMDL
3.29 +/-0.41
2.53 +/-0.43
4.04 +/-0.41
2.62 +/-0.40
2.05 +/-0.41
BMDL
BMDL
5.17 +/-0.45
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
3.576845
2.341335
2.520519
2.507421
0.03502
0
0
0.548763
0
1 .030786
2.280818
1.825329
1.158442
1 .003402
0
0
0.823229
3.290665
2.534361
4.044347
2.620081
2.050214
1.189458
0
0.333692
5.173891
2.199086
0
2.531876
0.847459
0.854037
0.603276
0
0
0.670143
3.1695315
1.9377305
2.1226271
2.0672864
0
0
0
0.1435265
0
0.6226435
1.8745821
1.4180882
0.7445464
0.5984503
0
0
0.4143985
2.8842142
2.1036029
3.6344263
2.2153431
1 .6446206
0.7833649
0
0
4.7242253
1.7809106
0
2.1031211
0.4389186
0.4379745
0.1920391
0
0
0.2701109
3.9841578
2.74493942
2.91840998
2.94755566
0.43588678
0.2162674
0
0.95399947
0.3493017
1.43892855
2.68705481
2.23257049
1.57233776
1 .40835365
0
0.1998168
1.23205906
3.69711673
2.96511848
4.45426801
3.02481984
2.45580662
1.59555127
0
0.74035797
5.62355618
2.61726216
0
2.96063039
1.25599947
1.2700991
1.01451365
0
0.05680574
1.07017511
-------
00
Table 21 (Continued)
55
56
57
58
59
60
61
62
63
64
68
69
70
71
72
73
74
75
76
78
79
80
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
11/14/90
11/14/90
12/5/90
12/5/90
12/5/90
12/5/90
12/5/90
12/5/90
12/6/90
12/6/90
7/30/91
8/9/91
8/9/91
8/16/91
BR60101W1P
BR60102W1P
BR60103W1P
BR60104W1P
BR60105W1P
BR60105W2P
BR60106W1P
TRIP-BLANK
BLANK1114A
BLANK1114B
BLANK1205A
BLANK1 205B
CSO-4W1P(Ba)
CSO-2W1P(Ca)
CSO-4W1P(Sm)
CSO-4W1P(Ha)
BLANK1206A
BLANK 1206B
BLANK910730A
CSO-SM0809
CSO-HM-0809
BLANK910816A
60.8
29
141.4
524.7
139.7
126.7
145.8
120
60.4
94
Test analysis
Test analysis
488.4
163.2
1949.2
2959.3
88.2
58.6
96.8
441.4
511.2
66.4
0
0
52.01 +/- 23.05
435.31 +/- 23.05
50.31 + /- 23.05
37.31 +/- 23.05
56.41 + 1- 23.05
30.61 +/- 23.05
0
4.61 + /- 23.05
399.01 +/- 23.05
73.81 +/- 23.05
859.81 +/- 23.05
869.91 +/- 23.05
0
0
7.41 + /- 23.05
352.01 +/- 23.05
421.81 +/- 23.05
0
A*Three levels calculated as per the suggestion by Dr. Marie Tuchman.
BMDL
BMDL
BMDL
8.00 +/-0.42
BMDL
BMDL
BMDL
BMDL
BMDL
20.83 + /- 1.20
3.96 + /- 1.24
99.03 +/- 1.23
152.66 +/- 1.23
BMDL
BMDL
BMDL
18.80 +/- 1.23
22.56 +/- 1.23
BMDL
•Average value obtained from 22 Blanks including 4 Trip Blanks. (Also, see below.)
Mean +/- S.D.= 89.39 + /- 23.05
* *Values are calculated based on the volume of water filtered.
0
0
0.967336
8.00356
0.890507
0.675482
1.001307
0
0
0.079683
0
0
20.82535
3.964213
99.03161
152.655
0
0
0.390192
18.80415
22.55688
0
0
0
0.5386608
7.5797718
0.482545
0.2582149
0.5921865
0
0
0
0
0
19.622327
2.7263045
97.804249
151.42893
0
0
0
17.572852
21.324267
0
0
0
1.3960106
8.42734859
1.29846885
1 .09274964
1.41042758
0
0
0.47778048
0
0
22.0283659
5.20212084
100.258972
153.881037
1.18887928
0
1.60334158
20.0354428
23.7894914
0.00334158
-------
ve
VD
able 21 (Continued^
Background Total PCBs level calculations.
Sam.
No.
2
5
6
15
16
24
25
34
35
44
53
54
63
64
74
75
76
80
47
14
26
62
Date
10/17/90
10/19,'90
10/19/90
10/23/90
10/23/90
10/29/90
10/29/90
10/31/90
10/31/90
11/6/90
11/9/90
11/9/90
11/14/90
11/14/90
12/6/90
12/6/90
7/30/91
8/16/91
11/9/90
10/22/90
10/31/90
11/13/90
Sample ID
BLANK1017B
BLANK1019A
BLANK1019B
BLANK1023A
BLANK1023B
BLANK1029A
BLANK1029B
BLANK1031A
BLANK1031B
BLANK 1106B
BLANK 1109A
BLANK 11 09 B
BLANK1114A
BLANK1114B
BLANK1 206A
BLANK 1206B
BLANK910730A
BLANK910816A
TRIP BLANK
TRIP-BLANK
TRIP-BLANK
TRIP-BLANK
Average(N = 22)
1 st extractio
(ng/samp)
40.7*
41.9*
67.9
46.4
56.2
45.7
39.4*
30.1**
38.9*
53.1
34.8*
64
30.2*
47
44.1
29.3*
48.4
33.2*
42.4*
29.8*
67.4
60
PCB Amount
2nd extraction
(ng/samp)
NRE
NRE
NRE
NRE
NRE
NRE
NRE
NRE
NRE
55.2
NRE
NRE
NRE
NRE
NRE
NRE
NRE
NRE
NRE
NRE
50
NRE
Average =
S.D (N = 22) Standard Deviation =
Total
(ng/samp)
81.40
83.80
135.80
92.80
112.40
91.40
78.80
60.20
77.80
108.30
69.60
128.00
60.40
94.00
88.20
58.60
96.80
66.40
84.80
59.60
117.40
120.00
89.39
23.05
'
NRE: no second time extraction. The total PCB amounts were calculated by multiplying the first time extraction by 2.
*These values were obtained from data which was below LOQ (Limit of Quantitation).
**This value was obtained from data which was below the IDL (Instrument Detection Limit).
-------
Table 2'*. ijata On Triplicate Sample Analysis
Sample
No ID
BR10105W1P
1
2
3
BR20104W1P
1
2
3
BR30104W1P
1
2
3
BR40101W1P
1
2
3
BR50104W1P
1
2
3
BR60104W1P
1
2
3
Analyte
Total PCBs
Total PCBs
Total PCBs
Total PCBs
Total PCBs
Total PCBs
Total PCBs
Total PCBs
Total PCBs
Total PCBs
Total PCBs
Total PCBs
Total PCBs
Total PCBs
Total PCBs
Total PCBs
Total PCBs
Total PCBs
Quantity
(ng/L
water,
PPt)
8.2
8.6
8.1
2.1
2.1
2.1
2.3
2.0
2.5
2.6
2.6
2.7
2.3
2.1
2.4
3.6
3.5
3.7
Detected
(ug/g,
sediment
ppm)
0.27
0.29
0.27
0.18
0.18
0.18
1.22
1.02
1.22
0.88
0.88
0.89
0.08
0.08
0.09
0.05
0.05
0.05
* Triplicate injection were carried out for the first extraction only.
100
-------
Table 23 Data On Matrix Check Analysis for Total PCBs
Sample
BR10106W1P
BR20105W1P
BR50104W1P
BR60104W1P
Actual
amount in
Sample
(ng)
27.6
33.2
31.7
49.5
Spiked
Amount
(ng)
50
50
40
80
Total
Recovered
Amount
(ng)
77.5
84.2
65.9
112
Recovery of
spiked
Amount
(%)
99.8
102
85.5
78.1
*Matrix spike recovery was carried out for the first extraction only.
101
-------
Table 24 Total PCBs (mg/kg) in Buffalo River Suspended Sediments Including CSO Samples, Fall 1990
PCB Quantitation: Total PCBs in Buffalo River Water Suspended Sediment Samples
Sam.
No.
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
(Glass liber filter samples)
(Revised - mg/kg)
IDLdnstrument detection limit): first time extraction, 64 pg/injection; second time extraction, 58 pg/injection in GC
LOQ(Limit of quantitation): first time extraction, 107 pg/injection in GC; second time extraction, 131 pg/injection in GC
MDUMethod detection limit) = 69.1ng/sample (3 x SD of background PCB levels)
BMDL(below method detection limit) =
-------
Table 24 (Continued)
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
10/27/90
10/27/90
10/27/90
10/27/90
10/29/90
10/29/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
1/5/90
1/5/90
1/5/90
1/5/90
1/5/90
1/5/90
1/5/90
11/6/90
11/6/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
BR10203W2P
BR20104W1P
BR20105W1P
BR20106W1P
BLANK1029A
BLANK1029B
TRIP-BLANK
BR30101W1P
BR30102W1P
BR30103W1P
BR30104W1P
BR30104W2P
BR30105W1P
BR30106W1P
BLANK1031A
BLANK1031B
BR40101W1P
BR40101W2P
BR40102W1P
BR40103W1P
BR40104W1P
BR40105W1P
BR40106W1P
BLANK 1106A
BLANK 1106B
BR50106W1P
BR50105W1P
TRIP BLANK
BR50104W1P
BR50103W1P
BR50102W1P
BR50102W2P
BR50101W1P
BLANK1109A
BLANK1109B
291.8
223.1
235.4
220.7
91.4
78.8
117.4
120.6
86.1
147.6
218.8
192.7
153.9
146.5
60.2
77.8
135.8
276
225
316.8
238.6
205.9
156.9
Sample was k
108.3
354.6
210.6
84.8
225.5
137.2
136.7
123.2
62.6
69.6
128
202.41 +/- 23.05
133.71 +/- 23.05
146.01 + /- 23.05
131.31 + /- 23.05
2.01 +/- 23.05
0
28.01 +/- 23.05
31.21 +/- 23.05
0
58.21 +/- 23.05
129.41 +/- 23.05
103.31 +/- 23.05
64.51 +/- 23.05
57.11 +/- 23.05
0
0
46.41 +/- 23.05
186.61 +/- 23.05
135.61 +/- 23.05
227.41 +/- 23.05
149.21 + /- 23.05
116.51 +/- 23.05
67.51 +/- 23.05
>st during analysis.
18.91 + /- 23.05
265.21 +/- 23.05
121.21 +/- 23.05
0
136.11 +/- 23.05
47.81 +/- 23.05
47.31 + /- 23.05
33.81 +/- 23.05
0
0
38.61 + /- 23.05
0.89 +/-0.10
0.20 + /- 0.034
0.84 +/-0.13
0.23 +/- 0.040
BMDL
BMDL
BMDL
1.14 +/-0.20
0.30 + /- 0.068
BMDL
BMDL
BMDL
1.65 +/-0.20
0.19 +/- 0.033
0.19 +/- 0.017
1.31 +/-0.20
0.26 + /- 0.051
BMDL
0.18 +/- 0.016
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
0.8942112
0.1951112
0.8401729
0.2279474
0.182921
0
0.2576965
1.1404092
0.3042216
0.0551639
1 .003402
0.2744096
1.6453327
0.1949508
0.1685145
1.3100407
0.2562767
0.2973645
0.1847818
0.0785388
0.0904241
0.0302664
0.0305013
0
0.7923829
0.1614775
0.7075424
0.1879351
0.0478422
0
0.1556609
0.9372911
0.236348
0.0354546
0.5984503
0.1381328
1.4421071
0.1618156
0.1514344
1.1076716
0.2055776
0.1958412
0
0.0156419
0.0156757
0.0751115
0.0636039
0.1687223
0.99603945
0.228744951
0.972803326
0.267959606
0.317999824
0.087325424
0.359732138
1.343527406
0.372095082
0.074873227
1.408353654
0.410686354
1.848558367
0.228086037
0.1855945
1.512409921
0.306975827
0.398887817
0
0.045360682
0.044857124
0.1057368
0.093473648
0.200841292
o
OJ
-------
Table 24 (Continued)
55
56
57
58
59
60
61
62
63
64
68
69
70
71
72
73
74
75
76
78
79
80
11/13,r90
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
11/14/90
11/14/90
12/5/90
12/5/90
12/5. '90
12/5. '90
12/5/90
12/5/90
12/6/90
12/6/90
7/30/91
8/9/91
8/9/91
8/16/91
BR60101W1P
BR60102W1P
BR60103W1P
BR60104W1P
BR60105W1P
BR60105W2P
BR60106W1P
TRIP-BLANK
BLANK1114A
BLANK1114B
BLANK1 205A
BLANK 1205B
CSO-4W1P(Ba)
CSO-2W1P(Ca)
CSO-4W1P(Sm)
CSO-4W1P(Ha)
BLANK1206A
BLANK1206B
BLANK910730A
CSO-SM0809
CSO-HM-0809
BLANK910816A
60.8
29
141.4
524.7
139.7
126.7
145.8
120
60.4
94
Test analysis
Test analysis
488.4
163.2
1949.2
2959.3
88.2
58.6
96.8
441.4
511.2
66.4
0
0
52.01 +/- 23.05
435.31 + /- 23.05
50.31 +/- 23.05
37.31 +/- 23.05
56.41 + /- 23.05
30.61 + /- 23.05
0
4.61 + /- 23.05
399.01 +/- 23.05
73.81 +/- 23.05
BMDL
BMDL
BMDL
0.11 +/- 0.0056
BMDL
BMDL
BMDL
859.81 +/- 23.05
869.91 + /- 23.05
0
0
7.41 +/- 23.05
352.01 +/- 23.05
421.81 +/- 23.05
0
A*Three levels calculated as per the suggestion by Dr. Marie Tuchman.
*Average v
-
Mean +/- S.D.= 89.39 +/- 23.05
0.522 +/- 0.0342
0.836 +/- 0.0456
***Values are calculated based on the TSS data obtained from Alfred Analytical Lab.
0
0
0.0604585
0.10531
0.2226267
0.0422176
0.1251634
0.5223374
0.83544
0
0
0.0336663
0.0997338
0.1206362
0.0161384
0.0740233
0.4881348
0.7897877
0
0
0.087250663
0.110886166
0.324617212
0.068296852
0.176303448
0.556540079
0.881092276
-------
Table 25 Total PCBs Data Represented As ng/L vs. mg/kg of Buffalo River Suspended Sediments Fall, 1990
PCB Quantitation: Total PCBs in Buffalo River Water Suspended Sediment Samples
Sam.
No.
1
2
3
4
5
6
7
8
9
10
(Glass fiber filter samples)
IDLdnstrument detection limit): first time extraction, 64 pg/injection; second time extraction, 58 pg/injection in GC
LOQdimit of quantitation): first time extraction, 107 pg/injection in GC; second time extraction, 131 pg/injection in GC
MDUMethod detection limit) = 69.1ng/sample (3 x SD of background PCB levels)
BMDLfbelow method detection limit) =
-------
Table 25 (Continued)
Sam.
No.
11
12
13
14
15
16
17
18
19
20
21
22
IDLHnstrument detection limit): first time extraction, 64 pg/injection; second time extraction, 58 pg/injection in GC
LOQ(Limit of quantitation): first time extraction, 107 pg/injection in GC; second time extraction, 131 pg/injection in GC
MDUMethod detection limit) = 69. Ing/sample (3 x SD of background PCB levels)
BMDLfbelow method detection limit) =
-------
Table 25 (Continued)
Sam.
No.
23
24
25
26
27
28
29
30
31
32
33
34
IDLdnstrument detection limit): first time extraction, 64 pg/injection; second time extraction, 58 pg/injection in GC
LOQ(Limit of quantisation): first time extraction, 107 pg/injection in GC; second time extraction, 131 pg/injection in GC
MDMMethod detection limit) = 69.1ng/sample (3 x SD of background PCB levels)
BMDLfbelow method detection limit) =
-------
Table 25 (Continued)
Sam.
No.
35
36
37
38
39
40
41
42
43
44
52
50
IDLdnstrument detection limit): first time extraction, 64 pg/injection; second time extraction, 58 pg/injection in GC
LOQ(Limit of quantitation): first time extraction, 107 pg/injection in GC; second time extraction, 131 pg/injection in GC
MDMMethod detection limit) = 69.1ng/sample (3 x SD of background PCB levels)
BMDLfbelow method detection limit) =
-------
Table 25 (Continued)
Sam.
No.
51
49
48
46
45
47
53
54
55
56
57
58
IDMInstrument detection limit): first time extraction, 64 pg/injection; second time extraction, 58 pg/injection in GC
LOQILimit of quantitation): first time extraction, 107 pg/injection in GC; second time extraction, 131 pg/injection in GC
MDLIMethod detection limit) = 69.1ng/sample (3 x SD of background PCB levels)
BMDLfbelow method detection limit) =
-------
Table 25 (Continued)
Sam.
No.
59
60
61
62
63
64
68
69
70
71
72
73
IDLdnstrument detection limit): first time extraction, 64 pg/injection; second time extraction, 58 pg/injection in GC
LOQ{Limit of quantitation): first time extraction, 107 pg/injection in GC; second time extraction, 131 pg/injection in GC
MDUMethod detection limit) = 69.1ng/sample (3 x SD of background PCB levels)
BMDLf below method detection limit) =
-------
Table 25 (Continued)
Sam.
No.
74
75
76
78
79
80
IDLdnstrument detection limit): first time extraction, 64 pg/injection; second time extraction, 58 pg/injection in GC
LOQ(Limit of quantitation): first time extraction, 107 pg/injection in GC; second time extraction, 131 pg/injection in GC
MDLIMethod detection limit) = 69.1ng/sample (3 x SD of background PCB levels)
BMDLfbelow method detection limit) =
-------
8.2.4. TOTAL PCBs (PARTICULATE PHASE) SPRING, 1992
112
-------
Table 26 Total PCBs In Buffalo River Suspended Sediments (Spring, 1992 Samples) (ng/L)
PCB Quantitation: Total PCBs in Buffalo River Suspended Sediment Samples (Spring Event Samples)
Sam.
No.
1P
2P
3P
4P
5P
6P
7P
8P
9P
10P
11P
12P
13P
UP
15P
16P
17P
18P
Glass fiber filter samples, ng/L)
DUInstrument detection limit) = 75 pg/injection in GC
LOCKLimit of quantitation) = 1 1 2 pg/injection in GC
MDUMethod detection limit) = 25.3ng/sample (3 x SD of background PCB levels)
BMDLfbelow method detection limit) =
-------
Table 26 (Continued)
These data were obtained using a Varian GC 3400 equipped with ECD detector and a DB-5 capillary
column-30m, 0.25 mm id, 0.25 micron film thickness.
* Average value obtained from 5 Blanks. (Also, see below.)
(Sample No.: 1P, 6P, 11P, 16P.17P)
Mean +/- S.D.= 64.908 + /- 8.421
**Three levels calculated as per the suggestion by Dr. Marc Tuchman.
**This sample has TCMX recovery is 85.77%
***This sample has TCMX recovery is 75.66%
Background Total PCBs level calculations.
Sam.
No.
1P
6P
11P
16P
17P
Date
April 16, '92
April 17, '92
April 18, '92
April 22, '92
April 22, '92
Sample ID
Blank (Initial)
Blank (af ter SBR1)
BlanMafter SBR2)
Blank (final)
Trip Blank
Average
S.D.
PCB
Amount- 1
(ng/samp)
62.254132
75.818264
55.404376
71.296244
59.76813
64.9082
8.4206
'
-------
Table 27 Total PCBs in Buffalo River Suspended Sediment Samples (Spring 1992 Samples) (mg/kg)
PCB Quantitation: Total PCBs in Buffalo River Suspended Sediment Samples (Spring Event Samples)
Sam.
No.
1P
2P
3P
4P
5P
6P
7P
8P
9P
10P
11P
12P
13P
14P
15P
16P
17P
18P
(Glass fiber filter samples, mg/kg)
IDLdnstrument detection limit) = 75 pg/injection in GC
LOQdimit of quantitation) = 112 pg/injection in GC
MDUMethod detection limit) = 25.3ng/sample (3 x SD of background PCB levels)
BMDUbelow method detection limit) =
-------
v
*
These data were obtained using a Varian GC 3400 equipped with ECD detector and a DB-5 capillary
column-30m, 0.25 mm id, 0.25 micron film thickness.
* Average value obtained from 5 Blanks. (Also, see below.)
(Sample No.: 1P, 6P, 1 1P, 16P.17P)
Mean +/-S.D.= 64.908 +/- 8.421
A*Three levels calculated as per the suggestion by Dr. Marc Tuchman.
Background Total PCBs level calculations.
Sam.
No.
1P
6P
11P
16P
17P
Date
April 16, '92
April 17, '92
April 18, '92
April 22, '92
April 22, '92
Sample ID
Blank (Initial)
Blankfafter SBR1)
BlanMafter SBR2)
Blank (final)
Trip Blank
Average
S.D.
PCB
Amount-1
(ng/samp)
62.254132
75.818264
55.404376
71.296244
59.76813
64.9082
8.4206
-------
8.2.5. PESTICIDES (DISSOLVED PHASE) FALL, 1990
117
-------
Table 28 Pesticide Levels in Buffalo River Water, Including CSO Samples, Fall 1990
Sam.
No.
1
2
3
4
5
6
7
|Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
IDL = Instrument detection limit
LOQ= Limit of quantitation
IDL
1 .40 pg
1.74pg
1 .90 pg
4.40 pg
BDL (below detection limit) = < IDL
LOQ
3.84 pg
4.25 pg
3.91 pg
9.62 pg
BQL (below quantitation limit) = < LOQ and > IDL
Surrogate standard used-
QL (ref. footnote P-12)
0.028 ng/L
0.031 ng/L
0.284 ng/L
0.070 ng/L
2,2',3,31,4,4',5,5I,6,6I-Decachlorobiphenyl
Test Analysis- ref. footnote page- 12
Date
10/17/90
10/17/90
10/18/90
10/18/90
10/19/90
10/19/90
10/22/90
Sample ID
BLANK 1017A
BLANK 1 01 7B
BR10101W1D
BR10102W1D
BLANK1019A"
BLANK1019B"
BR10101W1D*
Analyte
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
|
Quantity
Detected
(ng/L water)
(ppt)
Test analysis
Test analysis
Test analysis
Test analysis
Test analysis
Test analysis
Test analysis
Test analysis
BQL
0.02523126
BDL
BDL
BDL
0.02763067
BDL
BDL
Already reported
Already reported
Already reported
Already reported
Test analysis
Test analysis
Test analysis
Test analysis
BDL
BDL
Test analysis
BDL
Surrogate
Spike
Recovery
(%)
108.74581
119.2618
58.827313
118
-------
Table 28 (Continued)
Sam.
No.
8
9
10
11
12
13
15
|Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
IDL = Instrument detection limit
LOQ = Limit of quantitation
IDL
1 .40 pg
1 .74 pg
1 .90 pg
4.40 pg
BDL (below detection limit) = < IDL
LOQ
3.84 pg
4.25 pg
3.91 pg
9.62 pg
BQL (below quantitation limit) = < LOQ and > IDL
QL (ref. footnote P-12)
0.028 ng/L
0.031 ng/L
0.284 ng/L
0.070 ng/L
Surrogate standard used- 2,21,3,3',4,4',5,5',6,6'-Decachlorobiphenyl
Test Analysis- ref. footnote page-1 2
Date
10/22,'90
10/22/90
10/22/90
10/22/90
10/22/90
10/22/90
10/23/90
Sample ID
BR10102W1D"
BR10103W1D"
BR10103W2D"
BR10104W1D
BR10105W1D
BR10106W1D
BLANK 1023A
Analyte
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
Quantity
Detected
(ng/L water)
(ppt)
BDL
BDL
Test analysis
BDL
BDL
BQL
Test analysis
BQL
Already reported
Already reported
Already reported
Already reported
BQL
0.04559725
BDL
BDL
BDL
BQL
BDL
BDL
BDL
0.06804393
BDL
BDL
Test analysis
Test analysis
Test analysis
Test analysis
Surrogate
Spike
Recovery
(%)
56.613538
55.93799
118.56118
113.12187
109.41956
119
-------
Tat
ile 28 (Continued)
Sam.
No.
16
17
18
19
20
21
22
Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4' -DDT (DDT)
IDL = Instrument detection limit
LOQ= Limit of quantitation
IDL
1.40pg
1 .74 pg
1 .90 pg
4.40 pg
BDL (below detection limit) = < IDL
LOQ
3.84 pg
4.25 pg
3.91 pg
9.62 pg
BQL (below quantitation limit) = < LOQ and > IDL
Surrogate standard used-
QL (ref . footnote P-1 2)
0.028 ng/L
0.031 ng/L
0.284 ng/L
0.070 ng/L
2,2',3,3',4,4',5,5I,6,61-Decachlorobiphenyl
Test Analysis- ref. footnote page-12
Date
10/23/90
10/27/90
10/27/90
10/27/90
10/27/90
10/27/90
10/27/90
Sample ID
BLANK1023B
BR20101W1D
BR201 02W1 D
BR20103W1D
BR20103W2D
BR20104W1D
BR20105W1D
Analyte
G-CHL
A-CHL
Diet.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
Quantity
Detected
(ng/L water)
(ppt)
Test analysis
Test analysis
Test analysis
Test analysis
BQL
0.03338992
BDL
BDL
BQL
BQL
BDL
BDL
BDL
BQL
BDL
BDL
BQL
BQL
BDL
BDL
BQL
BQL
[BDL
BDL
BQL
BQL
BDL
BDL
Surrogate
Spike
Recovery
(%)
113.55612
99.57957
100.39658
96.499536
93.4486
106.68872
120
-------
Table 28 (Continued)
Sam.
No.
23
24
25
26
27
.28
29
Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
IDL = Instrument detection limit
LOQ= Limit of quantitation
IDL
1 .40 pg
1 .74 pg
1 .90 pg
4.40 pg
BDL (below detection limit) = < IDL
LOQ
3.84 pg
4.25 pg
3.91 pg
9.62 pg
BQL (below quantitation limit) = < LOO. and > IDL
Surrogate standard used-
QL (ref. footnote P-1 2)
0.028 ng/L
0.031 ng/L
0.284 ng/L
0.070 ng/L
2,2',3,3',4,4',5,5',6,6'-Decachlorobiphenyl
Test Analysis- ref. footnote page-12
Date
10/27/90
10/29. '90
10/29/90
10/31/90
10/31/90
10/31/90
10/31/90
Sample ID
BR20106W1D
BLANK1029A
BLANK1029B
TRIP-BLANK
BR30101W1D
BR30102W1D
BR30103W1D
Analyte
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
Quantity
Detected
(ng/L water)
(ppt)
BQL
BQL
BDL
BDL
Test analysis
Test analysis
Test analysis
Test analysis
Test analysis
Test analysis
Test analysis
Test analysis
BDL
BDL
BDL
BDL
BQL
BQL
BDL
BDL
BQL
BDL
BDL
BDL
BQL
BQL
BDL
BDL
Surrogate
Spike
Recovery
(%)
100.34286
98.29473
107.42067
111.42517
86.375266
121
-------
Table 28 (Continued)
Sam.
No.
30
31
32
33
34
35
36
|Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
IDL = Instrument detection limit
LOQ = Limit of quantitation
IDL
1 .40 pg
1 .74 pg
1.90pg
4.40 pg
BDL (below detection limit) - < IDL
LOQ
3.84 pg
4.25 pg
3.91 pg
9.62 pg
BQL (below quantitation limit) = < LOQ and > IDL
Surrogate standard used-
Date
10/31. '90
10/31. '90
10/31/90
10/31/90
10/31/90
10/31/90
11/5/90
Sample ID
BR30104W1D
BR30104W2D
BR30105W1D
BR30106W1D
BLANK1031A
BLANK 1 03 1B
BR40101W1D
QL (ref. footnote P-12)
0.028 ng/L
0.031 ng/L
0.284 ng/L
0.070 ng/L
2,2',3,3',4,41,5,5',6,6'-Decachlorobiphenyl
Analyte
G-CHL
A-CHL
Die).
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
Quantity
Detected
(ng/L water)
(ppt)
0.04370565
BQL
BDL
BQL
BQL
BQL
BDL
BDL
0.02937495
BQL
BDL
BDL
BQL
BQL
BDL
BDL
BDL
BDL
BDL
BDL
BQL
BDL
BDL
BDL
BDL
BQL
BDL
BDL
Surrogate
Spike
Recovery
(%)
68.584486
95.819063
85.9925
97.298643
89.900741
99.176658
50.809375
122
-------
Ta
le 28 fCoi
Sam.
No.
37
38
39
40
41
42
43
tinuetn
Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
IDL = Instrument detection limit
LOQ= Limit of quantitation
IDL
1 .40 pg
1 .74 pg
1.90pg
4.40 pg
BDL (below detection limit) = < IDL
LOQ
3.84 pg
4.25 pg
3.91 pg
9.62 pg
BQL (below quantitation limit) = < LOQ and > IDL
Surrogate standard used-
Date
11/5/90
11/5/90
11/5/90
11/5/90
11/5/90
11/5/90
11/6/90
Sample ID
BR40101W2D
BR40102W1D
BR40103W1D
BR40104W1D
BR40105W1D
BR40106W1D
BLANK 1106A
QL (ref. footnote P-12)
0.028 ng/L
0.031 ng/L
0.284 ng/L
0.070 ng/L
2,2',3,3',4,41,5,5'/6,61-Decachlorobiphenyl
Analyte
G-CHL
A-CHL
Diet.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
Quantity
Detected
(ng/L water)
(ppt)
BQL
BQL
BDL
BDL
BQL
BQL
BDL
BDL
BQL
BQL
BDL
BDL
BQL
BQL
BDL
BDL
BQL
BQL
BDL
BDL
BQL
BQL
BQL
BDL
BDL
BDL
BDL
BDL
Surrogate
Spike
Recovery
{%)
103.56839
87.310916
101.0972
87.494464
92.181668
111.19685
116.74584
123
-------
Table 28 (Continued)
I / ' ' .1.1
Sam.
No.
44
45
46
47
48
49
50
Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
L 4,4' -DDT (DDT)
IDL = Instrument detection limit
LOQ= Limit of quantitation
IDL
1 .40 pg
1 .74 pg
1 -90 pg
4.40 pg
BDL (below detection limit) = < IDL
LOQ
3.84 pg
4.25 pg
3.91 pg
9.62 pg
BQL (below quantitation limit) = < LOQ and > IDL
Surrogate standard used-
Date
11/6/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
Sample ID
BLANK1106B
BR50106W1D
BR50105W1D
TRIP BLANK
BR501O4W1D
BR50103W1D
BR50102W1D
QL (ref. footnote P-12)
0.028 ng/L
0.031 ng/L
0.284 ng/L
0.070 ng/L
2,2',3,3',4,4',5,5',6,6'-Decachlorobiphenyl
Analyte
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
Quantity
Detected
(ng/L water)
(ppt)
BDL
BDL
BDL
BDL
BQL
BQL
BDL
BDL
BQL
BQL
BDL
BDL
BDL
BDL
interefered
BDL
BQL
BQL
BDL
BDL
BDL
BDL
BDL
BDL
BQL
BQL
BDL
BDL
Surrogate
Spike
Recovery
(%)
100.80397
96.889017
98.133565
98.243247
102.80286
98.493947
109.43076
124
-------
Table 28 (Continued)
Sam.
No.
51
52
53
54
55
56
57
Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
IDL = Instrument detection limit
LOQ= Limit of quantitation
IDL
1 .40 pg
1 .74 pg
1 .90 pg
4.40 pg
BDL (below detection limit) = < IDL
LOQ
3.84 pg
4.25 pg
3.91 pg
9.62 pg
BQL (below quantitation limit) = < LOQ and > IDL
QL (ref. footnote P-12)
0.028 ng/L
0.031 ng/L
0.284 ng/L
0.070 ng/L
Surrogate standard used- 2,2',3,3',4,41,5,5'/6,6'-Decachlorobiphenyl
Date
11/9/90
11/9/90
11/9/90
11/9/90
11/13/90
11/13/90
11/13/90
Sample ID
BR50102W2D
BR50101W1D
BLANK1109A
BLANK1109B
BR60101W1D
BR60102W1D
BR60103W1D
Analyte
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
Quantity
Detected
(ng/L water)
(ppt)
0.02980954
BQL
BDL
BDL
BQL
BQL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BQL
BDL
BDL
BDL
BDL
BDL
BDL
0.03741038
0.0393753
BDL
BQL
Surrogate
Spike
Recovery
(%)
1 1 1 .02002
103.49453
104.81518
69.721592
99.644483
96.645031
98.892382
125
-------
Table 28
Sam.
No.
58
59
60
61
62
63
64
(Continued)
Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
IDL = Instrument detection limit
LOQ= Limit of quantitation
IDL
1 .40 pg
1.74pg
1 .90 pg
4.40 pg
r
BDL (below detection limit) = < IDL
LOQ
3.84 pg
4.25 pg
3.91 pg
9.62 pg
BQL (below quantitation limit) = < LOQ and > IDL
Surrogate standard used-
Date
11/13,'90
11/13/90
11/13/90
11/13/90
11/13/90
11/14/90
11/14/90
Sample ID
BR60104W1D
BR60105W1D
BR60105W2D
BR60106W1D
TRIP-BLANK
BLANK1114A
BLANK1114B*
QL (ref . footnote P-1 2)
0.028 ng/L
0.031 ng/L
0.284 ng/L
0.070 ng/L
2,2',3,3',4,41,5f5',6,6'-Decachlorobiphenyl
Analyte
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
Quantity
Detected
(ng/L water)
(ppt)
BQL
BQL
BDL
BDL
BQL
BQL
BDL
BDL
BDL
BQL
BDL
BDL
BQL
BQL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
Surrogate
Spike
Recovery
(%)
96.470436
106.7111
109.06814
99.078169
99.051308
100.12574
95.608654
126
-------
Table 28 (Continued)
Sam.
No.
68
69
„•>
70
71
72
73
74
Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
IDL = Instrument detection limit
LOQ= Limit of quantitation
IDL
1 .40 pg
1.74pg
1 .90 pg
4.40 pg
BDL (below detection limit) - < IDL
LOQ
3.84 pg
4.25 pg
3.91 pg
9.62 pg
BQL (below quantitation limit) = < LOG and > IDL
Surrogate standard used-
Date
12/5/90
12/5. '90
12/5/90
12/5/90
12/5/90
12/5/90
12/6/90
Sample ID
BLANK1205A
BLANK1205B
CSO-1W1D(Ba)
CSO-2W1D(Ca)
CSO-3W1D(Sm)
CSO-4W1 D(Ha)
BLANK1206A
QL (ref. footnote P-12)
0.028 ng/L
0.031 ng/L
0.284 ng/L
0.070 ng/L
2,2',3,3',4,4',5,5I/6,6'-Decachlorobiphenyl
Analyte
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
Quantity
Detected
(ng/L water)
(ppt)
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BQL
BQL
BDL
BDL
BQL
BDL
BDL
BDL
BQL
BQL
BDL
BDL
BQL
BQL
BDL
BQL
BDL
BDL
BDL
BDL
Surrogate
Spike
Recovery
(%)
85.305312
101.0793
93.992531
95.12516
109.71951
93.124033
100.85769
127
-------
Table 28 (Continued/)
Sam.
No.
75
76
78
79
80
81
JAnalyte IDL
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
IDL = Instrument detection limit
LOQ= Limit of quantitation
1 .40 pg
1.74pg
1.90pg
4.40 pg
BDL (below detection limit) - < IDL
LOQ
3.84 pg
4.25 pg
3.91 pg
9.62 pg
SQL (below quantitation limit) = < LOO. and > IDL
Surrogate standard used-
Date
12/6.'90
7/30/91
8/9/91
8/9/91
8/16/91
6/2, '92
Sample ID
BLANK1206B
BLANK910730A
CSO-SM0809
CSO-HM-0809
BLANK910816A
REAGENT BLANK
QL (ref . footnote P-1 2)
0.028 ng/L
0.031 ng/L
0.284 ng/L
0.070 ng/L
2,2',3,3',4,4',5,5'f6,61-Decachlorobiphenyl
Analyte
G-CHL
A-CHL
Diet.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
G-CHL
A-CHL
Diel.
DDT
Quantity
Detected
(ng/L water)
(ppt)
BDL
BDL
BDL
BDL
BQL
BDL
BDL
BDL
0.25316368
0.17909484
BQL
BQL
0.10533991
0.10565785
BQL
BQL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
Surrogate
Spike
Recovery
(%)
101.18674
97.341173
90.471532
106.83645
93.665725
86.733409
128
-------
Table 28 (Continued)
QL (quantitation limit):
Quantitation limit (generalized) was calculated based on fifty five
{litres of water sample
LOQ x100uLx4/55L. for chlordane and
DDT;
LOQ= Limit of quantitation of the instrument
100uL is final extract volume . GC injection volume 1uL
Original sample extract is 4mL (2mL goes to
PAHs portion, 1 mL goes to Dieldrin portion)
remaining 1 mL treated with concentrated sulfuric acid and microconcentration to 1 00 uL)
LOQx1000uLx4/55L for DIELDRIN)
LOQ= Limit of quantitation of the instrument
1 0OOuL is final extract volume . GC injection volume 1 uL.
Microconcentration of this extract
due to high
(1 mL) was not possible
amount of impurities in the sample. Sulfuric acid treatment also
could not be performed since dieldrin decomposes when treated with concentrated
sulfuric acid.
Original sample extract is 4mL (2mL goes to PAHs portion, 1mL goes to DDT and
chlordane, remaining 1mL is used
for Dieldrin
*Data for this sample had abnormal peaks at the analytes'
analysis).
retention times.
* The low percentage recovery of the surrogate standards
is due to the problem encountered
during the Soxhlet extraction of the XAD-2 resin. This problem was addressed to EPA
on the phone and Fax (Sept. 23, 91) to Richard G. Fox.
Test Analysis:
Soxhlet extraction of resin samples gave about 1 0-30ml liquid which is not
concentrated to lower volume. The boiling point of this liquid was >100 C and is
soluble in methylene chloride , hexane and other organic solvents. This caused
problem in analyzing trace organics.
This problem was discussed with Richard G. Fox , GLNPO, US EPA (March 24, 25,
1 992) and other scientists engaged in similar kind of analysis and also the
University of Wisconsin- Superior,
of identifying the causative factor
who supplied XAD-2 resin. In the process
we extracted blanks (not the samples).
GC-MS analysis of the extract revealed that the liquid is DIACETONE ALCOHOL
(boiling point 166 C). This diacetone alcohol might have formed due to
aldol condensation process that might have occurred during the storage
of resin samples in acetone under 4 C in refrigerator. We came to know
that Tom Markee's lab (Univ. Wisconsin-Superior) also encountered
similar problem in their samples. Since diacetone alcohol (b.p 166. C)
is soluble in
water, Wisconsin- Superior lab dissolved the diacetone alcohol
in excess amount of nanopure water and extracted the PCBs by hexane in
a separatory funnel. Since we analyze not only PCBs and pesticides but also
PAHs, we tested whether the hexane -water partitioning method works for our
analytes of
interest. We did recovery tests using PCB congener, pesticide and
PAHs. We repeated the test with
four more blanks and the recovery of the analytes
were 100 + 7-30%. The results were discussed with Richard Fox. After the tests
using blanks, the samples were analyzed.
129
-------
Table 29 Pesticide Levels in Buffalo River Water, Including CSO
Samples, Fall 1990, Triplicate Injections
Triplicate Injections for Pesticides in Water Samples
Sample ID
BR10105W1D
BR20106W1D
BR30102W1D
BR40101W1D
BR50103W1D
BR60102W1D
CSO-SM- 0809
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
Gamma-Chlordane
Amount
(ng/samp)
0.390478
0.38792
0.388772
0.639428
0.621524
0.608736
0.595095
0.594242
0.659038
0.541383
0.559287
0.554171
0.54053
0.518363
0.534562
0.316304
0.370016
0.351259
4.478557
4.625199
4.718982
Cone.
in Water
(ng/L)
BDL
BDL
BDL
BQL
BQL
BQL
BQL
BQL
BQL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
0.246075
0.254132
0.259285
Alpha-Chlordane
Amount
{ng/samp)
1 .603396
1.695752
1.747915
0.88764
0.926977
0.943224
0.584064
0.584919
0.625966
0.720887
0.716611
0.753382
0.513087
0.506246
0.519928
0.579788
0.59176
0.628531
3.217909
3.251259
3.309409
Cone.
in Water
(ng/L)
BQL
BQL
0.033421
BQL
BQL
BQL
BDL
BDL
BDL
BQL
BQL
BQL
BDL
BDL
BDL
BDL
BDL
BDL
0.176808
0.178641
0.181836
130
-------
Table 29 (Continued")
Triplicate Injections for Pesticides in Water Samples
Sample ID
BR10104W1D
BR20105W1D
BR30104W2D
BR40102W1D
BR50106W1D
BR60106W1D
CSO-SM0809
CSO-HM-0809
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
Dieldrin
Amount
(ng/samp)
5.729539
6.029613
5.729539
5.401333
4.70741 1
5.692029
4.313564
4.266678
3.994736
5.523238
5.241918
6.095254
5.354446
5.1669
5.476351
5.204409
5.232541
5.073127
14.73176
13.61586
15.7914
10.36193
9.874311
10.88706
Cone.
in Water
(ng/L)
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BQL
BQL
0.867659
BQL
BQL
BQL
131
-------
Table 29 (Continued)
Triplicate Injections for Pesticides in Water Samples
Sample ID
BR10105W1D
BR20106W1D
BR30102W1D
BR40101W1D
BR50103W1D
1
2
3
1
2
3
1
2
3
1
2
3
L 1
2
3
)
BR60102W1D
CSO-SM0809
1
2
3
1
2
3
4,4'-DDT
Amount
(ng/samp)
no peak
no peak
no peak
0.179623
0.317681
0.307289
0.461676
0.437924
0.461676
no peak
no peak
no peak
0.317681
0.310258
0.308774
no peak
no peak
no peak
3.629574
3.491517
3.537536
Cone.
r in Water
(ng/L)
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BQL
BQL
BQL
132
-------
8.2.6. PESTICIDES (DISSOLVED PHASE) SPRING, 1992
133
-------
Table 30 List of Sample Abbreviations
S
BR
1 through 6
01
01-06
W
1
2
D
P
IDL
LOQ
Spring Event
Buffalo River
Survey Number
Composite
Station
Sample Type; Water
Regular
Duplicate
Dissloved
Paniculate
Instrument Detection Limit
Limit of Quantitation
134
-------
1.0
Table 31 Pesticide Concentrations in Buffalo River Water (Spring, 1992 Samples)
Sam.
No.
1D
2D
3D
4D*
5D**
6D
7D
ANALYTE
Gamma-chlordane (G-CHL]
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
IDL
1.88
2.17
2.06
7.08
IDL = Instrument detection limit
LOQ= Limit of quantitation
BDL (below detection limit) = < IDL
LOQ
5.19
5.45
5.64
22.42
BQL (below quantitation limit) = < LOQ but > IDL
Date
1 6-Apr
4/1 7/92
4/1 7/92
4/1 7/92
4/1 7/92
4/1 7/92
4/1 8/92
Sample ID
BLANK
SBR10101W1D
SBR10101W2D
SBR10103W1D
SBR10106W1D
BLANK
SBR20101W1D
Analyte
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
Quantity
Detected
(ng/L water)
(ppt)
BDL
BDL
BDL
BDL
BQL
0.05
BDL
BDL
QLfref.page 3&4)
0.037ng/L
0.039ng/L
0.410ng/L
0.163ng/L
Surrogate
Spike@
Recovery
{%)
81.81
87.82
Sample lost during analysis .
BDL
BDL
BDL
BDL
BQL
0.05
BDL
BDL
Test analysis)?
BQL
BQL
BDL
BDL
82.49
86.35
84.00
135
-------
Table 31 (Continued)
Sam.
No.
8D**
9D
10D
11D
12D*
13D
14D
IANALYTE
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
| Dieldrin
4,4'-DDT (DDT)
IDL
1.88
2.17
2.06
7.08
IDL = Instrument detection limit
LOQ= Limit of quantitation
BDL (below detection limit) = < IDL
LOQ
5.19
5.45
5.64
22.42
SQL (below quantitation limit) - < LOQ but > IDL
Date
1 8-Apr
4/1 8/92
4/1 8/92
4/1 8/92
4/22/92
4/22/92
4/22/92
Sample ID
SBR20103W1D
SBR20103W2D
SBR20106W1D
BLANK
SBR30101W1D
SBR30103W1D
SBR30106W1D
Quantity
Analyte
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
Detected
(ng/L water)
(ppt)
BDL
BQL
BDL
BDL
BDL
BQL
BDL
BDL
BDL
BQL
BDL
BDL
BDL
BDL
BDL
BDL
BQL
BQL
BDL
BDL
BQL
0.06
BDL
BDL
BQL
BQL
BDL
BDL
QLIref .page 3&4)
0.037ng/L
0.039ng/L
0.410ng/L
0.163ng/L
Surrogate
Spike®
Recovery
(%)
85.79
91.49
88.29
86.04
87.28
95.84
94.77
136
-------
Table 31 (Continued)
Sam.
No.
15D
16D
17D
18D
ANALYTE
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
IDL
1.88
2.17
2.06
7.08
IDL = Instrument detection limit
LOQ= Limit of quantitation
BDL (below detection limit) = < IDL
LOQ
5.19
5.45
5.64
22.42
BQL (below quantitation limit) = < LOQ but > IDL
Date
4/22/92
4/22/92
4/22/92
8/31/92
Sample ID
SBR30106W2D
BLANK
Trip Blank
Reagent Blank
Analyte
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
Quantity
Detected
(ng/L water)
(ppt)
BQL
BQL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
QL(ref .page 3&4)
0.037ng/L
0.039ng/L
0.410ng/L
0.163ng/L
Surrogate
Spike@
Recovery
(%)
95.67
100.14
96.04
99.10
These data were obtained using Hewlett Packard GC Series II equiped with DB-1701
megabore column (30m,0.53mm id, 1 micron film thickness).
QL (Quantitation limit): Quantitation limit (generalized ) was calculated based on
55 liters of water sample(i.e. LOQ x 100uLx4/55L . for chlordane and DDT;
LOQ = Limit of quantitation of instrument
1 0OuL is final extract volume . GC injection volume 1 uL
Original sample extract is 4mL (2mL goes to PAHs portion, 1 mL goes to Dieldrin portion)
remaining 1 mL treated with concentrated sulf uric acid and microconcentration to 1 00 uL)
LOQx1000uLx4/55L for DIELDRIN)
LOQ= Limit of quantitation of the instrument
1000uL is final extract volume . GC injection volume 1uL.
137
-------
Table 31 (Continued)
Microconcentration of this extract (1 mL) was not possible
due to high amount of impurities in the sample. Sulfuric acid treatment also
could not be performed since dieldrin decomposes when treated with concentrated
sulfuric acid.
Original sample extract is 4mL (2mL goes to PAHs portion, 1mL goes to DDT and
chlordane, remaining 1mL is used for Dieldrin analysis).
@Decachlorobiphenyl (2,2',3,3I/4,4',5,5f,6,61-)
* Triplicate injections were made for Dieldrin analysis.
* * Triplicate injections were made for Chlordane and DDT analysis.
# Test analysis was performed in order to check the background PCBs in the XAD-2
resins . There was no problem with regard to background levels of pesticides in
the resin
columns .
138
-------
Table 32 Triplicate Injection Results, Spring 1992 Samples
Sprinq event sample - Water
Sample No.
5D
5D
5D
8D
8D
8D
Triplicate injection results:
Gamma - Chlordane
Sample ID
SBR10106W1D
SBR10106W1D
SBR10106W1D
SBR201031D
SBR201031D
SBR201031D
Amount
ng/samp.
1.2626
1.2756
1.3867
0.4507
0.4789
0.4655
Cone, in Water
. (ng/L)
BDL
BDL
BDL
BDL
BDL
BDL
Dieldrin
Sample No.
4D
4D
4D
12D
12D
12D
Sample ID
SBR10106W1D
SBR10106W1D
SBR10106W1D
SBR20103W1D
SBR20103W1D
SBR20103W1D
Amount
ng/samp.
2.9617
3.0031
3.2223
4.9596
4.7363
4.9183
Cone, in Water
. (ng/L)
BDL
BDL
BDL
BDL
BDL
BDL
DDT
Sample No.
5D
5D
5D
8D
8D
8D
Sample ID
SBR10101W1D
SBR10101W1D
SBR10101W1D
SBR20103W1D
SBR20103W1D
SBR20103W1D
Amount
ng/samp.
0.3469
0.2997
0.3454
0.1666
0.1824
0.1724
Cone, in Water
. (ng/L)
BDL
BDL
BDL
BDL
BDL
BDL
Alpha - Chlordane
Amount ng/samp
2.5577
2.7202
2.7296
1.1296
1.21
1.2211
Cone, in Water
(ng/L)
0.05
0.05
0.05
0.0209
0.0224
0.0226
139
-------
Table 33 Matrix Spike Recovery, Spring 1992 Samples
Snrina Event Samole - Water
Matrix Soike Recovery
Sample
No.
5D
Sample
ID
Gamma-chlordane f Water )
Actual
amount in
sample *(ng/ 0.1 ml)
SBR10106W1D 0.3283
* GC Sample
Sample
No.
Sample
ID
5D (SBR10106W1D
* GC Sample
Sample
No.
10D
Sample
ID
SBR20106W1D
* GC Sample
Sample
No.
5D
Sample
ID
SBR10106W1D
* GC Sample
Spiked
Amount
(ng)
0.91
Aloha-chlordane (Water I
Actual
amount in
sample*(ng)
0.667
DIELDRIN ( Water )
Actual
amount in
sample *(ng)
1 .0867
Spiked
Amount
(ng)
0.88
Spiked
Amount
(ng)
Total amount
recovered
(ng/lmL)
1.3968
Total amount
recovered
(ng)
1.3213
Total amount
recovered
(ng)
6 | 6.5015
4.4' - DDT ( Water >
Actual
amount in
sample*(ng)
0.0823
Spiked
Amount
(ng)
2.49
Total amount
recovered
(ng)
2.5934
Recovery
of Spiked
amount (%)
117.42
Recovery
of Spiked
amount (%)
74.35
Recovery
of Spiked
amount (%)
90.25
Recovery
of Spiked
amount {%)
1 00.85
140
-------
8.2.7. PESTICIDES (PARTICULATE PHASE) FALL, 1990
141
-------
Table 34 Pesticide Levels In Buffalo River Suspended Sediments,
Including CSO Samples (ng/L and mg/Kg), Fall 1990
Sam.
No.
1
2
3
4
5
6
7
Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHU
Dieldrin
4,4'-DDT (DDT)
IDL
0.75 pg
0.865 pg
2.285 pg
6.01 pg
IDL = Instrument detection limit
LOQ= Limit of quantitation
LOQ
1 .97 pg
2.090 pg
4.11 7 pg
9.98 pg
BDL (below detection limit) = < IDL
BQL (below quantitation limit) = < LOO. and > IDL
Date
10/17, '90
10/17/90
10/18/90
10/18/90
10/19/90
10/19/90
10/22/90
Sample ID
BLANK 1017A
BLANK1017B
BR10101W1P
BR10102W1P
BLANK1019A
BLANK1019B
BR10101W1P
Analyte
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
Quantity
(ng/L water)
(ppt)
QL (ref. footnote P-12)
0.014ng/L
0.015ng/L
0.299ng/L
0.073ng/L
Detected
(mg/kg
sediment#)
(ppm)
Surrogate
Spike@
Recovery
(%)
Test analysis, no data available
Test analysis, no data available
Test analysis, no data available
Test analysis, no data available
BDL
BDL
BDL
BDL
BQL
BQL
BDL
BDL
BDL
BQL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BQL
BQL
BDL
BDL
BQL
BQL
BDL
BDL
BDL
BQL
BDL
BDL
BQL
BQL
BDL
BDL
78.47
86.11
116.24
124.01
115.85
99.72
142
-------
Table 34 (Continued)
Sam.
No.
8
9
10
11
12
13
14
|Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
IDL
0.75 pg
0.865 pg
2.285 pg
6.01 pg
IDL = Instrument detection limit
LOQ= Limit of quantitation
BDL (below detection limit) = < IDL
LOQ
1 -97 pg
2.090 pg
4.11 7 pg
9.98 pg
BQL (below quantitation limit) = < LOQ and > IDL
Date
10/22,'90
10/22/90
10/22/90
10/22/90
10/22/90
10/22/90
10/22/90
Sample ID
BR10102W1P
BR10103W1P**
BR10103W2P**
BR10104W1P
BR10105W1P
BR10106W1P
TRIP-BLANK
Analyte
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
Quantity
(ng/L water)
(PPt)
0.0151
0.0210
BDL
BDL
BDL
BDL
BDL
BDL
BDL
0.0161
BDL
BDL
BDL
BQL
BDL
BDL
0.0399
0.0571
BDL
BDL
BQL
0.0171
BDL
BDL
G-CHL | BDL
A-CHL
Dieldrin
DDT
BDL
BDL
BDL
QL (ref. footnote P-12)
0.014ng/L
0.015ng/L
0.299ng/L
0.073ng/L
Detected
(mg/kg
sediment#)
(ppm)
0.0038
0.0053
BDL
BDL
BDL
BDL
BDL
BDL
BDL
0.0027
BDL
BDL
BDL
BQL
BDL
BDL
0.0013
0.001 9
BDL
BDL
BQL
0.0006
BDL
BDL
Surrogate
Spike
Recovery
{%)
103.66
78.44
94.50
109.47
67.43
73.92
120.86
143
-------
Table 34 (Continued)
Sam.
No.
15
16
17
18
19
20
21
Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
IDL
0.75 pg
0.865 pg
2.285 pg
6.01 pg
IDL = Instrument detection limit
LOQ= Limit of quantitation
BDL (below detection limit) = < IDL
LOQ
1.97pg
2.090 pg
4.11 7 pg
9.98 pg
BQL (below quantitation limit) = < LOQ and > IDL
Date
10/23/90
10/23/90
10/27/90
10/27/90
10/27/90
10/27/90
10/27/90
Sample ID
BLANK1023A
BLANK1023B
BR20101W1P
BR20102W1P
BR20103W1P
BR20103W2P
BR20104W1P
Analyte
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
Quantity
(ng/L water)
(Ppt)
BDL
BDL
BDL
L BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
0.0780
BDL
BDL
BDL
BDL
BDL
BQL
BDL
BDL
0.0145
0.0239
BDL
0.0859
BDL
BDL
BDL
QL (ref. footnote P-12)
0.014ng/L
0.015ng/L
0.299ng/L
0.073ng/L
Detected
(mg/kg
sediment#)
(ppm)
BDL
BDL
BDL
0.0260
BDL
BDL
BDL
BDL
BDL
BQL
BDL
BDL
0.0036
0.0060
BDL
0.0215
BDL
BDL
BDL
Surrogate
Spike
Recovery
(%)
115.60
96.07
102.98
119.26
76.08
107.57
95.67
144
-------
Table 34 (Continued)
Sam.
No.
22
23
24
25
26
27
28
Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
DDT
IDL
0.75 pg
0.865 pg
2.285 pg
6.01 pg
IDL = Instrument detection limit
LOQ = Limit of quantitation
BDL {below detection limit) = < IDL
BDL
LOQ
1.97pg
2.090 pg
4.11 7 pg
9.98 pg
BQL (below quantitation limit) = < LOQ and > IDL
Date
10/27/90
10/27,'90
10/29/90
10/29/90
10/31/90
10/31/90
10/31/90
Sample ID
BR20105W1P
BR20106W1P
BLANK 1029A
BLANK1029B
TRIP-BLANK
BR30101W1P
BR30102W1P
I
Analyte
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
Quantity
(ng/L water)
(ppt)
BDL
BDL
BDL
BDL
BQL
0.0197
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BQL
BDL
BDL
BDL
BQL
BDL
BDL
QL (ref . footnote P-1 2)
0.014ng/L
0.015ng/L
0.299ng/L
0.073ng/L
Detected
(mg/kg
sediment#)
(ppm)
BDL
BDL
BDL
BDL
BQL
0.0018
BDL
BDL
BDL
BQL
BDL
BDL
BDL
BQL
BDL
Surrogate
Spike
Recovery
(%)
91.02
125.46
61.92
111.74
105.62
1 24.22
90.68
145
-------
Table 34 (Continued)
Sam.
No.
29
30
31
32
33
34
35
Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
DDT
IDL
0.75 pg
0.865 pg
2.285 pg
6.01 pg
IDL = Instrument detection limit
LOQ= Limit of quantitation
BDL (below detection limit) = < IDL
BDL
LOQ
1 -97 pg
2.090 pg
4.11 7 pg
9.98 pg
BQL (below quantitation limit) =• < LOO. and > IDL
Date
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
Sample ID
BR30103W1P
BR30104W1P*
BR30104W2P*
BR30105W1P
BR30106W1P
BLANK1031A
BLANK1031B
Analyte
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
Quantity
(ng/L water)
-------
Table 34 (Continued)
Sam.
No.
43
44
52
50
51
49
48
Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
DDT
IDL
0.75 pg
0.865 pg
2.285 pg
6.01 pg
IDL = Instrument detection limit
LOQ= Limit of quantitation |
BDL (below detection limit) = < IDL
BDL
LOQ
1.97 pg
2.090 pg
4.11 7 pg
9.98 pg
BQL (below quantitation limit) = < LOQ and > IDL
Date
11/6/90
11/6/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
Sample ID
BLANK1106A
BLANK1106B
BR50101W1P
BR50102W1P
BR50102W2P
BR501 03W1 P
BR50104W1P
Analyte
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
Quantity
(ng/L water)
(ppt)
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
0.0140
0.0148
BDL
BDL
BQL
0.0159
BDL
BDL
0.0150
0.0195
BDL
BDL
0.0150
0.0191
BDL
BDL
0.0246
0.0332
BDL
BDL
QL (ref. footnote P-12)
0.014ng/L
0.015ng/L
0.299ng/L
0.073ng/L
Detected
(mg/kg
sediment*)
(ppm)
0.0005
0.0005
BDL
BDL
BQL
0.0006
BDL
BDL
0.0005
0.0007
BDL
BDL
0.0005
0.0007
BDL
BDL
0.0009
0.001 2
BDL
Surrogate
Spike
Recovery
(%)
90.65
95.85
110.63
94.22
104.34
96.45
97.26
147
-------
Table 34 (Continued)
Sam.
No.
36
37
38
39
40
-
41
42
Anaiyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
DDT
IDL
0.75 pg
0.865 pg
2.285 pg
6.01 pg
IDL = Instrument detection limit
LOQ= Limit of quantitation
BDL (below detection limit) = < IDL
BDL
LOQ
1 .97 pg
2 090 pg
4.117pg
9.98 pg
BQL (below quantitation limit) = < LOQ and > IDL
Date
11/5/90
11/5/90
11/5/90
11/5/90
11/5/90
11/5/90
11/5/90
Sample ID
BR40101W1P
BR40101W2P
BR40102W1P
BR40103W1P
BR40104W1P
BR40105W1P
BR40106W1P
Anaiyte
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
Quantity
(ng/L water)
(ppt)
0.0225
0.0387
BDL
BDL
0.0236
0.0390
BDL
0.0861
BDL
BDL
BDL
BDL
0.0200
0.0396
BDL
BDL
0.0205
0.0242
BDL
BDL
0.0169
0.0200
BDL
BDL
BDL
BDL
BDL
QL (ref . footnote P-1 2)
0.014ng/L
0.015ng/L
0.299ng/L
0.073ng/L
Detected
(mg/kg
sediment#)
(ppm)
0.0075
0.0129
BDL
BDL
0.0118
0.0195
BDL
0.0431
BDL
BDL
BDL
BDL
0.0008
0.001 6
BDL
BDL
0.0102
0.0121
BDL
BDL
0.0021
0.0025
BDL
BDL
BDL
BDL
BDL
Surrogate
Spike
Recovery
(%)
93.34
94.10
110.07
85.82
88.73
89.46
96.93
148
-------
Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
1
Sam.
No.
46
45
47
53
54
55
56
Dieldrin
4,4'-DDT (DDT)
DDT
IDL
0.75 pg
0.865 pg
2.285 pg
6.01 pg
IDL = Instrument detection limit
LOQ= Limit of quantitation
BDL (below detection limit) = < IDL
BDL
LOQ
1 .97 pg
2.090 pg
4.117pg
9.98 pg
BQL (below quantitation limit) = < LOQ and > IDL
Date
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
11/13/90
11/13/90
Sample ID
BR50105W1P
BR50106W1P**
TRIP BLANK
BLANK 1109A
BLANK1109B
BR60101W1P"
BR60102W1P"
Quantity
(ng/L water)
Analyte (ppt)
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
BDL
BDL
BDL
BDL
0.0476
0.0533
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BQL
BQL
BDL
BDL
BDL
BQL
BQL
BDL
QL (ref. footnote P-1 2)
0.014ng/L
0.015ng/L
0.299ng/L
0.073ng/L
Detected
(mg/kg
sediment*)
(ppm)
BDL
BDL
BDL
BDL
0.0017
0.0019
BDL
BDL
BQL
BQL
BDL
BDL
BDL
BQL
BQL
Surrogate
Spike
Recovery
(%)
130.79
91.82
89.23
122.88
95.60
89.56
103.49
149
-------
Table 14
Sam.
No.
57
58
59
60
61
62
63
(Continued1)
Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4' -DDT (DDT)
DDT
IDL
0.75 pg
0.865 pg
2.285 pg
6.01 pg
IDL = Instrument detection limit
LOQ= Limit of quantitation
BDL (below detection limit) = < IDL
BDL
LOQ
1.97pg
2.090 pg
4.117 pg
9.98 pg
BQL (below quantitation limit) = < LOO. and > IDL
Date
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
11/13/90
11/14/90
Sample ID
BR60103W1P
BR60104W1P
BR60105W1P
BR60105W2P
BR60106W1P
TRIP-BLANK
BLANK1114A
Analyte
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
Quantity
(ng/L water)
(ppt)
0.0172
0.0361
BDL
0.1072
BQL
BQL
BDL
BDL
BDL
BQL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
QL (ref. footnote P-12)
0.014ng/L
0.015ng/L
0.299ng/L
0.073ng/L
Detected
(mg/kg
sediment*)
(ppm)
0.0011
0.0023
BDL
0.0067
BQL
BQL
BDL
BDL
BDL
BQL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
Surrogate
Spike
Recovery
(%)
88.63
108.67
125.41
123.13
110.92
113.18
105.12
150
-------
Table 34 (Continued)
Sam.
No.
64
68
69
70
71
72
73
Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
DDT
IDL
0.75 pg
0.865 pg
2.285 pg
6.01 pg
IDL = Instrument detection limit
LOQ= Limit of quantitation
BDL (below detection limit) = < IDL
BDL
LOQ
1.97pg
2.090 pg
4.11 7 pg
9.98 pg
BQL (below quantitation limit) = < LOQ and > IDL
Date
11/14/90
12/5/90
12/5/90
12/5/90
12/5/90
12/5/90
12/5/90
Sample ID
BLANK1114B
BLANK1205A
BLANK1205B
CSO-1W1P(Ba)
CSO-2W1P(Ca)**
CSO-3W1 P(Sm)
CSO-4W1P(Ha)**
Analyte
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
Quantity
(ng/L water)
(ppt)
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
0.1534
0.1442
BDL
BDL
BQL
BQL
BDL
BDL
0.6764
0.7081
BDL
4.9520
0.0923
0.0934
BDL
QL (ref. footnote P-12)
0.014ng/L
0.015ng/L
0.299ng/L
0.073ng/L
Detected
(mg/kg
sediment#)
(ppm)
Surrogate
Spike
Recovery
(%)
78.14
96.84
110.35
96.22
72.98
98.51
151
-------
Table 34 (Continued)
Sam.
No.
74
75
76
78
79
80
Analyte
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
DDT
IDL
0.75 pg
0.865 pg
2.285 pg
6.01 pg
IDL = Instrument detection limit
LOQ = Limit of quantitation
BDL (below detection limit) = < IDL
0.2324
LOQ
1.97pg
2.090 pg
4.11 7 pg
9.98 pg
BQL (below quantitation limit) = < LOQ and > IDL
Date
12/6/90
12/6. '90
7/30/91
8/9/91
8/9/91
8/16/91
Sample ID
BLANK 1206A
BLANK1 206B
BLANK910730A
CSO-SM0809
CSO-HM-0809
BLANK910816A
Analyte
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
Quantity
(ng/L water)
(ppt)
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
0.0630
BQL
BQL
BDL
0.0432
BQL
1 .4074
0.2371
BDL
BDL
BDL
BDL
QL (ret. footnote P-1 2)
0.014ng/L
0.015ng/L
0.299ng/L
0.073ng/L
Detected
(mg/kg
sediment*)
(ppm)
0.0017
BQL
BQL
BDL
0.0016
BQL
0.0521
0.0088
Surrogate
Spike
Recovery
(%)
73.38
123.10
93.48
87.23
89.88
112.84
152
-------
Table 34 (Continued)
These data were obtained using Hewlett Packard GC Series II equipped with DB-1701
megabore column (30m, 0.53mm id, 1 micron film thickness) . Varian GC 3400
equipped with DB-5 capillary column (30m, 0.25mm id, 0.25 micron film thickness) was
used for qualitative confirmation of pesticides.
QL (quantitation limit): Quantitation limit (generalized) was calculated based on fifty five
litres of water sample (i.e. LOQ x100uLx4/55L. for chlordane and DDT;
LOQ= Limit of quantitation of the instrument
100uL is final extract volume . GC injection volume 1uL
Original sample extract is 4mL (2mL goes to PAHs portion, 1mL goes to Dieldrin portion)
remaining 1 ml treated with concentrated sulfuric acid and microconcentration to 1 00 uL)
LOQx1000uLx4/55L for DIELDRIN)
LOQ= Limit of quantitation of the instrument
1000uL is final extract volume . GC injection volume 1uL.
Microconcentration of this extract (1 mL) was not possible
due to high amount of impurities in the sample. Sulfuric acid treatment also
could not be performed since dieldrin decomposes when treated with concentrated
sulfuric acid.
Original sample extract is 4mL (2mL goes to PAHs portion, 1 mL goes to DDT and
chlordane, remaining 1mL is used for Dieldrin analysis).
@Decachlorobiphenyl (2,2'/3,3',4,4',5,51,6,6'-)
# Total suspended solids (TSS) data were obtained from Alfred Analytical Laboratory .
* BR30104W1P- This sample included BR30104W2P, they were combined mistakenly.
Therefore, the data presented here is after dividing the raw data by 2
* First time extraction only.
** Second time extraction only.
> BR201 03W1 P- Soxlet extraction efficiency was poor. Recovery of surrogate standard is
27.3% in PCB fraction. (Please refer to PCBs data.). However, BR20103W2P
was extracted properly and the surrogate recovery was close to 100%.
153
-------
Table 35 Triplicate Analysis Results; Pesticides,- Fall 1990
Triplicate Injections for chlordane 1
I \
Alpha-Chiordane I
Cone, in
Samcie ID Amount Water
(ng/samo) (ng/L)
Cone. 1
in S.S.*
(mg/kg) 1
1 Gamma-Chiordane
Amount
(ng/samp)
Cone, in
Water
(ng/U
Cone.
in S.S.*
(mg/kg)
BR10105W1P 1
1
2
3
3.3
3.24
2.82
0.06
0.059
0.051
0.002 1
0.002
0.002 |
1.14
1.14 J
0.99 I
0.02
0.02
0.02
0.0007
0.0007
0.0007
I
BR20105W1P
1 0.53
2 0.27
3
BR30104W1P
1
2
3
0
I
BQL
BDL
BDL
BQL 1
BDL I
BDL 1
0.15
0.09
0
BOL
BDL
BDL
BDL
BDL
BDL
I I
I
1 .61 0.028
1 .41 0.025
1.45
BR40105W1P
1
2
3
BR50106W1P
1
2
3
BR60103W1P
1
2
3
1.15
1.12
1.14
0.025
0.014
0.012 1
0.013 |
0.45
0.4
0.42
0.008
0.007
0.007
0.004
0.004
0.004
I
I
0.02
0.019
0.02
0.002
0.002
0.002 !
0.47
0.46
0.51
0.008
0.008
0.009
0.001
0.001
0.001
2.76
2.67
2.76
1.96
0.048
0.052
0.054
0.002
0.002
0.002
0.036
| 1 .95 0.036
I 1.91
I
CSO-3W1P{Sm)
1
2
3
11.89
11.46
0.035
0.002
0.002
0.002
1.23
1.2
1.22
0.024
0.023
0.024
0.48
0.46
0.45 .
0.009
0.009
0.008
0.63
0.61
12.48 0.66
"Calculated based on the total suspended solids
Laboratory
5.77
5.51
5.98
0.31
0.29
0.32
data obtained from Alfred Analytical
i
0.0009
0.0008
0.0009
0.0006
0.0006
0.0005
154
-------
Table 35 (Continued)
Triplicate Injections for 4,4' -DDT
Sample ID
|4,4t-ODT
Cone, in
Amount Water
(ng/samo) (ng/U
BR10105W1P
1
2
3
BR20105W1P
1
2
3
BR30104W1P
1
2
3
BR40105W1P
1
2
3
BR50106W1P
1
2
3
BR60103W1P
1
2
3
0.95 BDL
1 .81 BDL
1.19
1.49
2.06
1.64
BDL
BDL
BDL
BDL
I
2.15
2.15
2.14
0.65
0.66
0.91
0
0
0
5.63
5.84
5.81
CSO-3W1 P(Sm)
1
2
3
* Calculated
89.18
91.97
97.84
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
0.104
0.109
0.108
Cone.
in S.S.*
(mg/kg)
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
0.006
0.007
0.007
4.75 0.132
4.89
5.21
0.136
0.145
based on the total suspended solids data obtained from Alfred Analytical
Laboratory
155
-------
Table 35 (Continued)
Triplicate Injections for Dieldrin
Sample ID
BR40101W2P
1
2
3
BR50105W1P
1
2 I
3
CSO-Smrtn 08/09
1
2
3
lOieldrin
Amount
(ng/samp)
1.3
2.9
2.74
6.91
7.41
6.68
11.98
12.71
13.42
I
Cone, in Cone, i
Water in S.S.* |
(ng/U (mg/kg)
BDL
BDL
BDL
BDL
BDL
BDL
I
BDL
BDL
BDL | BDL
BDL
BDL
I
I
I
I
I
I - I
BQL
BQL
BQL
BQL
BQL
BQL
I
"Calculated based on the total suspended solids data obtained from Alfred Analytics! |
Laboratory I I !
I
I
156
-------
Table 36 Matrix Spike Recovery
Matrix Spike Recovery
Sample ID
Actual
Amount
Alpha-Chlordane
Spiked Total
Amount
Recovered
in Sample* Amount
BR50106W1P
BR60103W1P
CSO-3W1P{Sm)
Sairiote ID
Ing)
0.689
0.487
(ng) (ng)
1.5 2.13
I
1.5 2.11
1.189 ( 7.5 8.34
*lnjecrion sample I
BR50106W1P
BR60103W1P
CSO-3W1P(Sm)
Sample ID
Actual
Amount
in Sample*
(ng)
0.61
0.23
1.15
* Injection sample
Actual
Amount
|in Sample*
BRS0106W1P
BR60103W1P
CSO-3W1P(Sm)
(ng)
Gamma-Chicrdane -
Spiked
Amount
(ng)
1.5
Total
Recovered
Amount
Recovery of
Spiked
Amount
(%)
96.2
108.3
95.3
Recovery of
Spiked
Amount
(ng) I (%)
2.08
1.5 2.09
7.5 8.51
4r4'-ODT
Spiked I Total
Amount I Recovered
I Amount
(ng) (ng)
no peak 3.6 4.5
1.44
9.3
* Injection sample
3.6
18
5.35
28.03
I
98
124
98.1
Recovery of
Spiked
Amount
{%)
125
108
104
157
-------
Table 36 (Continued)
Matrix Spike Recovery
Sample ID
BR50106W1P
BR60103W1P
CSO-3W1P(Sm)
CSO-Ham08/09
Actual
Amount
in Sample*
{ng)
0.09
0.05
0.19
6.58
*!njection sample
Oieldrin
Spiked
Total
Recovery of
Amount I Recovered I Spiked
(no)
1.3
1.3
6.5
13
Amount
(ng)
1.59
1.58
Amount
(%)
115
117
7.58 ! 113
I
23.58
130
158
-------
8.2.8. PESTICIDES (PARTICULATE PHASE) SPRING 1992
159
-------
Table 37: Pesticide Concentrations in Buffalo River Suspended Sediments
Collected During Spring 1992 (Spring Event Samples-)
Sample
No.
1P
2P*
3P
4P
5P**
6P
7P
ANALYTE
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
IDL
1.88
2.17
2.06
7.08
IDL = Instrument detection limit
LOQ= Limit of quantitation
BDL (below detection limit) = < IDL
LOQ
5.19
5.45
5.64
22.42
BQL (below quantitation limit) = < LOQ but > IDL
Date
1 6-Apr
4/17/92
4/17/92
4/17/92
4/17/92
4/1 7/92
4/18/92
Sample
ID
BLANK
SBR10101W1P
SBR10101W2P
SBR10103W1P
SBR10106W1P
BLANK
SBR20101W1P
Analyte
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
Quantity
Detected
(ng/L water)
(ppt)
BDL
BDL
BDL
BDL
BQL
0.090
BDL
BQL
0.067
0.132
BDL
BQL
0.059
0.137
BDL
BDL
0.087
0.214
BDL
BDL
BDL
BDL
BDL
BDL
BQL
BQL
BDL
BDL
QL (ref . Page 3&4)
0.0377
0.0396
0.4102
0.1631
Detected
(mg/kg)
Sediment, #
(ppm)
BDL
BDL
BDL
BDL
BQL
0.001
BDL
BQL
0.001
0.003
BDL
BQL
0.001
0.002
BDL
BDL
0.003
0.008
BDL
BDL
BDL
BDL
BDL
BDL
BQL
BQL
BDL
BDL
ng/L
ng/L
ng/L
ng/L
Surrogate
Spike@
Recovery
(%)
87.12
82.33
79.34
67.44
78.53
96.07
91.10
160
-------
Table 37 (Continued)
Sample
No.
ANALYTE
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
IDL
1.88
2.17
2.06
7.08
IDL = Instrument detection limit
LOQ= Limit of quantitation
BDL (below detection limit) = < IDL
LOQ
5.19
5.45
5.64
22.42
BQL (below quantitation limit) = < LOQ but > IDL
Date
8P | 1 8-Apr
9P
10P
11P
12P
13P*/**
14P
4/1 8/92
4/18/92
4/1 8/92
4/22/92
4/22/92
4/22/92
Sample
ID
SBR20103W1P
SBR20103W2P
SBR20106W1P
BLANK
SBR30101W1P
SBR30103W1P
SBR30106W1P
Analyte
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
Quantity
Detected
(ng/L water)
(ppt)
BQL
0.056
BDL
BDL
BQL
0.052
BDL
BDL
0.060
0.090
BDL
BDL
BQL
BDL
BDL
BDL
0.038
0.039
BDL
0.450
BDL
BQL
BDL
BDL
BQL
BQL
BDL
BDL
QL (ref . Page 3&4)
0.0377
0.0396
0.4102
0.1631
Detected
(mg/kg)
Sediment , #
(ppm.)
BQL
0.002
BDL
BDL
BQL
0.002
BDL
BDL
0.002
0.003
BDL
BDL
BQL
BDL
BDL
BDL
0.001
0.001
BDL
0.013
BDL
BQL
BDL
BDL
BQL
BQL
BDL
BDL
ng/L
ng/L
ng/L
ng/L
Surrogate
Spike@
Recovery
(%}
90.62
85.95
81.47
93.03
86.39
89.14
86.94
161
-------
TAble 37 (Continued)
Sample
No.
15P
16P
17P
18P
ANALYTE
Gamma-chlordane (G-CHL)
Alpha-chlordane (A-CHL)
Dieldrin
4,4'-DDT (DDT)
IDL
1.88
2.17
2.06
7.08
IDL = Instrument detection limit
LOQ= Limit of quantitation
BDL (below detection limit) = < IDL
LOQ
5.19
5.45
5.64
22.42
BQL (below quantitation limit) = < LOQ but > IDL
Date
4/22/92
4/22/92
4/22/92
8/31/92
Sample
ID
SBR30106W2P
BLANK
Trip Blank
Reagent Blank
Analyte
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
G-CHL
A-CHL
Dieldrin
DDT
Quantity
Detected
(ng/L water)
(ppt)
0.092
0.210
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
QL (ref . Page 3&4)
0.0377
0.0396
0.4102
0.1631
Detected
(mg/kg)
Sediment, #
(ppm) -
0.005
0.010
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
These data were obtained using Hewlett Packard GC Series II equiped with DB-1701
megabore column (30m,0.53mm id, 1 micron film thickness).
QL (Quantitation limit): Quantitation limit (generalized ) was calculated based on
55 liters of water samplefi.e. LOQ x 100uLx4/55L . for chlordane and DDT;
LOQ = Limit of quantitation of instrument
1 0OuL is final extract volume . GC injection volume 1 uL
ng/L
ng/L
ng/L
ng/L
Surrogate
Spike@
Recovery
{%)
89.54
83.09
72.82
93.93
Original sample extract is 4-mL (2mL goes to PAHs portion, 1 mL goes to Dieldrin portion)
remaining 1mL treated with concentrated sulfuric acid and microconcentration to 100 uL)
162
-------
Table 37 (Continued)
I
LOQx1000uLx4/55L for DIELDRIN)
LOQ= Limit of quantitation of the instrument
1000uL is final extract volume . GC injection volume 1uL.
Microconcentration of this extract (1 mL) was not possible
due to high
amount of impurities in the sample. Sulfuric acid treatment also
could not be performed
sulfuric acid.
since dieldrin decomposes when treated with concentrated
Original sample extract is 4mL (2mL goes to PAHs portion, 1mL goes to DDT and
chlordane, remaining 1mL is used for Dieldrin analysis).
# Total suspended solids data were obtained from Alfred Analytical Lab.
@Decachlorobiphenyl (2,2'/3,3',4/4',5,5',6,61-)
* Triplicate
1
injections were made for Dieldrin analysis.
** Triplicate injections were made for Chlordane and DDT analysis.
163
-------
Table 38: Triplicate Analysis
Sorinq event samoie - Suspended sediments
Sample
No.
5P
5P
5P
13P
13P
13P
Triplicate infection results :
i
Gamma - Chlordane
Sample
ID
SBR10106W1P
SBR10106W1P
SBR10106W1P
SBR30103W1P
SBR30103W1P
SBR30103W1P
Amount
ng/samp.
4.521 5
4.8406
4.6234
0.5317
0.5502
0.5461
Cone, in
Water.
(ng/L)
0.085
0.091
0.087
BDL
BDL
BDL
DIELDR1N
Sample
No.
2P
2P
2P
13P
13P
13P
Sample
ID
SBR10101W1P
SBR10101W1P
SBR10101W1P
SBR30103W1P
SBR30103W1P
SBR30103W1P
Amount
ng/samp.
2.5563
2.7135
2.7632
L 3.3423
3.1106
3.0941
Cone, in
Water .
(ng/L)
BDL
BDL
BDL
BDL
BDL
BDL
DDT
Sample
No.
5P
5P
5P
13P
13P
13P
Sample
ID
SBR10106W1P
SBR10106W1P
SBR10106W1P
SBR30103W1P
SBR30103W1P
SBR30103W1P
Amount
ng/samp.
1 .9068
2.1135
1 .8581
0.9691
1 .0363
1 .0571
Cone, in
Water .
(ng/U
BDL
BDL
BDL
BDL
BDL
BDL
• Suspended solids ( S.S ) data obtained from the
Alfred Analytical Lab.
Cone, in
S.S *
(mg/Kg)
0.0034
0.0036
0.0034
BDL
BDL
BDL
Cone, in
S.S *
(mg/Kg)
BDL
BDL
BDL
BC
BL
BC
Cone, in
S.S*
(mg/Kg)
BDL
BDL
BDL
BDL
BDL
BDL
Alpha-Chiordane
Amount
ng/samp.
11.12115
1 1 .47775
11.69068
1.0544
1.0227
1.0125
•
Cone, in
Water
(ng/L)
0.2084
0.2151
0.2191
BQL
SQL
BQL
Cone, in
S.S*
(mg/Kg)
0.0082372
0.008502
0.0086601
BQL
BQL
BQL
164
-------
Table 39: Matrix Spike Recovery
Spring Event Samole - Susoended Sediments
Matrix Soike Recovery
Sample
No.
13P
Sample
ID
SBR30103W1P
* GC Sample
Sample
No.
13P
Sample
ID
SBR30103W1P
* GC Sample
Sample
No.
13P
Sample
ID
SBR30103W1P
* GC Sample
Sample
No.
13P
Sample
ID
SBR30103W1P
* GC Sample
Gamma-chlordane
Actual
amount in
sample*(ng)
0.1353
Aloha-chlordane
Actual
amount in
sample*{ng)
0.2576
DIELDRIN
Actual
amount in
sample*(ng)
0.7966
4.41 - DDT
Actual
amount in
sample*(ng)
0.255
Spiked
Amount
(ng)
0.91
Spiked
Amount
(ng)
0.88
Spiked
Amount
(ng)
6
Spiked
Amount
(ng)
2.49
Total amount
recovered
(ng)
1.2714
Total amount
recovered
(ng)
1 .2204
Total amount
recovered
(ng)
6.425
Total amount
recovered
(ng)
2.944
Recovery
of Spiked
amount (%)
124.85
Recovery
of Spiked
amount (%)
109.41
Recovery
of Spiked
amount (%)
93.81
Recovery
of Spiked
amount (%)
107.99
165
-------
8.2.9. PAHs (DISSOLVED PHASE) FALL, 1990
166
-------
Table 40 List of Sample Abbreviations
Abbreviations:
BR
1 through 6
01
01 -06
W
1
2
D
Buffalo River
Survey Number
Composite
Station
Sample type: Water
Regular
Duplicate
Dissolved
CSO
CA
BA
SM
HA, HM
B[a]A
BIb]F
B[k]F
B[a]P
B[ghi]P
IDL
BDL
LOQ
BQL
Combined Sewer Overflow
Cazenovia Creek
Babcock Street
Smith Street
Hamburg Street
Benzofajanthracene
Benzo[b]fluoranthene
Benzo[k]fluoranthene
Benzo[a]pyrene
Benzo[ghi]pery!ene
Instrument Detection Limit
Below Detection Limit
Limit of Quantitation
Below Quantitation Limit
167
-------
Table 41 PAHs Levels in Buffalo River Water Samples Including CSO Samples Fall, 1990
LEVELS OF PAHs IN BUFFALO RIVER WATER SAMPLES
(62; SET 2)
Analytical Procedure: HPLC/Fluorescence
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[ghi]P
Anthr.-d10
S.N.
1
2
3
4
IDL (ng)
0.1794
0.8053
0.9609
0.0714
0.1550
1.1785
0.0833
Date
10/18/90
10/18/90
10/22/90
10/22/90
LOQ (ng)
0.5890
L_ 0.9563
1.1722
0.1925
0.3131
2.1965
0.2030
Sample ID
BR10101W1D
BR10102W1D
BR10104W1D*
BR10105W1D
Surrogate
Spike
Recovery
of B[ghi]P
(%)
116.575
138.932
118.556
134.615
BDL= IDL
Analyte
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
BlaJP
B[a]A
Chrysene
Blb]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
Quantity
Detected
(ng/L
water, ppt)
2.4756
1.7533
1 .0608
0.2206
0.3014
3.7469
2.2268
1.4308
0.2877
0.3603
4.8884
2.4203
1.7259
0.3675
0.5107
4.5796
1 .8478
1.9381
0.2987
0.4567
168
-------
Table 41
5
6
7
8
9
10
11
12
ff!nntimiecn
10/22,'90
10/27/90
10/27/90
10/27/90
10/27/90
10/27/90
10/27/90
10/27/90
BR10106W1D
BR20101W1D
BR20102W1D*
BR20103W1D
BR20103W2D***
BR20104W1D
BR20105W1D ^
BR20106W1D
»100**
93.9107
85.9467
78.6527
77.9056
143.526
121.059
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
BfkJF
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
BtalP
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
BlalP
6.0833
2.8533
2.5855
0.4945
0.7722
2.2962
1.3663
1.2605
0.2197
0.37
0.8164
BQL
0.5505
0.1233
0.1516
1.9477
1 .8009
1.1652
0.2504
0.3437
1.7555
1.9932
0.8683
0.2107
0.3017
3.4673
1.4318
1 .2348
0.2724
0.2775
6.3333
5.2289
2.71
0.503
0.5901
5.8515
5.3392
2.5125
0.4985
0.513
169
-------
Table 41 (Continued)
13
14
15
16
17
18
19
20
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
10/31/90
TRIP-BLANK***
BR30101W1D
BR30102W1D
BR30103W1D
BR30104W1D***
BR30104W2D
BR30105W1D*
BR30106W1D
111.887
51.1116
125.189
97.8089
59.0543
103.194
BlalA
Chrysene
B[b]F
BIkJF
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
BIkJF
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
BtblF
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
BQL
BDL
BDL
BQL
BDL
3.5749
1.9228
1.355
0.2789
0.3743
6.0159
2.0604
1.7142
BQL
BDL
BQL
BDL
0.4263
0.1016
BQL
2.9977
1 .2464
1.4566
0.3112
0.4053
2.7146
1.1695
1.5121
0.3594
0.3855
0.4433
BDL
0.7975
0.181
0.1855
7.3426
3.0301
2.5263
0.4209
0.8577
170
-------
Tat..e 41 (Continued)
21
22
23
24
25
26
27
28
10/31/90
10/31/90
11/5/90
11/5/90
11/5/90
11/5/90
11/5/90
11/5/90
BLANK1031A
BLANK1031B
BR40101W1D
BR40101W2D***
BR40102W1D
BR40103W1D
63.9708
57.6877
122.487
159.759
»100**
i
BR40104W1D
BR40105W1D*
57.0585
75.4033
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
Bta]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
Bla]A
Chrysene
BlbJF
B[k]F
B[a]P
0.2459
0.1717
BDL
BQL
BQL
0.1941
0.1566
BDL
BQL
BQL
2.5964
1.6622
1.2702
0.2411
BQL
2.1021
1.5073
1.0632
0.1987
0.1835
24.02
12.635
10.733
2.5558
2.1938
26.632
15.675
13.615
2.9882
1.7712
2.4118
1.6191
BDL
BQL
BQL
0.4041
BQL
BDL
BQL
BQL
171
-------
Table 41 (Continued)
29
30
31
32
33
34
35
36
11/5/90
11/6/90
11/6/90
11/9/90
11/9/90
11/9/90
11/9/90
11/9/90
BR40106W1D
BLANK1106A
BLANK1106B
BR50101W1D*
BR50102W1D
BR50103W1D
BR50104W1D
BR50105W1D
74.5399
121.054
61.9274
79.0492
132.217
120.332
»100**
85.3301
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
1 .8748
1.1785
0.8502
0.2546
0.2283
0.5588
0.2579
BDL
BQL
0.0608
BQL
BDL
BDL
BQL
BDL
0.3361
BDL
0.5042
0.1228
0.1498
2.1989
2.0772
1.3081
0.3135
0.4053
4.6699
3.7753
2.6009
0.4672
0.5797
33.625
16.801
15.342
2.2867
3.371
4.3233
3.4555
2.546
0.3868
0.3825
172
-------
Table 41 (Continued)
37
38
39
40
41
42
43
44
11/9/90
11/9/90
11/9/90
11/9/90
11/13/90
11/13/90
11/13/90
11/13/90
BR50106W1D
TRIP BLANK
BLANK1109A
BLANK1109B
BR60101W1D
BR60102W1D*
BR60103W1D
BR60104W1D
109.869
79.0492
»100**
122.817
»100**
146.049
83.172
81.1761
B[a]A
Chrysene
B[b]F
B[k]F
BlalP
B[a]A
Chrysene
B[b]F
BIk]F
B[a]P
B[a]A
Chrysene
B[b]F
BlklF
BlalP
B[a]A
Chrysene
BlblF
BlklF
BlalP
B[a]A
Chrysene
B[b]F
Blk]F
BlalP
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
BlklF
B[a]P
B[a]A
Chrysene
BlblF
BlklF
BlalP
1.7697
BDL
4.122
0.9814
1.0691
50.98"
28.16"
26.90"
4.79"
1 1 .72"
0.9075
0.4571
0.2773
0.0683
0.1144
0.442
0.252
0.1688
0.0335
0.0496
3.6217
1.6575
1 .3044
0.2683
0.3837
0.3957
BDL
0.7341
0.1485
0.1697
1.0159
BDL
1.4199
0.3485
0.3299
5.3613
2.981
BQL
0.3599
BQL
173
-------
Table 41 (Continued)
45
46
47
48
49
50
51
52
11/13/90
11/13/90
11/13/90
11/13/90
11/14/90
11/14/90
12/5/90
12/5/90
BR60105W1D
BR60105W2D***
BR60106W1D
TRIP-BLANK
BLANK1114A
BLANK1114B
BLANK1205A
BLANK1205B
156.865
171.048
57.5003
101.385
63.0434
59.1523
86.6498
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
1.406
1.2451
2.0766
0.4317
0.5855
1.1944
BDL
2.9742
0.5622
0.6813
4.0094
2.0092
3.5503
0.6338
0.6891
BQL
BDL
BDL
BQL
BQL
0.3176
BDL
0.7432
0.1487
0.1994
0.1091
BQL
0.1814
0.0302
0.0504
BQL
BDL
BDL
BDL
BDL
BQL
BDL
BDL
BDL
BDL
174
-------
Table 41 (Continued)
53
54
55
56
57
58
59
60
12/5/90
12/5/90
12/5/90
12/5/90
12/6/90
12/6/90
7/30/91
8/9/91
CSO-1W1D(Ba) 154.034
CSO-2W1D(Ca)*
CSO-3W1D(Sm)
CSO-4W1D(Ha)
BLANK 1206 A
BLANK1206B
BLANK910730A
CSO-SM0809
91.7764
85.7295
78.8368
72.3663
60.2412
95.6787
»100**
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
Bla]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
5.9372
4.5928
8.0666
1.3258
1.7963
3.6472
2.6665
1.7165
0.3712
0.3911
1.5739
1.7033
BQL
BQL
BQL
20.465
4.5252
8.8476
2.0258
1.9174
no peak
BDL
BDL
BDL
BDL
BQL
BDL
BDL
BDL
no peak
0.9263
BDL
1.8826
0.3428
0.4946
22.788
14.258
9.6033
2.2697
2.3334
175
-------
Table 41 (Continued)
61
62
8/9/91
8/16/91
CSO-HM-0809
BLANK910816A
104.69
78.321
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
* Triplicate Injections have been taken, except S.N. 3, which was in
46.375
28.849
19.912
3.3375
4.5081
BQL
BDL
BDL
BDL
BDL
(duplicate because the peak interfered with resin contaminant
in the third run, sample not available.
** Surrogate Spike Recovery- greater than 100%; B[ghi]P present in
the sample.
*** B[ghi]P was not spiked, Anthracene-d10 was spiked, but could not be
analysed because of the interference with XAD-2 resin
contaminants.
" Quantity detected; ng/sample
176
-------
Table 42 Triplicate Analysis
B[a]A
Chrysene
B[b]F
B[k]F
B[a]P
B[ghi]P
Anthr.-d10
S.N.
3
3
7
7
7
19
19
19
28
28
28
32
32
32
42
42
42
54
54
54
Triplicate Injections
IDL (ng)
0.1794
0.8053
0.9609
0.0714
0.1550
1.1785
0.0833
Date
10/22/90
10/22/90
10/27/90
10/27/90
10/27/90
10/31/90
10/31/90
10/31/90
11/5/90
11/5/90
11/5/90
11/9/90
11/9/90
11/9/90
11/13/90
11/13/90
11/13/90
12/5/90
12/5/90
12/5/90
LOQ (ng)
0.5890
0.9563
L 1.1722
0.1925
0.3131
2.1965
0.2030
B[a]A
Sample ID
BR10104W1D*
BR10104W1D*
BR20102W1D
BR20102W1D
BR20102W1D
BR30105W1D
BR30105W1D
BR30105W1D
BR40105W1D
BR40105W1D
BR40105W1D
BR50101W1D
BR50101W1D
BR50101W1D
BR60102W1D
BR60102W1D
BR60102W1D
CSO-2W1D(Ca)
CSO-2W1D(Ca)
CSO-2W1D(Ca)
BDL= IDL
Quantity Detected
(ng/L water, ppt)
4.745
5.0317
0.785
0.8477
0.6998
0.4653
0.4355
0.4292
0.3868
0.3212
0.5044
0.3138
0.3529
0.3417
0.4184
0.3225
0.4462
4.4072
2.9233
3.611
177
-------
Table 42 (Continued)
S.N.
3
3
7
7
7
19
19
19
28
28
28
32
32
32
42
42
42
54
54
54
S.N.
3
3
7
7
7
Date
10/22/90
10/22/90
10/27/90
10/27/90
10/27/90
10/31/90
10/31/90
10/31/90
11/5/90
11/5/90
11/5/90
11/9/90
11/9/90
11/9/90
11/13/90
11/13/90
11/13/90
12/5/90
12/5/90
12/5/90
Date
10/22/90
10/22/90
10/27/90
10/27/90
10/27/90
Chrysene
Sample ID
BR10104W1D*
BR10104W1D*
BR20102W1D
BR20102W1D
BR20102W1D
BR30105W1D
BR30105W1D
BR30105W1D
BR40105W1D
BR40105W1D
BR40105W1D
BR50101W1D
BR50101W1D
BR50101W1D
BR60102W1D
BR60102W1D
BR60102W1D
CSO-2W1 D(Ca)
CSO-2W1 D(Ca)
CSO-2W1 D(Ca)
B[b]F
Sample ID
BR10104W1D*
BR10104W1D*
BR20102W1D
BR20102W1D
BR20102W1D
Quantity Detected
(ng/L water, ppt)
2.5618
2.2789
BQL (0.88 ng/inj.)
BQL (0.85 ng/inj.)
BQL (0.83 ng/inj.)
BDL (0.54 ng/inj.)
BDL (0.63 ng/inj.)
BDL (0.54 ng/inj.)
0.341
0.3469
0.3073
BDL (0.51 ng/inj.)
BDL (0.71 ng/inj.)
BDL (0.60 ng/inj.)
BDL (0.65 ng/inj.)
BDL (0.54 ng/inj.)
BDL (0.75 ng/inj.)
2.5337
2.9369
2.5289
Quantity Detected
(ng/L water, ppt)
1.6639
1.7879
0.6586
0.552
0.4408
178
-------
Table 42 (Continued)
19
19
19
28
28
28
32
32
32
42
42
42
54
54
54
S.N.
3
3
7
7
7
19
19
19
28
28
28
10/31. '90
10/31/90
10/31. '90
11/5/90
11/5/90
11/5/90
11/9/90
11/9/90
11/9/90
11/13/90
11/13/90
11/13/90
12/5/90
12/5/90
12/5/90
Date
10/22/90
10/22/90
10/27/90
10/27/90
10/27/90
10/31/90
10/31/90
10/31/90
11/5/90
11/5/90
11/5/90
BR30105W1D
BR30105W1D
BR30105W1D
BR40105W1D
BR40105W1D
BR40105W1D
BR50101W1D
BR50101W1D
BR50101W1D
BR60102W1D
BR60102W1D
BR60102W1D
CSO-2W1D(Ca)
CSO-2W1D(Ca)
CSO-2W1D(Ca)
B[k]F
Sample ID
BR10104W1D*
BR10104W1D*
BR20102W1D
BR20102W1D
BR20102W1D
BR30105W1D
BR30105W1D
BR30105W1D
BR40105W1D
BR40105W1D
BR40105W1D
0.7572
0.8508
0.7846
BDL (0.88 ng/inj.)
BDU0.88 ng/inj.)
BDL (1.09 ng/inj.)
0.5215
0.5272
0.4639
0.7549
0.6871
0.7604
1.5802
1 .6343
1.935
Quantity Detected
(ng/L water, ppt)
0.3662
0.3688
0.1223
0.1388
0.1087
0.1651
0.2065
0.1716
BQL (0.1 9 ng/inj.)
BQL (0.1 8 ng/inj.)
BQL (0.1 9 ng/inj.)
179
-------
Table 42 (Continued)
32
32
32
42
42
42
54
54
54
S.N.
3
3
7
7
7
19
19
19
28
28
28
32
32
32
42
42
42
11/9/90
11/9, '90
11/9/90
11/13/90
11/13/90
11/13/90
12/5/90
12/5/90
12/5/90
Date
10/22/90
10/22/90
10/27/90
10/27/90
10/27/90
10/31/90
10/31/90
10/31/90
11/5/90
11/5/90
11/5/90
11/9/90
11/9/90
11/9/90
11/13/90
11/13/90
11/13/90
BR50101W1D
BR50101W1D
BR50101W1D
BR60102W1D
BR60102W1D
BR60102W1D
CSO-2W1D(Ca)
CSO-2W1D(Ca)
CSO-2W1D(Ca)
B[a]P
Sample ID
BR10104W1D*
BR10104W1D*
J3R20102W1D
BR20102W1D
BR20102W1D
BR30105W1D
BR30105W1D
BR30105W1D
BR40105W1D
BR40105W1D
BR40105W1D
BR50101W1D
BR50101W1D
BR50101W1D
BR60102W1D
BR60102W1D
BR60102W1D
0.1144
0.136
0.1179
0.1486
0.159
0.1379
0.4054
0.3149
0.3933
Quantity Detected
(ng/L water, ppt)
0.4865
0.5349
0.2075
0.1486
0.0988
0.1803
0.1814
0.1949
BQL (0.22 ng/inj.)
BQL (0.22 ng/inj.)
BQL (0.21 ng/inj.)
0.1607
0.1547
0.1338
0.1571
0.1779
0.1739
180
-------
Table 42 (Continued)
54
54
54
12/5/90
12/5/90
12/5/90
CSO-2W1D(Ca)
CSO-2W1 D(Ca)
CSO-2W1 D(Ca)
0.3902
0.3544
0.4287
* Peak interfered with resin contaminant in the third run, sample not available.
181
-------
Table 43 PAHs Concentrations in Water Samples (5, Set 1)
LEVELS OF PAHs IN BUFFALO RIVER WATER SAMPLES
(5;SET1)
Analytical Procedure: HPLC/UV, Poor Surrogate Spike Recovery
B[a]A
Chrysene
B[b]F
B[k]F
BlalP
Anthr.-d10
S.N.
1
2
3
4
5
IDL (ng)
1.62
1.07
1.71
2.57
2.85
1.57
Date
10/19, '90
10/19, '90
10/22, '90
10/22, '90
10/22, '90
BDL=
-------
Table 44: List of Samples Used for Test Analysis
S. N.
1
2
3
4
5
6
7
8
Date
10/17/90
10/17/90
10/22/90
10/23/90
10/23/90
10/29/90
10/29/90
11/9, '90
Test Analysis, no data available:
Sample ID
BLANK 1017A
BLANK1017B
BR10103W2D
BLANK1023A
BLANK1023B
BLANK1029A
BLANK1029B
BR50102W2D
183
-------
Table 45: Matrix Spike Recovery
Sample ID
BR20102W1D
BR30105W1D
BR50101W1D
* Injection Sample
Matrix Spike Recovery
Analyte
B[a]A
Chrys.
B[b)F
B[k]F
B[a]P
B[a]A
Chrys.
B[b]F
B[k]F
B[a]P
B[a]A
Chrys.
B[b]F
B[k]F
B[a]P
Actual
Amount
in sample*
(ng)
2.3744
1.1757
1.8523
0.34
0.58
1.1804
0.5397
2.1576
0.47
0.54
0.9585
0.6046
1.3013
0.33
0.38
Amount
spiked
(ng)
2.5
1.5
2
1
1
1.5
1
2.5
1
1
1.5
1
1.5
1
1
Total Amt.
Recovered
(ng)
6.2075
1.8974
3.9377
1.2637
1.1819
2.0274
2.2705
4.5555
1.3231
1.3999
1.8980
2.1202
1.9170
1.0316
0.9735
Recovery
of Spiked
Amount
(%)
127.3495
70.9110
102.2165
94.3085
74.8060
75.6376
147.4661
97.8076
90.0059
90.9030
77.2018
132.1305
68.4334
77.5608
70.5460
184
-------
8.2.10. PAHs (DISSOLVED PHASE) SPRING, 1992
185
-------
Table 46: Levels of PAHs in Buffalo River Water, Including
Triplicate Injection and Matrix Spike Recovery Results
Spring, 1992 Samples
LEVELS OF PAHs IN BUFFALO RIVER WATER
SPRING EVENT SAMPLES
| Instrument Used: HPLC / Ruoresence Detector
PAH
B(a)a
Chrysene
B(b)f
B(k)f
B(a)p
B(ghi)p
S.N.
ID
1
IDL (ng)
0.9985
0.8084
0.3493
0.0994
0.2251
1.917
LOQ {ng)
3.2055
2.3558
0.7947 |BDL: Below IDL
0.2313 |BQL: Below LOQ, but hiqher than IDL
0.5709 |
5.393
Date
April, 16, '92
2D | April, 17, '92
3D | April, 17, '92
4D | April, 17, '92
5D (April, 17, '92
6D
April, 17, '92
Surrogate
Soike
Recovery
of B(ghi)p
Sample ID { % ) •
Initial Blank 1 68
SBR10101W1D
523
!
SBR10101W2D 544
SBR10103W1D
91
SBR10106W1D
Blank after SBR-1
161
365
|
I
Analyte
Blala
Chrysene
Quantity
Detected
I (ng/L)
water, ppt
4.704
BQL
Blblf 0.38
Blklf | 0.138
Blalp 0.286
Blaia
Chrysene
Blblf
B[k]f
B[a]p
Blala
Chrysene
Blblf
Blklf
Blajp
Blala
Chrysene
B[b]f
B[k]f
B[a]p
Blala
Chrysene
Blblf
Blklf
|Bla]p
Blala
Chrysene
Blblf
Blklf
Blalp
23.63
8.57
5.9
1.349
2.196
24.71
9.101
6.2
1.313
2.16
BDL
BQL
0.88
0.286
BQL
BQL
8.29
4.23
1.526
1.022
19.45
15.22
6.65
0.787
BDL
186
-------
Table 46 (Continued)
7D**
8D
9D**
• 10D
11D
12D
13D
14D
15D
16D
April, 18, '92
April, 18, '92
April, 18, '92
April, 18, '92
April, 1 8, '92
April, 22, '92
April, 22, '92
~pril, 22, '92
April, 22, '92
.s
April, 22, '92
SBR20101W1D
SBR20103W1D
SBR20103W2D
SBR20106W1D
Blank after SBR-2
SBR30101W1D
SBR30103W1D
SBR30106W1D
SBR30106W2D
Final Blank SBR
384
84
90
100
118
175
159
89
51
143
B(a]a
Chrysene
Blbjf
Btklf
Btalp
B[a]a
Chrysene
Btblf
B(k]f
B{a]p
Btala
Chrysene
Btblf
Btklf
Btalp
Blala
Chrysene
Btblf
Blk]f
Btalp
B[a]a
Chrysene
Btb]f
Btklf
Bfalp
B[a]a
Chrysene
Btblf
Btklf
Btalp
Btala
Chrysene
Btblf
BIkJf
Btalp
Btala
Chrysene
Btblf
Btklf
Btalp
Btala
Chrysene
Btblf
Blklf
Blalp
Btala
Chrysene
Blb]f
Blklf
Blalp
2.21
1.34
0.783
0.195
0.12
BQL
BQL
BQL
0.179
BDL
2.94
1.99
1.03
0.367
BDL
BDL
3.36
0.9
0.32
BQL
2.06
BQL
BDL
BDL
BDL
* 2.64
6.43
3.39
0.77
0.896
BDL
11.25
5.48
1.1
1.277
BDL
BQL
2.02
0.55
0.66
BDL
1.92
1.86
0.499
0.413
BDL
BDL
BDL
BDL
BDL
187
-------
Table 46 (Continued)
17D |April, 22, '921 Trip Blank
51
|B[ala
BDL
(Water Samples)
Chrysene
BDL
BIblf
BDL
Btkjf
BDL
Blalp
BDL
18D
Aug. 31, '92 | Reagent Blank***
0
B[a]a
BDL
(Water Samples)
Chrysene
BDL
Blblf
BDL
B[k]f
BDL
Btalp
BDL
Foot Notes: SBR Water Samples
Samples showing surrogate standard [ B(gni)p ] recovery over 130% indicate!
that these samples contain B(ghi)p
Triplicate injections were taken
: Reagent blank does not contain the surrogate standard recovery. When this blank was
injected into the HPLC, the pump failed and no peaks were received. Since we had ~
limited amount of sample reinjections could not be performed
ABBREVIATIONS USED :
|B(a)A
Benzo (a) Anthracene
Chry
- | Chrysene
B(b)F
Benzo (b) Fluoranthene
BOOF
Benzo (k) Ruoranthene
B(a)P
Benzo (a) Pyrene
|B(ghi)P
Benzo (ghi) Perylene
188
-------
Table 46 (Continued)
Sample #
7D
7D
7D
9D
9D
9D
Sample #
12D
TRIPLICATE INJECTION RESULTS :
Sample I.D.
SBR20101W1D
SBR20101W1D
SBR20101W1D
SBR20103W1D
SBR20103W1D
S8R20103W1D
B(a)A
(ng/U
2.39
2.16
2.09
3.05
3.01
2.34
Chry
(ng/L)
1.29
1.41
1.33
1.95
1.81
1.91
MATRIX SPIKE RECOVERY RESULTS :
Sample I.D.
SBR30101W1D
Analvte
BlajA
Chry
B(b)F
B(k)F
B(a)P
Actual
Amount
in Sample
(ng)
14.78
35.98
19
4.3
5.02
B(b)F
(ng/L)
0.87
0.77
0.71
0.73
0.93
1.27
Amount
Spiked
(ng)
40
40
20
5
10
I
B(k)F
(ng/U
0.22
0.18
0.19
0.39
0.21
0.44
Amount of
Spike
Recovered
{ng)
73.55
23.24
13.72
3.35
8.24
B(a)P
(ng/U
0.13
0.11
0.12
0.28
0.21
0.21
(%) Recovery
of Spiked
. Amount
183
58
69
67
82
189
-------
8.2.11. PAHs (PARTICULATE PHASE) FALL, 1990
190
-------
Table 47: Levels of PAHs in Buffalo River Suspended Sediment Samples, (set 1, 12 samples)
S.N. Sample ID
Surro- Analyte
gate Spike
Recovery of
Anthracene-
IDL
(ng)
Quantity Quantity
Detected Detected
(ng/L water, (ug/g sedi-
ppt) ment, ppm)
1 Blank, System A 4.4
Oct. 17, 1990 Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
2 BR10101WIP 40.8 Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
3 BR10102WIP 54.6
Oct. 18, 1990 Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
1.57
1.62
1.07
1.71
2.57
2.85
1.57
1.62
1.07
1.71
2.57
2.85
1.57
1.62
1.07
1.71
2.57
2.85
ND
ND
ND
ND
ND
<5
6.86
<5
<5
<5
<5
5.69
5.60
<5
<5
ND
ND
ND
ND
ND
BDL
0.86
BDL
BDL
BDL
BDL
0.41
0.40
BDL
BDL
* Samples extracted with acetone : hexane (1:1) and the extracts analyzed by HPLC-UV detector
(detection limit = 5ppt)
191
-------
Table 47 (Continued)
Blank, System B 0.6
Oct. 19, 1990
5 BR10103WIP 17.0
6 BR10104WIP 45.5
7 BR10105WIP 58.5
8 BR10106WIP 31.4
9 Trip Blank 3.8
Oct. 22, 1990
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d10'
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-dIO
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-djo
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
1.57
1.62
1.07
1.71
2.57
2.85
1.57
1.62
1.07
1.71
2.57
2.85
1.57
1.62
1.07
1.71
2.57
2.85
1.57
1.62
1.07
1.71
2.57
2.85
1.57
1.62
1.07
1.71
2.57
2.85
1.57
1.62
1.07
1.71
2.57
2.85
ND
ND
ND
ND
ND
<5
9.48
<5
<5
<5
<5
12.06
7.8
<5
<5
4.78
8.96
<5
<5
<5
<5
5.79
<5
<5
<5
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
BDL
0.68
BDL
BDL
BDL
BDL
0.50
0.33
BDL
BDL
0.16
0.30
BDL
BDL
BDL
BDL
0.21
BDL
BDL
BDL
ND
ND
ND
ND
ND
192
-------
Table 47 (Continued)
10
Blank, System A 10.5
Oct. 23, 1990
11 Blank, System B 1.9
Oct. 23, 1990
12 CSO BLANK 14.7
Dec. 5, 1990
Abbreviations Used:
B(a)A : Benzo(a)Anthracene
B(b)F : Benzo(b)Fluoranthene
B(k)F : Benzo(k)Fluoranthene
B(a)P : Benzo(a)Pyrene
ND : Not Detectable
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
1.57
1.62
1.07
1.71
2.57
2.85
1.57
1.62
1.07
1.71
2.57
2.85
1.57
1.62
1.07
1.71
1.71
2.57
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
IDL : Instrument Detection Limit
BDL : Below Detection Limit
193
-------
Table 48: Levels of PAHs in Buffalo River Suspended Sediment
Samples, including CSO samples (set 2, 29 samples)
S.N. Sample ID
Surro- Analyte
gate Spike
Recovery of
Anthracene-
d,0 (%)
IDL
(ng)
Quantity
Detected
(ng/L water,
PPO
Quantity
Detected
(ug/g sedi-
ment, ppm)
Blank, System B 134.0
Oct. 17, 1990 Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
2 Blank, System A 118.0
Oct. 19, 1990 Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
3 BR10101WIP »100*
Oct. 22, 1990 Anthracene-dj0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
8.555
17.507
14.211
4.965
12.983
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.07
2.19
1.78
0.62
1.62
* Samples extracted with methylene chloride and the extracts analyzed by HPLC-flourescence detector
(detection limit = 0.1 ppt)
194
-------
Table 48 (Continued)
BR10102WIP 153.7
Oct. 22, 1990
5 BR10103WIP 147.8
Oct. 22, 1990
6 Blank, System A 121.0
Oct. 29, 1990
7 Blank, System B 125.0
Oct. 29, 1990
8 Blank, System A 145.0
Nov. 6, 1990
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-djo
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-dj0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
3.125
5.5497
4.284
1.485
3.62
1.942
3.305
2.333
0.915
1.973
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.22
0.40
0.31
0.11
0.26
0.32
0.55
0.39
0.15
0.33
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
195
-------
Table 48 (Continued)
9 Blank, System B 45.0
Nov. 6, 1990
10 BR50102WIP 120.1
11 Blank, System A 107.0
Nov. 9, 1990
12 Blank, System B 79.0
Nov. 9, 1990
13 BR60102WIP »100*
Nov. 13, 1990
Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-di0
B(a)A
Chiysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d,0
B(a)A
Chiysene
B(b)F
B(k)F
B(a)P
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
ND
ND
ND
ND
ND
1.589
2.94
2.56-
0.879
0.023
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
3.565
5.968
5.308
1.936
4.241
2ND
ND
ND
ND
ND
0.06
0.11
0.09
0.03
0.07
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.27
0.50
0.44
0.16
0.35
196
-------
Table 48 (Continued)
14 **BR60102WIP
Nov. 13, 1990
15 BR60103WIP
Nov. 13, 1990
16 BR60104WIP
Nov. 13, 1990
17 BR60105WIP
Nov. 13, 1990
18 BR60105WIP
Nov. 13, 1990
-
»100*
Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
»100*
Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
»100*
Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
184.7
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
191.9
Anthracene-dio
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
2.14
3.794
3.143
1.284
2.584
2.976
6.989
6.168
2.237
4.105
6.348
12.816
9.753
4.306
2.584
2.052
3.879
2.918
1.0
1.96
2.063
3.827
2.786
0.985
1.961
0.11
0.19
0.16
0.06
0.13
0.19
0.44
0.39
0.14
0.26
0.08
0.17
0.13
0.06
0.13
0.51
0.97
0.73
0.25
0.49
0.13
0.24
0.17
0.06
0.12
197
-------
Table 48 (Continued')
19
20
21
22
23
24
BR60106WIP »100*
Nov. 13, 1990
Trip Blank 78.0
Nov. 13, 1990
Blank, System A 33.9
Nov. 14, 1990
Blank, System B 73.0
Nov. 14, 1990
**CSO-4WIP »100*
Nov. 13, 1990
Blank, System A 127.0
Dec. 6, 1990
Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-di0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d,0
B(a)A
Chiysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
2.66
5.182
3.463
1.25
2.719
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
132.0
178.03
139.067
66.549
144.717
ND
ND
ND
ND
ND
0.33
0.65
0.43
0.16
0.34
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
—
—
—
—
—
ND
ND
ND
ND
ND
198
-------
Table 48 (Continued)
25
26
27
28
29
Blank, System B 117.0
Dec. 6, 1990
Blank, System A 89.6
prior to CSO sampling
July 30, 1991
CSO Smith Street »100*
Aug. 9, 1991
CSO -Hamburg 211.1
Street
Aug. 9, 1991
Blank, System A 70.8
Final
Aug. 16, 1991
Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-dj0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
18.777
21.819
5.35
12.165
27.163
2.733
8.294
3.832
1.754
2.836
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2'
—
—
—
—
3*
—
—
—
—
—
ND
ND
ND
ND
ND
**
Surrogate Spike Recovery - greater than 100%;
Anthracene present in sample.
Triplicate runs have been taken.
199
-------
Abbreviations Used:
B(a)A : Benzo(a)Anthracene
B(b)F : Benzo(b)Fluoranthene
B(k)F : Benzo(k)Fluoranthene
B(a)P : Benzo(a)Pyrene
ND : Not Detectable
IDL : Instrument Detection Limit
1*, 2*, 3* - concentration of PAH (ug/g sediment) is not reported because of unavailability of data on the
weight of suspended sediment in water for these samples.
200
-------
Table 49: Samples Collected During Recovery Test for XAD-2 Resin
S.N. Sample ID
Surro- Analyte
gate Spike
Recovery of
Anthracene-
d,0 (%)
IDL
(ng)
Quantity
Detected
(ng/L water,
PPt)
Quantity
Detected
(ug/g sedi-
ment, ppm)
Site 4 130.1
System A Anthracene-d10
Nov. 30, 1990 B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
0.172
0.157
0.104
0.012
0.023
0.039
1.422
3.002
2.361
0.997
1.926
Site 4
System B
Nov. 30, 1990
98.9
Anthracene-d
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
10
0.039
0.172
0.157
0.104
0.012
0.023
0.676
1.419
1.304
0.59
1.063
201
-------
Table 50 Levels of PAHs in Buffalo River Suspended Sediment Samples, Polynuclear Aromatic
Hydrocarbons Analyses of 31 Samples of Buffalo River Project *
S.N. Sample ID
1 BR20103WIP
2 BR20102WIP
3 BR20103WIP
Surro- Analyte
gate Spike
Recovery of
Anthracene-
d10 (%)
'89.9
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
*oo c
OO.J
Anthracene-djo
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
*88.3
Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
IDL
(ng)
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
Quantity
Detected
(ng/L water,
PPt)
1.7
2.5
2.5
0.519
1.58
0.447
0.623
0.89
0.323
0.419
2.495
4.462
3.845
1.408
2.139
Quantity
Detected
(ug/g sedi-
ment, ppm)
0.57
0.83
0.83
0.17
0.53
0.45
0.62
0.89
0.32
0.42
0.16
0.28
0.24
0.09
0.13
* Samples extracts analyzed by HPLC-flourescence detector
202
-------
Table 50 (Continued)
***BR20105WIP '73.1
5 BR20106WIP '100.2
6 **CSO-CAZENOVIA * 108.4
7 Blank, System B *63.6
prior to CSO
sampling
July 31, 1991
8 Trip Blank 78.4
Oct. 31, 1990
9 BR30101WIP 80.2
Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-dio
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
1.076
2.107
2.112
0.818
1.172
0.76
1.155
0.952
0.367
0.421
2.349
4.345
5.072
1.813
3.145
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.82
2.693
2.536
0.923
1.605
0.36
0.70
0.70
0.27
0.39
0.07
0.11
0.09
0.03
0.04
—
—
—
—
____
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.61
0.90
0.85
0.31
0.54
203
-------
Table 50 (Continued)
10 BR30102WIP 77.3
11 ***BR30103WIP 88.4
12 BR30104WIP 70.0
13 BR30104W2P 93.2
14 BR30105WIP 76.6
15 BR30106WIP 75.0
Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d]0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-dIO
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-dio
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
1.495
2.509
1.965
0.694
1.332
0.967
2.45
2.541
1.019
1.803
2.218
3.82
3.867
1.499
2.394
3.623
7.614
6.914
2.453
4.513
3.817
6.531
6.018
2.304
3.778
1.968
4.149
3.405
1.321
2.075
0.37
0.63
0.49
0.17
0.33
0.24
0.61
0.64
0.25
0.45
1.11
1.91
1.93
0.75
1.20
0.60
1.27
1.15
0.41
0.75
0.18
0.31
0.29
0.11
0.18
1.97
4.15
3.41
1.32
2.08
204
-------
Table 50 (Continued)
16 Blank, System A 82.1
Oct. 31, 1990
17 Blank, System B 89.0
Oct. 31, 1990
18 BR40105WIP 77.5
19 BR40101WIP 97.8
20 ***BR40102W1P »100**
21 ***BR40103W1P »100**
Anthracene-di0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d]0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
4.35
6.443
8.144
3.117
5.607
4.336
8.49
8.199
3.128
6.293
4.348
8.254
7.839
2.993
5.612
6.814
9.99
9.167
3.69
7.055
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.45
2.15
2.71
1.04
1.87
2.17
4.25
4.10
1.56
3.15
0.33
0.63
0.60
0.23
0.43
0.28
0.42
0.38
0.15
0.29
205
-------
Table 50 (Continued)
22 BR40104W1P »100**
23 BR40104W1P »100**
24 BR40106W1P 72.4
25 ***BR40102W1P »100**
26 BR50102W2P »100**
27 BR50103W1P »100**
Anthracene-d,o
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-djo
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
Anthracene-djo
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
2.527
4.17
3.349
1.276
2.374
2.749
4.289
3.449
1.407
2.428
0.756
1.221
1.110
0.415
0.729
2.146
3.809
3.359
1.407
2.428
2.839
4.996
3.97
1.52
3.258
2.136
4.043
3.38
1.319
2.359
1.26
2.09
1.67
0.64
1.19
0.34
0.54
0.43
0.18
0.30
0.19
0.31
0.28
0.10
0.18
0.08
0.14
0.12
0.05
0.09
0.10
0.18
0.14
0.05
0.12
0.08
0.14
0.12
0.05
0.08
206
-------
Table 50 (Continued)
28 BR50104W1P »100**
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
29 BR50105W1P »100**
Anthracene-d,0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
30 BR50106W1P »100**
Anthracene-d10
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
31 Trip Blank »100**
Nov. 9,1990 Anthracene-d]0
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
0.039
0.172
0.157
0.104
0.012
0.023
2.131
3.923
3.052
1.13
2.167
1.368
2.456
1.875
0.702
1.548
3.352
6.386
4.797
1.809
3.425
ND
ND
ND
ND
ND
0.08
0.14
0.11
0.04
0.08
0.05
0.09
0.07
0.03
0.06
0.12
0.23
0.17
0.06
0.12
ND
ND
ND
ND
ND
S.N. Sample ID
Matrix Spike Recovery Test
Analyte % Recovery
1 BR40106W1P
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
99.2
114.9
113.4
108.57
112.8
207
-------
Table 50 (Continued)
2 BR50102W2P
B(a)A
Chrysene
B(b)F
B(k)F
B(a)P
101.8
111.4
80.2
128.9
95.2
* : Surrogate Spike Recovery of Anthracene-d,0
based on UV detector.
** : Surrogate Spike Recovery - greater than 100%;
anthracene present in the sample.
***: Triplicate runs have been taken.
Abbreviations Used:
B(a)A: Benzo(a)Anthracene
B(b)F: Benzo(b)Fluoranthene
B(k)F: Benzo(k)Fluoranthene
B(a)P: Benzo(a)Pyrene
ND : Not Detectable
IDL : Instrument Detection Limit
1* - Concentration of PAH (ug/g sediment) is not reported because of
unavailability of data on the weight of suspended sediment hi water
for this sample
208
-------
8.2.12. PAHs (PARTICULATE PHASE) SPRING, 1992.
209
-------
Table 51: PAHs, Suspended Sediments, Spring 1992, Including Triplicate Injection
and matrix Spike Recovery Results
LEVELS OF PAHs IN BUFFALO RIVER SUSPENDED SEDIMENTS -
SPRING EVENT SAMPLES
PAH
B(a)a
Chrysene
B(b)f
B(k)f
B(a)p
B(ghi)p
S.N.
1P
2P
3P
4P»*
5P
6P
Instrument used: HPLC / Fluoresence
IDL (ng)
0.9985
0.8084
0.3493
0.0994
0.2251
1.917
Date
April 16, '92
April 17, '92
April 17, '92
April 17, '92
April 17, '92
April 17, '92
LOQ (ng)
3.2055
2.3558
0.7947
0.2313
0.5709
5.393
Sample ID
Initial Blank
SBR10101W1P
SBR10101W2P
SBR10103W1P
SBR10106W1P
Blank after SBR-1
(Sediments)
Surrogate
Spike
Recovery
of B(ghi)p
( % ) *
112.696
2758.026
4288.206
3861.153
4110.473
147.13
BDL: Below Detection Limit
BQL: Below LOQ, but higher than IDL
|
Analyte
B[a]a
Chrysene
B[b]f
B[k]f
B[a]p
B[a]a
Chrysene
B[b]f
BIkJf
Blalp
B[a]a
Chrysene
BIb]f
Btklf
B[a]p
B[a]a
Chrysene
B[b]f
B[k]f
B[a]p
B[a]a
Chrysene
B[b]f
Blklf
B[a]p
B[a]a
Chrysene
B[b]f
B[k]f
B[a]p
Quantity
Detected
(ng/L)
BDL
BDL
BDL
BDL
BDL
55.049
64.917
75.94
33.367
48.39
42.616
47.514
59.205
25.184
36.084
25.556
36.346
44.826
19.463
26.842
135.448
91.598
86.921
35.942
43.156
BDL
BDL
BDL
BDL
BDL
Quantity
Detected
(mg/kg)
BDL
BDL
BDL
BDL
BDL
0.357
0.422
0.493
0.217
0.314
0.82
0.914
1.139
0.484
0.694
1.536
L 0.491
0.606
0.263
0.363
5.353
3.62
3.435
1.421
1.706
BDL
BDL
BDL
BDL
BDL
210
-------
FINALRPT.XLS
Table 51 (Continued)
7P
8P
9P
10P
11P
12P
13P**
14P
1 5P
April 18, '92
April 18, '92
April 18, '92
April 18, '92
April 18, '92
April 22, '92
April 22, '92
April 22, '92
April 22, '92
SBR20101W1P
SBR20103W1P
SBR20103W2P
SBR20106W1P
Blank after SBR-2
(Sediments)
SBR30101W1P
SBR30103W1P
SBR30106W1P
SBR30106W2P
770.33
682.205
614.707
1833.198
84.166
1097.804
1431.458
193.552
491.972
B[a]a
Chrysene
B[b]f
B[k]f
B[a]p
B[a]a
Chrysene
B[b]f
B[k]f
B[a]p
B[a]a
Chrysene
B[b]f
B[k]f
B[a]p
B[a]a
Chrysene
B[b]f
B[k]f
B[a]p
B(a]a
Chrysene
B[b]f
B[k]f
B[a]p
B[a]a
Chrysene
B[b]f
B[k]f
B[a]p
B[a]a
Chrysene
B[b]f
B[k]f
B[a]p
B[a]a
Chrysene
B[b]f
B[k]f
B[a]p
B[a]a
Chrysene
Btblf
B[k]f
B[a]p
8.5
20.013
15.14
5.785
8.84
6.277
9.944
9.35
4.132
6.057
7.393
10.216
10.707
4.725
6.979
90.563
52.77
40.367
15.316
23.467
BDL
BDL
BDL
BDL
BDL
13.94
30.635
37.489
16.063
21.243
32.751
59.185
73.81
31.419
37.585
5.3
9.185
11.117
4.832
6.109
7.738
25
18.208
6.989
9.479
0.115
0.27
0.205
0.078
0.119
0.224
0.355
0.334
0.147
0.216
0.308
0.426
0.446
0.196
0.291
3.019
1.759
1.345
0.511
0.782
BDL
BDL
BDL
BDL
BDL
0.41
0.901
1.102
0.472
0.625
1.129
2.041
2.545
1.083
1.3
0.265
0.459
0.556
0.242
0.305
0.407
1.316
0.958
0.367
0.499
211
-------
Table 51 (Continued)
16P
17P
18P
April 22, '92
April 22, '92
July 21, '92
Final Blank SBR
(Sediments)
Trip Blank
(Sediments)
Reagerr Blank
(Sediments)
73.56
32.38
58.86
B[a]a
Chrysene
Blblf
B[k]f
B[a]p
B[a]a
Chrysene
B[b]f
B[k]f
B[a]p
B[a]a
Chrysene
B[b]f
B[k]f
B[a]p
BQL
BDL
BQL
0.215
BQL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BQL
BDL
BQL
0.215
BQL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
* : Samples showing surrogate standard I B(ghi)P ] recovery over 130% indicates that
these samples contain B(ghi)P. Please note that the blanks posses surrogate
recovery within or near to the acceptable limits, with exception to the Trip and Reagent
blanks which are below those limits
* * : Triplicate injections were taken
/ •
ABBREVIATIONS USED :
B(a)A
Chry
B{b)F
B(k)F
B(a)P
B(ghi)P -
Benzo (a) Anthracene
Chrysene
Benzo (b) Fluoranthene
Benzo (k) Fluoranthene
Benzo (a) Pyrene
Benzo (ghi) Perylene
212
-------
N)
Table 51 (Continued)
TRIPLICATE INJECTION RESULTS : SUSPENDED SEDIMENT
Sample #
4P
4P
4P
13P
13P
13P
Sample I.D.
BR10103W1
BR10103W1
BR10103W1
BR30103W1
BR30103W1
BR30103W1
B(a)A
(ng/L)
25.31
26.04
22.42
39.67
29.59
28.99
(mg/Kg)
0.34
0.35
0.3
1.36
1.02
0.99
Chry
Ing/L)
38.3
35.92
34.81
61.1
57.63
58.31
(mg/Kg)
0.52
0.49
0.47
2.11
1.99
2.03
B(b)F
(ng/L)
47.83
44.87
41.78
66.54
82.75
72.14
(mg/Kg)
0.65
0.61
0.56
2.29
2.85
2.49
B(k)F
(ng/L)
19.87
18.66
17.67
30.7
31.91
31.64
(mg/Kg)
0.27
0.25
0.24
1.06
1.1
1.09
B(a)P
(ng/L)
27.88
25.73
23.87
35.66
40.47
36.63
(mg/Kg)
0.38
0.35
0.32
1.23
1.4
1.26
-------
Table 51 (Continued)
Sample #
9P
MATRIX SPIKE RECOVERY RLo-jLTS : SUSPENDED SEDIMENTS
Sample I.D.
SBR20103W2P
Analyte
B(a)a
Chry
B(b)F
B(k)F
B(a)P
Actual
Amount
in Sample
(ng)
6.08
6.46
5.77
2.55
3.76
Amount
Spiked
(ng)
10
10
10
2.5
5
Amount of
Spike
Recovered
(ng)
12.41
10.09
9.97
1.804
4.05
(%) Recovery
of Spiked
Amount
124.08
100.97
99.71
72.15
81.07
-------
8.2.13 COMPARISON OF LEVELS OF ORGANICS IN THE BUFFALO
RIVER SAMPLES COLLECTED DURING FALL, 1990 AND
SPRING, 1992
215
-------
Figure 16
Total RGBs Residue Levels in Suspended Sediments of the Buffalo River
Collected during Fall '90 and Spring '92
Fall 1990
Survey :
Sitel
1
2
3
4
5
6
ng/L
BMDL
BMDL
BMDL
BMDL
BMDL
BMDL
Survey :
Site3
1
2
3
4
5
6
ng/L
1.86 +/-0.46
3.58
BMDL
4.04 +/-0.41
BMDL
BMDL
Survey :
Site6
1
2
3
4
5
6
ng/L
2.44 + /0.42
2.61 +/-0.44
BMDL
BMDL
6.17 +/-0.65
BMDL
Spring 1992
Survey :
Survey :
Survey :
Site - 1
1 = 2.00 +/- 0.1 6 ng/L
2 « BMDL
3= 0.65 +/- 0.15 ng/L
Survey :
Survey :
Survey :
Site -3
1 B 1.34 +/- 0.16 ng/L
2 B 0.71 +/- 0.16 ng/L
3 B 4.38 +/- 0.15 ng/L
Survey :
Survey :
Survey :
Site - 6
1 B 8.42 +/- 0.16 ng/L
2 = 1.88+/-0.16ng/L
3 =1.47+7- 0.15 ng/L
CM
-------
Figure 17
Gamma-Chlordane residue levels in water samples of the Buffalo River collected during
Fall '90 and Spring '92
K)
0.5 -i
0.45 -
04. -
.^
0.35
0.3 -
u
o> 0.25 -
0.2
0.15
0.1 -
0.05
r>
1 Survey 1
D Survey 2
• Survey 3
H Survey 4
^& Survey 5
11 Survey 6
"
Hi I ^ - -I - 1 ... . 1 .-. 1 II
Site 1
Site 3
Site 6
Site 1
Site 3
Site 6
-------
Figure 18
NJ
t--
oo
Alpha-Chlordane residue levels in water samples of the Buffalo River collected during Fall
'90 and Spring '92
0.5
0.45
0.4 +
0.35
0.3 +
o» 0.25 +
• Survey 1
D Survey 2
• Survey 3
H Survey 4
Hi Survey 5
M Survey 6
Site 1
Site 3
Site 6
Site 1
Site 3
Site 6
-------
Figure 19
Gamma-Chlordane residue levels in suspended sediments of the Buffalo River collected
during Fall '90 and Spring '92
0.5 -
0.45 -
0.4 -
0.35
0.3 -
0.25
0.2 -
0.15 -
0.1 -
0.05 -
0 -
I
Ilii n 1
' ' • '
Site 1 Site 3 Site 6
• Survey 1
D Survey 2
• Survey 3
^ Survey 4
Hi Survey 5
S Survey 6
Site 1
Site 3
Site 6
-------
Figure 20
ro
ho
o
Alpha-Chlordane residue levels in suspended sediments of the Buffalo River collected
during Fall '90 and Spring '92
0.5 -r
0.45
0.4
0.35
0.3
75. 0.25
_c
0.2
0.15
0.1 -
0.05 --
0
• Survey 1
D Survey 2
• Survey 3
11 Survey 4
H Survey 5
Hi Survey 6
Site 1
Site 3
Site 6
Site 1
Site 3
Site 6
-------
Figure 21
4,4'-DDT residue levels in suspended sediments of the Buffalo River collected during Fall
'90 and Spring '92
0.5 T
0.45
0.4
0.35 --
0.3
0.25
0.2 -
0.15
0.1
0.05 +
0
• Survey 1
D Survey 2
• Survey 3
HI Survey 4
^ Survey 5
H Survey 6
Site 1
Site 3
Site 6
Site 1
Site 3
Site 6
-------
Figure 22
Benzo (a) Anthracene residue levels in water samples of the Buffalo River collected during
Fall '90 and Spring '92
N>
ro
^)
140 T
120
100 --
80
60
40 -
20 --
-I
• Survey 1
D Survey 2
• Survey 3
HI Survey 4
u!& Survey 5
H Survey 6
Site 1
Site 3
Site 6
Site 1
Site 3
Site 6
-------
Figure 23
ro
Chrysene residue levels in water samples of the Buffalo River collected during Fall '90 and
Spring '92
100
90 +
80
70 +
60
j
"ro 50
_c
40 --
30
20
10 +
0
• Survey 1
D Survey 2
• Survey 3
Bl Survey 4
H Survey 5
M Survey 6
Site 1
Site 3
Site 6
Site 1
Site 3
Site 6
-------
Figure 24
t-o
.e-
90 T
80
70
60 +
50
40 --
30 --
20
10
0
Benzo (b) Fluoranthene residue levels in water samples of the Buffalo River collected
during Fall '90 and Spring '92
• Survey 1
D Survey 2
• Survey 3
^ Survey 4
H Survey 5
^ Survey 6
Site 1
Site 3
Site 6
Site 1
Site 3
Site 6
-------
Figure 25
Ul
20 T
18
16
14
12 --
o. 10 +
8
6
4
2 +
0
Benzo (k) Fluoranthene residue levels in water samples of the Buffalo River collected
during Fall '90 and Spring '92
Survey 1
Survey 2
Survey 3
Survey 4
Survey 5
Survey 6
Site 1
Site 3
Site 6
Site 1
Site 3
Site 6
-------
Figure 26
N>
NJ
0\
Benzo (a) Pyrene residue levels in water samples of the Buffalo River collected during Fall
'90 and Spring '92
20 T
18
16
14
12 +
o> 10 +
8
6
4 H
2
0
• Survey 1
D Survey 2
• Survey 3
S Survey 4
^ Survey 5
^ Survey 6
Site 1
Site 3
Site 6
Site 1
Site 3
Site 6
-------
Figure 27
to
N3
Benzo (a) Anthracene residue levels in suspended sediments of the Buffalo River collected
during Fall '90 and Spring '92
O)
140 T
120
100 --
80
60 --
40
20 -
• Survey 1
D Survey 2
• Survey 3
HI Survey 4
^^ Survey 5
M Survey 6
Site 1
Site 3
Site 6
Site 1
Site 3
Site 6
-------
Figure 28
Chrysene residue levels in suspended sediments of the Buffalo River collected during Fall
'90 and Spring '92
140
N5
OO
U>
120
100
80 -
60
40
20
Survey 1
Survey 2
Survey 3
Survey 4
Survey 5
Survey 6
Site 1 Site 3 Site 6
Site 1 Site 3 Site 6
-------
Figure 29
Benzo (b) Fluoranthene residue levels in suspended sediments of the Buffalo River
collected during Fall '90 and Spring '92
140
to
NO
VO
120
100
80 --
o>
60
40 -
• Survey 1
D Survey 2
• Survey 3
iH Survey 4
^^ Survey 5
M Survey 6
Site 1
Site 3 Site 6
Site 1
Site 3 Site 6
-------
Figure 30
Benzo (k) Fluoranthene residue levels in suspended sediments of the Buffalo River
collected during Fall '90 and Spring '92
N3
OJ
O
D>
140 T
120
100
80 --
60
40 --
20 --
• Survey 1
D Survey 2
H Survey 3
SI Survey 4
^ Survey 5
M Survey 6
Site 1
Site 3 Site 6
Site 1
Site 3
Site 6
-------
Figure 31
Benzo (a) Pyrene residue levels in suspended sediments of the Buffalo River collected
during Fall '90 and Spring '92
N)
Co
60
50 -
40
15> 30 +
e
20
10 -
• Survey 1
D Survey 2
I Survey 3
^1 Survey 4
^ifa Survey 5
^ Survey 6
Site 1
Site 3 Site 6
Site 1
Site 3 Site 6
-------
9. METALS LEVELS IN THE BUFFALO RIVER WATER AND SUSPENDED SEDIMENT
As approved in the QAPP, Alfred Analytical Laboratory (State University of New York at Alfred)
was subcontracted to perform analyses of Pb (EPA Method 239.2), Cu (EPA Method 220.2) and Fe (EPA
Method 236.2). The levels of Pb, Cu and Fe were determined directly in both the "total" and "dissolved"
form (i.e. both filtered and unfiltered water samples were analyzed separately). The "Particulate" phase
for the metals was determined by Alfred Analytical Laboratory as the difference between the total and
dissolved concentrations. Although differencing to indirectly determine particulate concentrations often is
done, it has been suggested that mis approach may underestimate particle-bound metals concentrations
(e.g. Droppo et al, 1992). The total, dissolved and particulate levels of Pb, Cu and Fe are presented in
Table 56 and previously have been submitted to the U.S. EPA by Dr. Harish Sikka.
For summary purposes, the means and standard deviations of the total concentrations determined
for the fall, 1990 and spring, 1992 samples are presented in Tables 57 through 62. Summary statistics
were calculated only for the total concentrations to limit possible bias associated with the use of censored
data. For the few samples that were below method detection limit, a value of one-half the detection limit
was used in the calculation of the means and standard deviations. This is a typically-used treatment of
censored data, although bias, increases with the number of censored values in the data set (El-Shaarawi
and Dolan. 1989; Newman et al., 1989). More rigorous treatments of censored data sets are available and
increasingly are being applied (e.g. Newman et al., 1989; El-Shaarawi and Dolan, 1989; Dolan and El-
Shaarawi, 1991). however, because of tgw limited number of total concentration values below the
detection limit in this study, it was decided that these approaches were not necessary. For the sites are
which duplicate samples were taken, an average of the two samples was calculated and is presented hi
Tables 57 through 62.
The standard deviations hi Tables 57 through 62 typically are large as compared to the mean
values, suggesting that given the limited data, statistically significant trends may not be determined.
Nonetheless, nonpooled Student's t tests were performed using the data in Tables 57 through 62 to
evaluate various hypotheses related to the mean values. The nonpooled t tests do not require that the
standard deviations of the two samples be equal and for small samples the test may be slightly
conservative (Ryan et al., 1992; Blalock, 1979) (i.e. slightly less likely to reject a true null hypothesis
because of a larger confidence interval). Given the small data set with considerable variance, it was
decided to use the more conservative approach. It also is recognized that the Student's t test and
corresponding tabulated critical values are based on the assumption that the sampled population is
normally distributed. Water quality data often have been found log-normally distributed (Marsalek,
1990). However, Mendenhall (1979) notes that the distribution of the t statistic possesses nearly the same
shape as the theoretical t distribution for populations that are nonnormal but possess a mound-shaped
probability distribution. Therefore, the assumption of normality is not particularly restrictive, because of
the limited number of data, tests for normality were not done, but the t tests were applied to both the raw
data (i.e. assumed normally-distributed) and data that were transformed using the base of natural
logarithms.
The difference between mean Pb, Cu and Fe levels associated with event (spring, 1992; n=3) and
interevent (fall, 1990; n=6) periods at the same site was examined. Typically, there was no significant
different (a = 0.05) between the event and interevent levels at the individual sites. This testing was
limited to sites 1,3 and 6 because of the reduced sampling and analytical effort for the event surveys.
The exceptions to this generalization were: i) Pb (In transformation only) was significantly greater (a =
0.05) for the event samples at site 3; ii) Cu (both raw data and hi transformation) was significantly greater
for the interevent samples at site 3; and iii) Cu (in transformation only) was significantly greater for the
232
-------
Table 52 Metals Levels for the Buffalo River, Fall 1990 and Spring, 1992 Surveys
Iron (Fe) Levels (ppm); Fall, 1990 Survey
Survey #
1
1
1
1
1
1
1
2
2
2
2
2
2
2
3
3
3
3
3
3
3
Site*
1
2
3
3d
4
5
6
1
2
3
3d
4
5
6
1
2
3
4
4d
5
6
Total
1.193
1.078
2.037
1.2S3
2.001
2.102
1.767
0.746
0.782
0.838
0.668
0.623
0.891
0.863
0.875
0.814
0.886
0.619
0.59S
1.156
1.242
Dissolved
0.727
0.288
0.297
0.268
0.314
0.314
0.353
0.227
0.714
0.460
0.403
0.545
0.794
0.484
0.364
0.411
0.187
0.259
0.200
0.299
0.453
Paniculate
0.466
0.790
1.74
0.985
1.687
1.687
1.414
0.519
0.068
0.378
0.265
0.078
0.097
0.379
0.511
0.403
0.699
0.360
0.395
0.860
0.790
Survey #
4
4
4
4
4
4
4
5
5
5
5
5
5
5
6
6
6
6
6
6
6
Site*
1
Id
2
3
4
5
6
1
2
2d
3
4
5
6
1
2
3
4
5
5d
6
Total
0.781
0.908
1.229
0.436
0.865
0.405
0.383
0.463
0.704
0.714
0.789
1.043
1.959
0.845
0.850
0.801
1.162
4.624
1.567
1.516
1.098
Dissolved
0.438
0.493
0.667
0.421
0.515
0.374
0.247
0.212
0.190
0.179
0.183
0.273
0.253
0.382
0.341
0.385
0.382
2.544
0.503
0.508
0.656
Paniculate
0.343
0.415
0.562
<0.03
0.350
0.031
0.136
0.251
0.514
0.535
0.6%
0.770
1.706
0.463
0.509
0.416
0.780
2.080
1.064
1.008
0.442
d - duplicate sample
233
-------
Table 52 Continued) Lead (Pb) Levels (ppm); Fall, 1990 Survey
Survey*
1
1
1
1
1
1
1
2
2
2
2
2
2
2
3
3
3
3
3
3
3
Site*
1
2
3
3d
4
5
6
1
2
3
3d
4
5
6
1
2
3
4
4d
5
6
Total
0.0005
0.0005
0.010
0.009
0.0065
0.038
0.010
0.011
0.0035
BDL
BDL
0.0085
0.003
BDL
0.055
0.018
0.011
0.004
0.003
0.002
0.026
Dissolved
BDL
BDL
BDL
BDL
BDL
0.004
0.003
BDL
BDL
BDL
BDL
BDL
BDL
BDL
0.003
BDL
BDL
BDL
BDL
BDL
0.017
Paniculate
<0.001
O.001
0.010
0.009
0.007
0.034
0.007
0.011
0.004
<0.001
<0.001
0.009
0.003
O.001
0.052
0.018
0.011
0.004
0.003
0.002
0.009
Survey*
4
4
4
4
4
4
4
5
5
5
5
5
5
5
6
6
6
6
6
6
6
Site *
1
Id
2
3
4
5
6
1
2
2d
3
4
5
6
1
2
3
4
5
5d
6
Total
0.008
0.007
0.007
0.008
0.013
0.004
0.010
0.025
0.056
0.017
0.015
0.018
0.011
0.013
0.024
0.035
0.005
0.082
0.068
0.014
0.024
Dissolved
0.003
0.003
BDL
0.004
0.001
0.001
0.002
BDL
0.004
BDL
0.005
0.005
0.003
0.005
0.003
0.004
0.001
0.003
0.002
0.001
BDL
Paniculate
0.005
0.004
0.007
0.004
0.012
0.003
0.008
0.025
0.052
0.017
0.010
0.013
0.008
0.008
0.021
0.031
0.004
0.079
0.066
0.013
0.024
234
-------
Table 52 Continued) Copper (Cu) Levels (ppm); Fall, 1990 Survey
Surveys
1
1
1
1
1
1
1
2
2
2
2
2
2
2
3
3
3
3
3
3
3
Site*
1
2
3
3d
4
5
6
1
2
3
3d
4
5
6
1
2
3
4
4d
5
6
Total
1.316
0.0205
0.386
0.071
0.065S
0.034
0.029
O.OS6
0.0325
1.128
0.014
0.0605
0.048
0.267
0.100
0.047
0.103
0.071
0.054
0.079
0.02)
Dissolved
0.010
0.011
0.007
0.012
BDL
0.010
0.008
0.011
BDL
BDL
BDL
BDL
0.003
BDL
0.014
0.007
BDL
0.002
BDL
BDL
0.005
Paniculate
1.3061
0.0091
0.379
0.059
0.065
0.024
0.021
0.045
0.032
1.1281
0.0141
0.060
0.045
0.2671
0.086
0.040
0.103
0.069
0.054
0.079
0.016
Survey*
4
4
4
4
4
4
4
5
5
5
5
5
5
5
6
6
6
6
6
6
6
Sites
1
Id
2
3
4
5
6
I
2
2d
3
4
5
6
1
2
3
4
5
5d
6
Total
0.050
0.060
0.096
0.033
0.071
0.047
0.082
0.038
0.041
0.460
0.161
0.064
0.050
0.051
0.067
1.074
0.160
0.106
1.066
0.098
0.087
Dissolved
0.017
0.019
0.027
0.032
0.003
0.032
0.024
0.015
0.021
0.046
0.023
0.022
0.014
0.025
0.040
0.036
0.026
0.054
0.028
0.056
0.044
Paniculate
0.033
0.041
0.069
0.001
0.068
0.015
0.058
0.023
0.020
0.414
0.138
0.042
0.036
0.026
0.027
1.038
0.134
0.052
1.038
0.042
0.043
235
-------
Table 52 (Continued) Iron (Fe) Levels (ppm); Spring, 1992 Survey
Survey #
1
1
1
1
2
2
2
2
3
3
3
3
Site#
1
Id
3
6
1
3
3d
6
1
3
6
6d
Total
2.93
2.64
2.68
1.30
1.21
1.45
1.38
1.90
1.12
1.41
0.64
0.79
Dissolved
0.61
0.50
0.48
0.43
0.28
0.30
0.32
0.39
0.33
0.46
0.20
0.21
Particulate
2.32
2.14
2.20
0.86
0.93
1.15
1.05
1.51
0.79
0.94
0.44
0.58
236
-------
Table 52 (Continued) Pb Levels (ppm); Spring, 1992 Survey
Survey #
1
1
1
1
2
2
2
2
3
3
3
3
Site#
1
Id
3
6
1
3
3d
6
1
3
6
6d
Total
0.0205
0.0362
0.0212
0.0936
0.0282
0.042
0.0484
0.0499
0.0291
0.0231
0.0112
0.0117
Dissolved
0.0102
0.0222
0.0161
0.0052
0.0053
0.006
0.0078
0.0081
0.0061
0.0092
0.0029
0.0054
Particulate
0.0103
0.0140
0.0051
0.0884
0.0229
0.036
0.0406
0.0418
0.0230
0.0139
0.0083
0.0063
237
-------
Table 52 (Continued) Copper (Cu) Levels (ppm); Spring, 1992 Survey
Survey #
1
1
1
1
2
2
2
2
3
3
3
3
Site#
1
Id
3
6
1
3
3d
6
1
3
6
6d
Total
0.105
0.1045
0.018
0.026
0.015
0.015
0.015
0.009
0.017
0.017
0.019
0.014
Dissolved
0.007
0.009
0.012
0.007
0.009
0.009
0.007
0.007
0.008
0.011
0.005
0.007
Particulate
0.098
0.095
0.006
0.019
0.006
0.006
0.008
0.002
0.008
0.006
0.014
0.007
238
-------
Table 53 Total (Unfiltered) Pb Levels (ppm) in River Water; Fall, 1990
Survey 1
Survey 2
Survey 3
Survey 4
Survey 5
Survey 6
X
s.d.
Site 1
O.OOOS'
0.011
0.055
0.0075
0.025
0.024
0.021
0.019
Site 2
0.0005'
0.0035
0.018
0.007
0.036
0.035
0.017
0.016
Site 3
0.0095
0.0005'
0.011
0.008
0.015
0.005
0.008
0.005
She 4
0.0065
0.0085
00035
0.013
0.018
0.082
0.022
0.030
Site 5
0.038
0.003
0.002
0.004
0.011
0.041
0.017
0.018
Site 6
0.01
0.0005"
0.026
0.01
0.013
0.024
0.014
0.010
X
0.011
0.005
0.019
0.008
0.020
0.035
below method detection limit ot U.U01 ppm
s.d
0.014
0.004
0.020
0.003
0.009
0.026
Table 54 Total (Unfatered) Cu Levels (ppm) in River Water; Fall, 1990
Survey 1
Survey 2
Survey 3
Survey 4
Survey 5
Survey 6
X
s.d
Site 1
1.316
0.056
0.10
0.055
0.038
0.067
0.272
0.512
Site 2
0.02
0.032
0.047
0.096
0.25
1.074
0.253
0.411
Site 3
0.228
0.571
0.103
0.033
0.161
0.16
0.209
0.189
Site 4
0.065
0.06
0.062
0.071
0.064
0.106
0.071
0.017
Site 5
0.034
0.048
0.079
0.047
0.05
0.582
0.140
0.217
Site 6
0.029
0.267
0.021
0.082
0.051
0.087
0.090
0.091
X
0.282
0.172
0.069
0.064
0.102
0.346
s.d
0.513
0.214
0.032
0.023
0.085
0.406
method detection limit - u.uui ppm
239
-------
Table 55 Total (Unffltered) Fe Levels (ppm) in River Water; Fall, 1990
Survey 1
Survey 2
Survey 3
Survey 4
Survey 5
Survey 6
X
s.d.
Site 1
1.193
0.746
0.875
0.844
0.463
0.85
0.829
0.235
Site 2
1.078
0.782
0.814
1.229
0.709
0.801
0.902
0.204
Site 3
1.645
0.753
0.886
0.436
0.879
1.162
0.960
0.410
Site 4
2.001
0.623
0.607
0.865
1.043
4.624
1.627
1.555
SiteS
2.102
0.891
1.156
0405
1.959
1.542
1.343
0.650
Site 6
1.767
0.863
1.242
0.383
0.845
1.098
1.033
0.463
X
1.631
0.776
0.930
0.694
0.983
1.680
s.d.
0.418
0.096
0.233
0.342
0.516
1.467
method detection limit - 0.003 ppm
Table 56 Total (Unffltered) Pb Levels (ppm) in River Water; Spring 1992
Survey 1
Survey 2
Survey 3
X
s.d.
Site 1
0.0284
0.0282
0.0291
0.0286
0.0005
Site 3
0.0212
0.0452
0.0231
0.0298
0.0133
Site 6
0.0936
0.0499
0.0114
0.0516
0.0411
Table 57 Total (Unffltered) Cu Levels (ppm) in River Water; Spring 1992
Survey 1
Survey 2
Survey 3
X
s.d.
Site 1
0.1048
0.015
0.017
0.0456
0.0513
Site3
0.018
0.015
0.017
0.0167
0.0015
Site 6
0.026
0.009
0.0165
0.0172
0.0085
240
-------
Table 58 Total (Unffltered) Fe Levels (ppm) in River Water; Spring 1992
Survey 1
Survey 2
Survey 3
X
s.d.
Site 1
2.78
1.21
1.12
1.70
0.93
Site 3
2.68
1.42
1.41
1.84
0.73
Site 6
1.30
1.90
0.72
1.31
0.59
Table 59 articulate: dissolved Ratios, Fe
Surveys
Fall, 1990
Spring, 1992
Site 1
X
1.30
3.23
s.d.
0.58
0.80
Site 3
X
2.53
3.39
s.d.
1.90
1.28
Site 6
X
1.49
2.81
s.d.
1.31
0.96
Table 60 Participate: dissolved Ratios, Cu
Surveys
Fall, 1990
Spring, 1992
Site 1
X
24.19
4.56
s.d.
52.17
6.45
Site 3
X
230.30
0.64
s.d.
453.64
0.20
Site 6
X
90.71
1.56
s.d.
217.17
1.22
241
-------
interevent samples at site 6.
The possibility of significant spatial differences in metals levels for event and interevent periods
also was examined using a Student's t test. There was no significant different (a = 0.05) in mean Pb, Cu
or Fe levels between the individual sites during the fall interevent sampling. Similarly, mere was no
significant difference in mean Pb, Cu or Fe levels between the individual sites during the spring event
sampling.
Finally, it appeared that although the fall, 1990 sampling was done during nearly baseline, steady-
state conditions, there was variability in the mean metals concentrations calculated from all sites for each
survey (Tables 57 through 59). The Student's t tests for Pb calculated from all sites for each survey
(Tables 57 through 59). The Student's t tests for Pb indicated a significant different (a = 0.05) in the
means between surveys 4 and 5 (raw data and in transformation) and in the means between surveys 4 and
6 (in transformation only). There was no significant difference between Pb means from the other surveys.
There was a significant difference hi the Cu means between surveys 4 and 6 (in transformation only).
There was no difference between Cu means from the other surveys. There also was a significant
difference in the Fe means between surveys 4 and 6 (in transformation only), as well as between surveys
1 and 2; and surveys 1 and 4. It is difficult to make generalizations about the Student's t test results
between survey mean values for the fall, 1990 sampling. The only weak trend linking the metals levels
was that the mean values for survey 6 appeared elevated as compared to the intermediate surveys (e.g.
survey 4). The reason(s) for the apparent elevation in metals levels for survey 6 cannot be definitively
determined. However, the field notes indicated that an oil spill had occurred at Mobil Oil the evening
prior to the sampling for survey 6. In addition, the discharge data presented hi Section 7.1 indicate that a
small runoff event was experienced during survey 6.
A particulatecdissolved ratio was calculated for Fe and Cu levels to determine if there were shifts
in the ratio associated with storm events. The ratio was not calculated for Pb because of the large number
of below detection limit observations associated with the dissolved phase. The ratio means and standard
deviations are presented hi Tables 63 and 64. On average, Fe and Cu concentrations associated with the
paniculate phase are greater than those of the dissolved phase. Higher concentrations of metals in the
paniculate phase commonly are observed hi natural and polluted environments (e.g. Allen, 1986; Benes et
al., 1985), although the ratios are dynamic and can vary with factors such as discharge (2water-particle
and particle-particle interaction), season, pH, and organic carbon levels (Forstner and Wittmann, 1983;
Karlsson et al., 1987). It has been suggested (e.g. Forstner and Witmann, 1983, p. 104-105) that
dissolved concentrations tend to decrease with discharge due to dilution and paniculate concentrations
tend to increase because of resuspension of bed and bank material. Recognizing data limitations, the Fe
ratios (Table 63) generally support the particulate-dissolved concentration relationship described by
Forstner and Wittmann (1983). However, the paniculate: dissolved ratio for Cu (Table 64) is greater
during steady-state periods, suggesting that there may be particulate Cu sources hi addition to
resuspension of bed and bank material. The large standard deviations in Table 64 limit the certainty with
which conclusion can be drawn.
The IUC ambient water quality criteria for Cu, Pb and Fe levels in whole water samples (i.e.
unfiltered), as quoted by Marsalek (1990), are 0.005 mg I'1, 0.02 mg I'1 and 0.3 mg I'1, respectively. The
total concentrations of Cu and Fe from the Buffalo River sites exceeded IJC criteria in all 45 "samples"
(six surveys at six sites, fall, 1990; three surveys at three sites, spring, 1992; duplicates were averaged
with the sample at each site). The total concentrations of Pb from the Buffalo River sites exceeded IJC
criteria hi 18 of 45 "samples".
242
-------
10. RESULTS OF CONVENTIONAL PARAMETER ANALYSIS
AND METALS QA/QC
243
-------
10.1 FALL 1990 SAMPLING
The data presented in this section reflect the reporting format from Alfred Analytical Laboratory.
The data include results for Pb, Cu and Fe from the preliminary samples collected on October 18, 1990 at
sites 1 and 2 (and not discussed in the previous section), as well as QA/QC results for metals.
The following abbreviations are used for each sample:
BR - Buffalo river
1-6- Survey Number
01 - Composite
01-06- Station
W- Water Sample
1- Regular
2- Duplicate
Therefore, BR10103W1 is Buffalo River, Survey 1, Composite, from Station 3, Water Sample (Regular).
244
-------
Table 61 Conventional Parameters and Metals QA/QC; Fall, 1990
Date SAMPLE RECEIVED: Oct 23, 1990
Sample: BR10101W1
Collected on: Oct 18, 1990 AT: n/a
Date REPORTED: Apr 8, 1991
method
ID# analyte code
2307 Alkalinity EPA310.1
2307 Sulfides EPA376.1
2307 T.Organic Carbon EPA415.1
2307 D.Organic Carbon EPA415.1
2307 Chloride SM407A
2307 T.S.Solids SM209C
2307 Calcium EPA215.1
2307 Magnesium EPA242.1
2307 Hardness SM314A
method
detection
limit
1.0
0.01
1.
1.
.0
.0
0.2
0.1
0.01
0.001
0.1
result
143
0.136
9.7
7.54
32.04
8.0
54.74
11.59
184.4
unit
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
Date SAMPLE RECEIVED: Oct 23, 1990
Sample #: BR10102W1
Collected on Oct 18, 1990 AT: n/a
method method
ID# analyte code detection
limit
2308 Alkalinity EPA310.1 1.0
2308 Sulfides EPA376.1 0.01
2308 T.Organic Carbon EPA415.1 1.0
2308 D.Organic Carbon EPA415.1 1.0
2308 Chloride SM407A 0.2
2308 T.S.Solids SM209C 0.1
2308 Calcium EPA215.1 0.01
2308 Magnesium EPA242.1 0.001
2308 Hardness SM314A 0.1
Date REPORTED: Apr 8, 1991
result
117
0.22
12.2
9.88
27.16
14
42.93
10.10
149
unit
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
Date SAMPLE RECEIVED: Oct 23, 1990
Sample #: BR10101W1
Collected on: Oct 22, 1990 AT: 8:38 am
Date REPORTED: Apr 8, 1991
2309
2309
2309
2309
2309
2309
2309
2309
2309
analyte
Alkalinity
Sulfides
T. Organic Carbon
D. Organic Carbon
Chloride
T.S. Solids
Calcium
Magnesium
Hardness
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
method
detection
limit
1.0
0.01
.0
.0
1.
1.
0.2
0.1
0.01
0.001
0.1
result
111.3
0.18
11.4
9.84
23.45
6
42.46
9.48
145.1
unit
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
245
-------
Date SAMPLE RECEIVED: Oct. 23, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR10102W1
Collected on: Oct 22, 1990 AT: 9:50 am (1/3 point): 10:17 am (2/3 point)
.
ID#
2310
2310
2310
2310
2310
2310
2310
2310
2310
2311
2311
analyte
Alkalinity
Sulfides
T. Organic Carbon
D . Organic Carbon
Chloride
T.S. Solids
Calcium
Magnesium
Hardness
Alkalinity
Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
result
106
0.153
11.6
10.9
12.12
4
38.5
8.59
131.53
106.5
0.17
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
Date SAMPLE RECEIVED: Oct 23, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR10103W1
Collected on: Oct 22, 1990 AT: 11:22 am (1/3 site); 11.57 am (2/3 site)
ID# analyte
2312 Alkalinity
2312 Sulfides
2312 T.Organic Carbon
2312 D.Organic Carbon
2312 Chloride
2312 T.S.Solids
2312 Calcium
2312 Magnesium
2312 Hardness
2313 Alkalinity
2313 Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
result
100
0.2
11.2
10.5
20.20
14
34.55
7.70
118
95.4
0.20
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
Date SAMPLE RECEIVED: Oct 23, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR10103W2 Field duplicate
Collected on: Oct 22, 1990 AT: 11:23 am (1/3 site); 11:58 (2/3 site)
ID# analyte
2314 Alkalinity
2314 Sulfides
2314 T.Organic Carbon
2314 D.Organic Carbon
2314 Chloride
2314 T.S.Solids
2314 Calcium
2314 Magnesium
2314 Hardness
2315 Alkalinity
2315 Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242 . 1
SM314A
EP A3 10.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
result
95.4
0.21
11.4
10.5
19.96
6
32.84
8.20
116
95.4
0.20
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
246
-------
Date SAMPLE RECEIVED: Oct 23, 1990
Sample #: BR10104W1
Collected on: Oct 22, 1990 AT: 3:18 pm
method method
ID# analyte code detection
limit
2316 Alkalinity EPA310.1 1.0
2316 Sulfides EPA376.1 0.01
2316 T.Organic Carbon EPA415.1 1.0
2316 D.Organic Carbon EPA415.1 1.0
2316 Chloride SM407A 0.2
2316 T.S.Solids SM209C 0.1
2316 Calcium EPA215.1 0.01
2316 Magnesium EPA242.1 0.001
2316 Hardness SM314A 0.1
Date REPORTED: Apr 8, 1991
result
27
0.09
12.2
10.94
17.64
24
28.06
6.96
98
unit
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
Date SAMPLE RECEIVED: Oct 23, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR10105W1
Collected on: Oct 22, 1990 AT: 4:52 pm (1/3 site); 5:14 pm (2/3 site)
ID# analyte
2317 Alkalinity
2317 Sulfides
2317 T.Organic Carbon
2317 D.Organic Carbon
2317 Chloride
2317 T.S.Solids
2317 Calcium
2317 Magnesium
2317 Hardness
2318 Alkalinity
2318 Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
result
137
0.36
14.2
12.5
18.80
30
29.88
6.28
100.5
83
0.114
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
Date SAMPLE RECEIVED: Oct 23, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR10106W1
Collected on Oct 22, 1990 AT: 6:10 pm (1/3 site); 6:31 pm (1/2 site); 6:46 pm
(2/3 site)
»
ID#
2319
2319
2319
2319
2319
2319
2319
2319
2319
2320
2320
2321
2321
analyte
Alkalinity
Sulfides
T. Organic Carbon
D. Organic Carbon
Chloride
T.S. Solids
Calcium
Magnesium
Hardness
Alkalinity
Sulfides
Alkalinity
Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
0.
0.
.2
.1
0.01
0.001
0.1
1.0
0.01
1.0
0.01
result
unit
85.4
0.14
13.2
12.74
19.04
28
23.20
7.51
111.33
84.8
0.60
90.6
0.02
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (1/2 site)
ppm (1/2 site)
ppm (2/3 site)
ppm (2/3 site)
247
-------
Date SAMPLE RECEIVED: Oct 28, 1990
Sample #: BR20101W1
Collected on: Oct 27, 1990 AT: 8:26 am
Date REPORTED: Apr 8, 1991
m
ID#
2333
2333
2333
2333
2333
2333
2333
2333
2333
analyte
D. Organic Carbon
T. Organic Carbon
Sulfides
Alkalinity
Chloride
T.S. Solids
Calcium
Magnesium
Hardness
method
code
EPA415.1
EPA415.1
EPA376.1
EPA310.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
method
detection
limit
1.0
1.0
0.01
1.0
0.
0.
.2
.1
0.01
0.001
0.1
result
11.0
12.3
0.24
121
25.00
3.0
36.08
7.90
124.12
unit
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
Date SAMPLE RECEIVED: Oct 28, 1990 Date REPORTED: Apr 8, 1991
Sample # BR20102W1
Collected on: Oct 27, 1990 AT: 9:23 am (1/3 site); 9:49 am (2/3 site)
•
ID#
2334
2334
2334
2334
2334
2334
2334
2334
2334
2335
2335
method
analyte code
D. Organic Carbon EPA415.1
T. Organic Carbon EPA415.1
Sulfides EPA376.1
Alkalinity EPA310.1
Chloride SM407A
T.S. Solids SM209C
Calcium EPA215.1
Magnesium EPA242.1
Hardness SM314A
Sulfides EPA376.1
Alkalinity EPA310.1
method
detection
limit
1.0
1.0
0.01
1.0
0.2
0.1
0.01
0.001
0.1
0.01
1.0
result
12.92
13.1
0.264
116
26.93
1.0
42.06
8.34
127.2
0.08
118
unit
ppm
ppm
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
Date SAMPLE RECEIVED: Oct 28, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR20103W1
Collected on: Oct 27, 1990 AT: 10:48 am (1/3 site); 11:27 am (2/3 site)
ID# analyte
2336 D.Organic Carbon
2336 T.Organic Carbon
2336 Sulfides
2336 Alkalinity
2336 Chloride
2336 T.S.Solids
2336 Calcium
2336 Magnesium
2336 Hardness
2337 Sulfides
2337 Alkalinity
method
code
EPA415.1
EPA415 . 1
EPA376.1
EPA310.1
SM407A
SM209C
EPA215.1
EPA242 . 1
SM314A
EPA376.1
EPA310.1
method
detection
limit
1.0
1.0
0.01
1.0
0.2
0.1
0.01
0.001
0.1
0.01
1.0
result
7.02
9.5
0.18
114
26.47
16
36.03
9.03
127.2
0.25
109
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
248
-------
Date SAMPLE RECEIVED: Oct 28, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR20103W2
Collected on: Oct 27, 1990 AT: 10:47 am (1/3 site); 11.28 am (2/3 site)
•
ID#
•
2338
2338
2338
2338
2338
2338
2338
2338
2338
2338
2338
2338
2339
2339
method
analyte code
D. Organic Carbon EPA415.1
T. Organic Carbon EPA415.1
Sulfides EPA376.1
Alkalinity EPA310.1
Chloride SM407A
T.S. Solids SM209C
Lead EPA239.2
Copper EPA2 20.2
Iron EPA236.2
Calcium EPA215.1
Magnesium EPA242.1
Hardness SM314A
Sulfides EPA376.1
Alkalinity EPA310.1
method
detection
limit
1.0
1.0
0.01
1.0
0.2
0.1
0.001
0.001
0.03
0.01
0.001
0.1
0.01
1.0
result
7.64
10.6
0.164
113
26.23
4.0
<.001
.014
.205
38.08
8.98
132.1
0.242
112.5
unit
ppm
ppm
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
Date SAMPLE RECEIVED: Oct 28, 1990
Sample #: BR20104W1
Collected on: Oct 27, 1990 AT: 3:14 pm
Date REPORTED: Apr 8, 1991
»
ID#
2340
2340
2340
2340
2340
2340
2340
2340
2340
analyte
D. Organic Carbon
T. Organic Carbon
Sulfides
Alkalinity
Chloride
T.S. Solids
Calcium
Magnesium
Hardness
method
code
EPA415.1
EPA415.1
EPA376.1
EPA310.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
method
detection
limit
1.0
1.0
0.01
1.0
0.2
0.1
0.01
0.001
0.1
result
6.07
14.3
0.213
114
26.00
12.0
42.90
8.48
142.0
unit
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
Date SAMPLE RECEIVED: Oct 28, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR20105W1
Collected on: Oct 27, 1990 AT: 4:51 pm (1/3 site); 5:14 pm (2/3 site)
ID# analyte
2341 D.Organic Carbon
2341 T.Organic Carbon
2341 Sulfides
2341 Alkalinity
2341 Chloride
2341 T.S.Solids
2341 Calcium
2341 Magnesium
2341 Hardness
2342 Sulfides
2342 Alkalinity
method
code
EPA415.1
EPA415.1
EPA376.1
EPA310.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA376.1
EPA310.1
method
detection
limit
1.0
1.0
0.01
1.0
0.2
0.1
0.01
0.001
0.1
0.01
1.0
result
8.6
15.9
0.14
120
27.39
3.0
38.35
9.38
134.4
0.29
125
unit
ppm
ppm
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
249
-------
Date SAMPLE RECEIVED: Oct 28, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR20106W1
Collected on: Oct 27, 1990 AT: 6:08 pm (1/3 site); 6:24 pm (1/2 site); 6:39
pm (2/3 site)
•
ID#
2343
2343
2343
2343
2343
2343
2343
2343
2343
2344
2344
2345
2345
analyte
D. Organic Carbon
T. Organic Carbon
Sulfides
Alkalinity
Chloride
T.S. Solids
Calcium
Magnesium
Hardness
Sulfides
Alkalinity
Sulfides
Alkalinity
method
code
EPA415.1
EPA415 . 1
EPA376.1
EP A3 10.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA376.1
EPA310.1
EPA376.1
EPA310.1
method
detection
limit
1.0
1.0
0.01
1.0
0.2
0.1
0.01
0.001
0.1
0.01
1.0
0.01
1.0
result
7.85
12.7
0.15
110
25.54
11.0
34.53
9.27
124.4
0.33
109
0.17
111
unit
ppm
ppm
ppm (1/3
ppm (1/3
ppm
ppm
ppm
ppm
ppm
ppm (1/2
ppm (1/2
ppm (2/3
ppm (2/3
site)
site)
site)
site)
site)
site)
Date SAMPLE RECEIVED: Oct 28, 1990
Sample # BR PROJECT BOTTLE BLANK
Collected on: Oct 27, 1990 AT: 9:57 am
Date REPORTED: Apr 8, 1991
ID#
2346
2346
2346
2346
2346
analyte
Lead
Copper
Iron
Calcium
Magnesium
method
code
EPA239.2
EPA220.2
EPA236.2
EPA215.1
EPA242.1
method
detection
limit
0.001
0.001
0.03
0.01
0.001
result
<.001
.068
<.03
<0.01
<.001
unit
ppm
ppm
ppm
ppm
ppm
Date SAMPLE RECEIVED: Nov 1, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR30101W1
Collected on: Oct 31, 1990 AT: 6:55 am
method method
ID# analyte code detection result unit
limit
2362 Alkalinity EPA310.1 1.0 179 ppm
2362 Sulfides EPA376.1 0.01 0.02 ppm
2362 T.Organic Carbon EPA415.1 1.0 14.02 ppm
2362 D.Organic Carbon EPA415.1 1.0 11.7 ppm
2362 Chloride SM407A 0.2 21.59 ppm
2362 T.S.Solids SM209C 0.1 3.0 ppm
2362 Calcium EPA215.1 0.01 37.68 ppm
2362 Magnesium EPA242.1 0.001 7.95 ppm
2362 Hardness SM314A 0.1 127 ppm
250
-------
Date SAMPLE RECEIVED: Nov 1, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR30102W1
Collected on: Oct 31, 1990 AT: 7:43 am (1/3 site); 8:05 am (2/3 site)
ID# analyte
2363 Alkalinity
2363 Sulfides
2363 T.Organic Carbon
2363 D.Organic Carbon
2363 Chloride
2363 T.S.Solids
2363 Calcium
2363 Magnesium
2363 Hardness
2364 Alkalinity
2364 Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
result
115
0.12
14.9
10.25
21.00
4.0
42.60
8.45
141.2
116
0.053
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
Date SAMPLE RECEIVED: Nov 1, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR30103W1
Collected on: Oct 31, 1990 AT: 9:30 am (1/3 site); 9:50 am (2/3 site)
,
ID#
*
2365
2365
2365
2365
2365
2365
2365
2365
2365
2366
2366
2366
analyte
Alkalinity
Sulfides
T. Organic Carbon
D . Organic Carbon
Chloride
T.S. Solids
Calcium
Magnesium
Hardness
Alkalinity
Sulfides
Chloride
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415 . 1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
SM407A
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
0.2
result
116
0.08
11.42
10.96
25.07
4.0
40.40
9.64
140.6
99
0.06
21.59
unit
ppm (1/3
ppm (1/3
ppm
ppm
ppm (1/3
ppm
ppm
ppm
ppm
ppm (2/3
ppm (2/3
ppm (2/3
site)
site)
site)
site)
site)
site)
Date SAMPLE RECEIVED: Nov 1, 1990
Sample #: BR30104W1
Collected on: Oct 31, 1990 AT: 10:40 am
method method
ID# analyte code detection
limit
2367 Alkalinity EPA310.1 1.0
2367 Sulfides EPA376.1 0.01
2367 T.Organic Carbon EPA415.1 1.0
2367 D.Organic Carbon EPA415.1 1.0
2367 Chloride SM407A 0.2
2367 T.S.Solids SM209C 0.1
2367 Calcium EPA215.1 0.01
2367 Magnesium EPA242.1 0.001
2367 Hardness SM314A 0.1
Date REPORTED: Apr 8, 1991
result
135
0.06
12.7
12.11
28.56
2.0
36.43
7.22
121
unit
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
251
-------
Date SAMPLE RECEIVED: Nov 1, 1990
Sample #: BR30104W2
Collected on: Oct 31, 1990 AT: 10:41 am
Date REPORTED: Apr 8, 1991
ID# analyte
2368 Alkalinity
2368 Sulfides
2368 T.Organic Carbon
2368 D.Organic Carbon
2368 Chloride
2368 T.S.Solids
2368 Calcium
2368 Magnesium
2368 Hardness
method
code
EPA310.1
EPA376.1
EPA415.
EPA415.
SM407A
SM209C
EPA215.
EPA242.
SM314A
.1
.1
.1
.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
result
110
0.055
12.0
11.84
25.3
6.0
31.09
6.10
103
unit
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
Date SAMPLE RECEIVED: Nov 1, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR30105W1
Collected on: Oct 31, 1990 AT: 12:50 pm (1/3 site); 1:11 pm (2/3 site)
ID# analyte
2369 Alkalinity
2369 Sulfides
2369 T.Organic Carbon
2369 D.Organic Carbon
2369 Chloride
2369 T.S.Solids
2369 Calcium
2369 Magnesium
2369 Hardness
2370 Alkalinity
2370 Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242 . 1
SM314A
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
result
130
0.11
9.8
07.64
26.93
21.0
22.65
8.18
90.24
82
0.18
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
Date SAMPLE RECEIVED: Nov 1, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR30106W1
Collected on: Oct 31, 1990 AT: 1:57 pm (1/3 site); 2:16 pm (1/2 site); 2:40
pm (2/3 site)
^
ID#
2371
2371
2371
2371
2371
2371
2371
2371
2371
2372
2372
2373
2373
analyte
Alkalinity
Sulfides
T. Organic Carbon
D. Organic Carbon
Chloride
T.S. Solids
Calcium
Magnesium
Hardness
Alkalinity
Sulfides
Alkalinity
Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
1.0
0.01
result
130
0.09
13.82
11.24
40.86
1.0
13.06
2.53
43.03
160
0.082
100
0.16
unit
ppm (1/3
ppm (1/3
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (1/2
ppm (1/2
ppm (2/3
ppm (2/3
site)
site)
site)
site)
site)
site)
252
-------
Date SAMPLE RECEIVED: Nov 6, 1990
Sample #: BR40101W1
Collected on: Nov 5, 1990 AT: 7:06 am
Date REPORTED: Apr 8, 1991
*
ID#
2407
2407
2407
2407
2407
2407
2407
2407
2407
analyte
Alkalinity
Sulfides
T. Organic Carbon
D. Organic Carbon
Chloride
T.S. Solids
Calcium
Magnesium
Hardness
method
code
EPA310.1
EPA376.1
EPA415 . 1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
result
130
0.14
11.86
8.65
42.49
3.0
34.47
7.22
118
unit
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
Date SAMPLE RECEIVED: Nov 6, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR40101W2 Field duplicate
Collected on: Nov 5, 1990 AT: 7:08 am
method
ID# analyte code
2408 Alkalinity EPA310.1
2408 Sulfides EPA376.1
2408 T.Organic Carbon EPA415.1
2408 D.Organic Carbon EPA415.1
2408 Chloride SM407A
2408 T.S.Solids SM209C
2408 Calcium EPA215.1
2408 Magnesium EPA242.1
2408 Hardness SM314A
method
detection
limit
1.0
0.01
0.2
0.1
0.01
0.001
0.1
result
132
0.14
12.08
8.27
35.06
2.0
31.66
6.10
109.2
unit
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
Date SAMPLE RECEIVED: Nov 6, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR40102W1
Collected on: Nov 5, 1990 AT: 10:02 am (1/3 site); 10:27 am (2/3 site)
method method
ID# analyte code detection result
limit
2409 Alkalinity EPA310.1 1.0 128
2409 Sulfides EPA376.1 0.01 0.33
2409 T.Organic Carbon EPA415.1 1.0 12.34
2409 D.Organic Carbon EPA415.1 1.0 8.0
2409 Chloride SM407A 0.2 39.7
2409 T.S.Solids SM209C 0.1 13
2409 Calcium EPA215.1 0.01 46.92
2409 Magnesium EPA242.1 0.001 10.45
2409 Hardness SM314A 0.1 139
2410 Alkalinity EPA310.1 1.0 124
2410 Sulfides EPA376.1 0.01 0.25
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
253
-------
Date SAMPLE RECEIVED: Nov 6, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR40103W1
Collected on: Nov 5, 1990 AT: 11:09 am (1/3 site); 11:29 am (2/3 site)
ID# analyte
2411 Alkalinity
2411 Sulfides
2411 T.Organic Carbon
2411 D.Organic Carbon
2411 Chloride
2411 T.S.Solids
2411 Calcium
2411 Magnesium
2411 Hardness
2412 Alkalinity
2412 Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
result
124
0.06
9.18
7.35
34.36
24
45.19
4.26
130.4
126
0.1
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
Date SAMPLE RECEIVED: Nov 6, 1990
Sample #: BR40104W1
Collected on: Nov 5, 1990 AT: 12:25 pm
Date REPORTED: Apr 8, 1991
method
ID# analyte code
2413 Alkalinity EPA310.1
2413 Sulfides EPA376.1
2413 T.Organic Carbon EPA415.1
2413 D.Organic Carbon EPA415.1
2413 Chloride SM407A
2413 T.S.Solids SM209C
2413 Calcium EPA215.1
2413 Magnesium EPA242.1
2413 Hardness SM314A
method
detection
limit
1.0
0.01
1.
1.
,0
.0
0.2
0.1
0.01
0.001
0.1
result
114
0.17
9.6
8.59
28.32
2
43.99
7.65
141.4
unit
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
Date SAMPLE RECEIVED: Nov 6, 1990
Sample #: BR40105W1
Collected on: Nov 5, 1990 AT:
ID# analyte
2414 Alkalinity
2414 Sulfides
2414 T.Organic Carbon
2414 D.Organic Carbon
2414 Chloride
2414 T.S.Solids
2414 Calcium
2414 Magnesium
2414 Hardness
2415 Alkalinity
2415 Sulfides
Date REPORTED: Apr 8, 1991
2:11 pm (1/3 site); 2:35 pm (2/3 site)
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242 . 1
SM314A
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
result
118
0.18
10.4
8.04
25.07
8.0
40.57
8.63
137
112
0.133
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
254
-------
Date SAMPLE RECEIVED: Nov 6, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR40106W1
Collected on: Nov 5, 1990 AT: 3:30 pm (1/3 site); 3:54 pm (1/2 site); 4:13
pm (2/3 site)
method method
ID# analyte code detection result unit
limit
2416 Alkalinity
2416 Sulfides
2416 T.Organic Carbon
2416 D.Organic Carbon
2416 Chloride
2416 T.S.Solids
2416 Calcium
2416 Magnesium
2416 Hardness
2417 Alkalinity
2417 Sulfides
2418 Alkalinity
2418 Sulfides
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
EPA310.1
EPA376.1
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
1.0
0.01
138
0.082
10.66
9.29
24.38
4.0
19.53
10.00
90
102.2
0.1
131.8
0.197
ppm (1/3
ppm (1/3
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (1/2
ppm (1/2
ppm (2/3
ppm (2/3
site)
site)
site)
site)
site)
site)
Date SAMPLE RECEIVED: Nov 11, 1990
Sample #: BR50101W1
Collected on: Nov 9, 1990 AT: 1:22 pm
ID# analyte
2422 Alkalinity
2422 Sulfides
2422 T.Organic Carbon
2422 D.Organic Carbon
2422 Chloride
2422 T.S.Solids
2422 Calcium
2422 Magnesium
2422 Hardness
Date REPORTED: Apr 8, 1991
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
result
85.4
0.27
13.46
8.46
19.04
28
38.75
8.30
131
unit
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
Date SAMPLE RECEIVED: Nov 11, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR50102W1
Collected on: Nov 9, 1990 AT: 11:44 am (1/3 site); 12:24 pro (2/3 site)
ID# analyte
2423 Alkalinity
2423 Sulfides
2423 T.Organic Carbon
2423 D.Organic Carbon
2423 Chloride
2423 T.S.Solids
2423 Calcium
2423 Magnesium
2423 Hardness
2424 Alkalinity
2424 Sulfides
method
code
method
detection
limit
result
unit
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
85.4
0.21
14.19
9.2
19.04
28
38.26
8.16
129.14
85.4
0.26
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
255
-------
Date SAMPLE RECEIVED: Nov 11, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR50102W2 Field duplicate
Collected on: Nov 9, 1990 AT: 11:46 am (1/3 site); 12:25 pm (2/3 site)
ID# analyte
2425 Alkalinity
2425 Sulfides
2425 T.Organic Carbon
2425 D.Organic Carbon
2425 Chloride
2425 T.S.Solids
2425 Calcium
2425 Magnesium
2425 Hardness
2426 Alkalinity
2426 Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
result
85.4
0.21
13.74
8.65
19.04
28
37.98
8.08
128.11
85.4
0.29
unit
ppm (1/3 site)
ppra (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
Date SAMPLE RECEIVED: Nov 11, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR50103W1
Collected on: Nov 9, 1990 AT: 10:29 am (1/3 site); 10:50 am (2/3 site)
ID# analyte
2427 Alkalinity
2427 Sulfides
2427 T.Organic Carbon
2427 D.Organic Carbon
2427 Chloride
2427 T.S.Solids
2427 Calcium
2427 Magnesium
2427 Hardness
2428 Alkalinity
2428 Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.
0.
.2
.1
0.01
0.001
0.1
1.0
0.01
result
85.4
0.21
7.5
7.04
19.04
28
37.16
7.92
125.4
85.4
0.19
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
Date SAMPLE RECEIVED: Nov 11, 1990
Sample #: BR50104W1
Collected on: Nov 9, 1990 AT: 9:28 am
method method
ID# analyte code detection
limit
2429 Alkalinity EPA310.1 1.0
2429 Sulfides EPA376.1 0.01
2429 T.Organic Carbon EPA415.1 1.0
2429 D.Organic Carbon EPA415.1 1.0
2429 Chloride SM407A 0.2
2429 T.S.Solids SM209C 0.1
2429 Calcium EPA215.1 0.01
2429 Magnesium EPA242.1 0.001
2429 Hardness SM314A 0.1
Date REPORTED: Apr 8, 1991
result
85.4
0.14
6.6
5.89
19.04
28
37.02
7.92
125.2
unit
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
256
-------
Date SAMPLE RECEIVED: Nov 11, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR50105W1
Collected on: Nov 9, 1990 AT: 8:17 am (1/3 site); 8:39 am (2/3 site)
ID# analyte
2430 Alkalinity
2430 Sulfides
2430 T.Organic Carbon
2430 D.Organic Carbon
2430 Chloride
2430 T.S.Solids
2430 Calcium
2430 Magnesium
2430 Hardness
2431 Alkalinity
2431 Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415 . 1
SM407A
SM209C
EPA215 . 1
EPA242.1
SM314A
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
result
85.4
0.21
7.53
6.08
19.04
28
36.09
7.30
120.2
85.4
0.09
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
Date SAMPLE RECEIVED: Nov 11, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR50106W1
Collected on: Nov 9, 1990 AT: 6:50 am (1/3 site); 7:12 am (1/2 site); 7:31
am (2/3 site)
^
ID#
2432
2432
2432
2432
2432
2432
2432
2432
2432
2433
2433
2434
2434
analyte
Alkalinity
Sulfides
T. Organic Carbon
D. Organic Carbon
Chloride
T.S. Solids
Calcium
Magnesium
Hardness
Alkalinity
Sulfides
Alkalinity
Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
0.
0.
.2
.1
0.01
0.001
0.1
1.0
0.01
1.0
0.01
result
85.4
0.18
7.98
6.96
19.04
28
41.02
8.22
136.3
85.4
0.17
85.4
0.18
unit
ppm (1/3
ppm (1/3
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (1/2
ppm (1/2
ppm (2/3
ppm (2/3
site)
site)
site)
site)
site)
site)
Date SAMPLE RECEIVED: Nov 14, 1990
Sample #: BR60101W1
Collected on: Nov 13, 1990 AT: 7:56 am
Date REPORTED: Apr 8, 1991
method
ID# analyte code
2442 Alkalinity EPA310.1
2442 Sulfides EPA376.1
2442 T.Organic Carbon EPA415.1
2442 D.Organic Carbon EPA415.1
2442 Chloride SM407A
2442 T.S.Solids SM209C
2442 Calcium EPA215.1
2442 Magnesium EPA242.1
2442 Hardness SM314A
method
detection
limit
1.0
0.01
1.0
1.0
0.
0.
.2
.1
0.01
0.001
0.1
result
107
0.15
10.3
9.53
27.86
12.0
41.02
7.85
135
unit
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
257
-------
Date SAMPLE RECEIVED: Nov 14, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR60102W1
Collected on: Nov 13, 1990 AT: 8:46 am (1/3 site); 9:10 am (2/3 site)
ID# analyte
2443 Alkalinity
2443 Sulfides
2443 T.Organic Carbon
2443 D.Organic Carbon
2443 Chloride
2443 T.S.Solids
2443 Calcium
2443 Magnesium
2443 Hardness
2444 Alkalinity
2444 Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
result
102.2
0.18
17.7
8.27
26.93
20.0
39.35
7.67
130
108
0.19
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
Date SAMPLE RECEIVED: Nov 14, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR60103W1
Collected on: Nov 13, 1990 AT: 10:00 am (1/3 site); 10:31 am (2/3 site)
ID# analyte
2445 Alkalinity
2445 Sulfides
2445 T.Organic Carbon
2445 D.Organic Carbon
2445 Chloride
2445 T.S.Solids
2445 Calcium
2445 Magnesium
2445 Hardness
2446 Alkalinity
2446 Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
result
99.6
0.23
9.1
2.41
23.68
16.0
38.70
7.69
129
101.2
0.08
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
Date SAMPLE RECEIVED: Nov 14, 1990
Sample #: BR60104W1
Collected on: Nov 13, 1990 AT: 11:21 am
method method
ID# analyte code detection
limit
2447 Alkalinity EPA310.1 1.0
2447 Sulfides EPA376.1 0.01
2447 T.Organic Carbon EPA415.1 1.0
2447 D.Organic Carbon EPA415.1 1.0
2447 Chloride SM407A 0.2
2447 T.S.Solids SM209C 0.1
2447 Calcium EPA215.1 0.01
2447 Magnesium EPA242.1 0.001
2447 Hardness SM314A 0.1
Date REPORTED: Apr 8, 1991
result
88.8
0.17
14.61
7.70
20.89
76.0
36.34
7.18
120.3
unit
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
258
-------
Date SAMPLE RECEIVED: Nov 14, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR60105W1
Collected on: Nov 13, 1990 AT: 12:22 pm (1/3 site); 12:58 pm (2/3 site)
ID# analyte
2448 Alkalinity
2448 Sulfides
2448 T.Organic Carbon
2448 D.Organic Carbon
2448 Chloride
2448 T.S.Solids
2448 Calcium
2448 Magnesium
2448 Hardness
2449 Alkalinity
2449 Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
result
87.6
0.19
13.0
9.7
19.50
4.0
34.07
6.44
112
86.4
0.14
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppra (2/3 site)
Date SAMPLE RECEIVED: Nov 14, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR60105W2 Field duplicate
Collected on: Nov 13, 1990 AT: 12:20 pm (1/3 site); 12:20 pm (2/3 site)
ID# analyte
2450 Alkalinity
2450 Sulfides
2450 T.Organic Carbon
2450 D.Organic Carbon
2450 Chloride
2450 T.S.Solids
2450 Calcium
2450 Magnesium
2450 Hardness
2451 Alkalinity
2451 Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
result
84.2
0.19
16.26
9.32
19.50
16.0
33.37
6.93
112
87
0.14
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppra
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
Date SAMPLE RECEIVED: Nov 14, 1990 Date REPORTED: Apr 8, 1991
Sample #: BR60106W1
Collected on: Nov 13, 1990 AT: 2:10 pm (1/3 site); 2:29 pm (1/2 site); 2:48
pm (2/3 site)
.
ID#
2452
2452
2452
2452
2452
2452
2452
2452
2452
2453
2453
2454
2454
analyte
Alkalinity
Sulfides
T. Organic Carbon
D. Organic Carbon
Chloride
T.S. Solids
Calcium
Magnesium
Hardness
Alkalinity
Sulfides
Alkalinity
Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
1.0
0.01
result
90
0.20
19.68
7.19
19.96
8.0
34.64
7.25
116.4
92
0.21
90.2
0.18
unit
ppm (1/3
ppm (1/3
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (1/2
ppm (1/2
ppm (2/3
ppm (2/3
site)
site)
site)
site)
site)
site)
259
-------
Date SAMPLE RECEIVED: Nov 11, 1990
Sample #: laboratory bottle blank.
Collected on: AT:
Date REPORTED: Apr 8, 1991
ID#
2520
2520
2520
2520
2520
analyte
Lead
Copper
Iron
Calcium
Magnesium
method
code '
EPA239.2
EPA220.2
EPA236.2
EPA215.1
EPA242.1
method
detection
limit
0.001
0.001
0.03
0.01
0.001
result
<0.001
0.009
0.024
0.16
0.23
unit
ppm
ppm
ppm
ppm
ppm
Date SAMPLE RECEIVED: Dec 11, 1990
Sample #: W #1 Check sample
Collected on: AT:
Date REPORTED: Mar 21, 1991
ID#
analyte
2541 Lead
2541 Copper
2541 Iron
method
code
EPA239.2
EPA220.2
EPA236.2
method
detection
limit
0.001
0.001
0.03
result
.007
.133
0.2
unit
ppm
ppm
ppm
Date SAMPLE RECEIVED: Dec 11, 1990
Sample #: W #2 Check sample
Collected on: AT:
Date REPORTED: Mar 21, 1991
ID#
2542
2542
2542
analyte
Lead
Copper
Iron
method
code
EPA239.2
EPA220.2
EPA236.2
method
detection
limit
0.001
0.001
0.03
result
<.001
<.001
<.001
unit
ppm
ppm
ppm
Date SAMPLE RECEIVED: Dec 11, 1990
Sample #: W #3 Check sample
Collected on: AT:
Date REPORTED: Mar 21, 1991
ID#
analyte
2543 Lead
2543 Copper
2543 Iron
method
code
EPA239.2
EPA220.2
EPA236.2
method
detection
limit
0.001
0.001
0.03
result
<.001
<.001
<.001
unit
ppm
ppm
ppm
Date SAMPLE RECEIVED: Dec 11, 1990
Sample #: W #4 Check sample
Collected on: AT:
Date REPORTED: Mar 21, 1991
ID#
analyte
2544 Lead
2544 Copper
2544 Iron
method
code
EPA239.2
EPA220.2
EPA236.2
method
detection
limit
0.001
0.001
0.03
result
0.063
0.069
1.05
unit
ppm
ppm
ppm
260
-------
Date SAMPLE RECEIVED: Dec 11, 1990
Sample #: S #1 Check sample
Collected on: AT:
Date REPORTED: Mar 21, 1991
ID#
2545
2545
2545
analyte
Lead
Copper
Iron
method
code
EPA239.2
EPA220.2
EPA236.2
method
detection
limit
0.001
0.001
0.03
result
5.47
16.9
18.1
unit
mg/kg
mg/kg
g/kg
Date SAMPLE RECEIVED: Dec 11, 1990
Sample #: S #2 Check sample
Collected on: AT:
Date REPORTED: Mar 21, 1991
ID#
2546
2546
2546
analyte
Lead
Copper
Iron
method
code
EPA239.2
EPA220.2
EPA236.2
method
detection
limit
0.001
0.001
0.03
result
399
1840
23.67
unit
mg/kg
mg/kg
g/kg
261
-------
10.2 Spring, 1992 Sampling
The data presented in this section reflect the reporting format from Alfred Analytical
Laboratory. This section also includes a summary of the QA/QC checks reported by Alfred
Analytical Laboratory. All spring sample metal data are reported in Section 9. The sample
abbreviation scheme is the same as that used in Section 10.1 with the exception that an "S'
appears before the "BR", thereby denoting a Spring Buffalo River sample.
262
-------
Table 62 Conventional Parameters and QA/AC; Spring, 1992
Date SAMPLE RECEIVED: April 20, 1992 Date REPORTED: July 15, 1992
Sample #: SBR10101W1
Collected on: April 17, 1992 AT: 1:50 pm am (2/3 site)
method
ID# analyte code
5432 Alkalinity EPA310.1
5432 Sulfides EPA376.1
5432 T.Organic Carbon EPA415.1
5432 D.Organic Carbon EPA415.1
5432 Chloride SM407A
5432 T.S.Solids SM209C
5432 Calcium EPA215.1
5432 Magnesium EPA242.1
5432 Hardness SM314A
method
detection
limit
1.0
0.01
1.
1.
.0
.0
0.2
0.1
0.01
0.001
0.1
result
72.15
1.08
13
10
36.6
154
31.57
5.85
100
unit
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
Date SAMPLE RECEIVED: April 20, 1992
Sample #: SBR10101W2 (Field duplicate)
Collected on: April 17, 1992 AT: 1:50 pm
method method
ID# analyte code detection
limit
5433 Alkalinity EPA310.1 1.0
5433 Sulfides EPA376.1 0.01
5433 T.Organic Carbon EPA415.1 1.0
5433 D.Organic Carbon EPA415.1 1.0
5433 Chloride SM407A 0.2
5433 T.S.Solids SM209C 0.1
5433 Calcium EPA215.1 0.01
5433 Magnesium EPA242.1 0.001
5433 Hardness SM314A 0.1
Date REPORTED: July 15, 1992
result
72.15
0.60
17
10
38.2
52
29.82
6.07
92
unit
ppm
ppra
ppm
ppm
ppm
ppm
ppm
ppm
ppm
Date SAMPLE RECEIVED: April 20, 1992
Sample #: SBR60103W1
Collected on: April 17, 19920 AT: 5:30 pm (1/3 site)
Date REPORTED: July 15, 1992
ID# analyte
5435 Alkalinity
5435 Sulfides
5434 T.Organic Carbon
5434 D.Organic Carbon
5434 Chloride
5434 T.S.Solids
5434 Calcium
5434 Magnesium
5434 Hardness
5436 Alkalinity
5436 Sulfides
method
code
EPA310.1
EPA376.1
EPA415.
EPA415.
SM407A
SM209C
EPA215.
EPA242.
SM314A
EPA310.1
EPA376.1
.1
.1
,1
.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
result
83.25
0.32
11
10
38.9
74
32.77
7.69
112
86
0.48
unit
(1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppaa (2/3 site)
263
-------
Date SAMPLE RECEIVED: April 20. 1992
Sample #: SBR10106W1
Collected on: April 17, 1992 AT: 7:40 (1/3 site);
site)
Date REPORTED: July 15, 1992
(1/2 site);
(2/3
•
ID#
5438
5438
5437
5437
5437
5437
5437
5437
5437
5440
5440
5439
5439
analyte
Alkalinity
Sulfides
T. Organic Carbon
D. Organic Carbon
Chloride
T.S. Solids
Calcium
Magnesium
Hardness
Alkalinity
Sulfides
Alkalinity
Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
1.0
0.01
result
100
0.76
15
11
52.23
25.3
36.63
8.23
125.8
102.7
0.56
100
0.24
unit
ppm (1/3
ppm (1/3
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (1/2
ppm (1/2
ppm (2/3
ppm (2/3
site)
site)
site)
site)
site)
site)
Date SAMPLE RECEIVED: April 20. 1992
Sample #: SBR20101W1
Collected on: April 18, 1992 AT: 9:52 am
Date REPORTED: July 15, 1992
method
ID# analyte code
5441 Alkalinity EPA310.1
5441 Sulfides EPA376.1
5441 T.Organic Carbon EPA415.1
5441 D.Organic Carbon EPA415.1
5441 Chloride SM407A
5441 T.S.Solids SM209C
5441 Calcium EPA215.1
5441 Magnesium EPA242.1
5441 Hardness SM314A
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
result
72.15
0.56
13
13
32.4
74.0
27.80
6.09
103.4
unit
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
Date SAMPLE RECEIVED: April 20, 1992
Sample #: SBR20103W1
Collected on: April 18, 1992 AT: 1:00 pm
ID# analyte
5443 Alkalinity
5443 Sulfides
5442 T.Organic Carbon
5442 D.Organic Carbon
5442 Chloride
5442 T.S.Solids
5442 Calcium
5442 Magnesium
5442 Hardness
5444 Alkalinity
5444 Sulfides
Date REPORTED: July 15, 1992
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415 . 1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
result
72.15
0.36
13.9
12.6
32
28
25.81
5.91
102.6
72.15
0.40
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
264
-------
Date SAMPLE RECEIVED: April 20, 1992
Sample #: SBR20103W2 (Field duplicate)
Collected on: April 18, 1992 AT: 1:00 pm
Date REPORTED: July 15, 1992
ID# analyte
5446 Alkalinity
5446 Sulfides
5445 T.Organic Carbon
5445 D.Organic Carbon
5445 Chloride
5445 T.S.Solids
5445 Calcium
5445 Magnesium
5445 Hardness
5447 Alkalinity
5447 Sulfides
method
code
method
detection
limit
result
EPA310.1
EPA376.1
EPA415.1
EPA415 . 1
SM407A
SM209C
EPA215.1
EPA242 . 1
SM314A
EPA310.1
EPA376.1
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
72.15
0.36
12.40
11.45
33.2
24
26.21
6.43
88
72.15
0.40
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
Date SAMPLE RECEIVED: April 20. 1992
Sample #: SBR20106W1
Collected on: April 18, 1992 AT: 3:15 pm (1/3 site);
site)
Date REPORTED: July 15, 1992
(1/2 site);
(2/3
*
ID#
*
5449
5449
5448
5448
5448
5448
5448
5448
5448
5451
5451
5450
5450
analyte
Alkalinity
Sulfides
T. Organic Carbon
D. Organic Carbon
Chloride
T.S. Solids
Calcium
Magnesium
Hardness
Alkalinity
Sulfides
Alkalinity
Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.1
EPA242.1
SM314A
EPA310.1
EPA376.1
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.
1.
.0
.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
1.0
0.01
result
78
0.36
18
16
37.3
30.0
29.52
6.30
108
83.25
0.36
81.03
0.20
unit
ppm (1/3
ppm (1/3
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (1/2
ppm (1/2
ppm (2/3
ppm (2/3
site)
site)
site)
site)
site)
site)
Date SAMPLE RECEIVED: April 23. 1992
Sample #: SBR30101W1
Collected on: April 22, 1992 AT: 12:15 pm
Date REPORTED: July 15, 1992
method
ID# analyte code
5455 Alkalinity EPA310.1
5455 Sulfides EPA376.1
5455 T.Organic Carbon EPA415.1
5455 D.Organic Carbon EPA415.1
5455 Chloride SM407A
5455 T.S.Solids SM209C
5455 Calcium EPA215.1
5455 Magnesium EPA242.1
5455 Hardness SM314A
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
result
108.8
0.32
14
10
37.0
34.0
34.0
7.74
118.8
unit
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
265
-------
Date SAMPLE RECEIVED: April 23, 1992
Sample #: SBR30103W1
Collected on: April 22, 1992 AT: 1:30 pm
ID# analyte
5457 Alkalinity
5457 Sulfides
5456 T.Organic Carbon
5456 D.Organic Carbon
5456 Chloride
5456 T.S.Solids
5456 Calcium
5456 Magnesium
5456 Hardness
5458 Alkalinity
5458 Sulfides
Date REPORTED: July 15, 1992
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415 . 1
SM407A
SM209C
EPA215.1
EPA242 . 1
SM314A
EPA310.1
EPA376.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
resul
22.20
<0.01
15
9
41.5
29.0
34.45
7.46
126
94.35
0.24
unit
ppm (1/3 site)
ppm (1/3 site)
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm (2/3 site)
ppm (2/3 site)
Date SAMPLE RECEIVED: April 23. 1992
Sample #: SBR20106W1
Collected on: April 22, 1992 AT: 3:55 pm (1/3 site);
site)
Date REPORTED: July 15, 1992
(1/2 site);
(2/3
ID# analyte
5460 Alkalinity
5460 Sulfides
5459 T.Organic Carbon
5459 D.Organic Carbon
5459 Chloride
5459 T.S.Solids
5459 Calcium
5459 Magnesium
5459 Hardness
5461 Alkalinity
5461 Sulfides
5462 Alkalinity
5462 Sulfides
method
code
EPA310.1
EPA376.1
EPA415.1
EPA415.1
SM407A
SM209C
EPA215.
EPA242.
SM314A
EPA310.1
EPA376.1
EPA310.1
EPA376.1
.1
.1
method
detection
limit
1.0
0.01
1.0
1.0
0.2
0.1
0.01
0.001
0.1
1.0
0.01
1.0
0.01
result
77.7
<0.01
19
13
32.36
20.0
31.96
7.04
109
76.6
0.28
76.6
0.08
unit
ppn (1/3
ppn (1/3
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppn (1/2
ppm (1/2
ppm (2/3
ppm (2/3
site)
site)
site)
site)
site)
site)
266
-------
Date SAMPLE RECEIVED: April 23. 1992 Date REPORTED: July 15, 1992
Sample #: SBR20106W1 (Field duplicate)
Collected on: April 22, 1992 AT: 3:55 pm (1/3 site); (1/2 site); (2/3
site)
method method
ID# analyte code detection result unit
limit
5464 Alkalinity EPA310.1 1.0 63.3 ppm (1/3 site)
5464 Sulfides EPA376.1 0.01 0.20 ppm (1/3 site)
5463 T.Organic Carbon EPA415.1 1.0 13 ppm
5463 D.Organic Carbon EPA415.1 1.0 11 ppm
5463 Chloride SM407A 0.2 32.0 ppm
5463 T.S.Solids SM209C 0.1 19.0 ppra
5463 Calcium EPA215.1 0.01 30.55 ppm
5463 Magnesium EPA242.1 0.001 6.92 ppm
5463 Hardness SM314A 0.1 104 ppm
5465 Alkalinity EPA310.1 1.0 83.25 ppm (1/2 site)
5465 Sulfides EPA376.1 0.01 <0.01 ppm (1/2 site)
5466 Alkalinity EPA310.1 1.0 84.36 . ppm (2/3 site)
5466 Sulfides EPA376.1 0.01 0.36 ppm (2/3 site)
267
-------
Summary of QC/QA Information
Date: July 3, 1992
Analyte
Alkalinity
Chlorides
Chlorides
Hardness
Sulfides
TSS
TOC
DOC
Copper
Iron
Lead
MDL
ppm
1.0
0.2
0.2
0.0001
0.01
1.0
1.0
1.0
0.001
0.03
0.001
EPAQC
Expt.
Value
77.7
115.0
122.4
98.0
N/A
30.0
45.8
45.8
0.121
0.141
0.118
Check STD
Accept
Limits
59.36-
89.04
96.8-
145.2
96.8-
145.2
84.0-
126.0
N/A
25.6-
38.52
32.8-
49.2
32.8-
49.2
89.6-
134.4
100.8-
151.2
81.6-
122.4
RSD Blank
1.2 <1.0
2.60 2.45
#5432
1.86 0.18
#5455
3.17 2.0
#5454
18.14 0.36
#5443
1.86 <1.0
#5437
7.83 <1.0
#5442
2.023 <1.0
#5448
9.29 <0.00
#5448
0.93 <0.03
#5433
3.36 0.001
#5434
Matrix
Spike
Recovery
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
198.5
100.4
100.8
Date
Analyzed
4/21/92
4/22/92
5/05/92
6/01/92
5/05/92
5/14/92
6/01/92
6/01/92
6/08/95
6/05/92
6/05/92
268
-------
COPPEI
0.6 -
0.4
0.2
0 -
c
I
Cone x
10
50
100
enter X
enter X
enter X
enter X
enter X
enter X
enter X
enter X
enter X
enter X
enter X
enter X
CAL FEID63
Width: 9 Men
Data and Least Squares Fit
. Calibration Curve
.^^
^^
5 O O
i- CN
Abs Y
.068
.245
.433
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
aory: 225
oooooooooo
CONCENTRATION (ppm)
Analyst: SC Date: 6/8/92
X Y
3 3 = Total entries
33.33333 .2486667 = Mean
45.09250 .1825276 = St. Dev. (Sample)
36.81787 . 1490332 = St. Dev. (Pop.)
Y= A + B*X 95% confidence limits
.0330164 = A (Intercept) ± .0882774
.0040434 = B (Slope) ± .0023977
.9978240 = R2
.9989225 = R (Correlation)
.0001450 = residual Variance
.0120413 = S
12.698 ~(t.025)
Text = "6/8/92
Last Col/Row: 1127
READY Fl:Help F3:Names Ctrl-Backspace: Undo Ctrl-Break:Cancel CAPS NUM CALC
269
-------
0.08
0.06 --
0.04
0.02 -
Data and Least Squares Fit
Calibration Curve
0.5 1 1.5
CONCENTRATION (ppm)
2.5
LEAST SQUARES
IRON
Cone x
.5
1
2
X
X
X
X
X
X
X
X
X
X
X
X
enter
enter
enter
enter
enter
enter
enter
enter
enter
enter
enter
enter
CAL_PB!A77
Width: 9 Memory:
.016
.034
.067
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
Analyst: SC Date: 6/1/92
X Y
3 3 = Total entries
1.166667 .039 = Mean
.7637626 .0258650 = St. Dev. (Sample)
.6236096 .0211187 = St. Dev. (Pop.)
Y= A + B*X 95% confidence limits
-.0005 = A (Intercept) ± .0058806
.0338571 = B (Slope) ± .0094258
.9995195 = R2
.9997597 = R (Correlation)
.0000006 - Residual Variance
.0008018 = s
12.698 ~ (t025)
P Form = SQRT (A76)
225 Last Col/Row:I127
270
-------
0.6 i
0.4 -
0.2
0 •
c
Data and
Least Squares Fit
Calibration Curve
S
1 O
^
o
CM
/
^
O O O O O O O
000
CONCENTRATION (ppm)
LEAST SQUARES
LEAD
Cone
enter
enter
enter
enter
enter
enter
enter
enter
enter
enter
enter
enter
X
10
50
100
X
X
X
X
X
X
X
X
X
X
X
X
Abs Y
.116
.332
.548
enter
enter
enter
enter
enter
enter
enter
enter
enter
enter
enter
enter
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Analyst:
X
3
53.33333
45.09250
36.81787
SC Date: 6/5/92
Y
3=Total entries
.332 = Mean
.216 = St Dev. (Sample)
.1763633 = St. Dev. (Pop.)
Y= A + B*X 95% confidence limits
.0770492
.0047803
.9959016
.9979487
.0003824
.0195557
12.698 ~
= A (Intercept) ± .1433687
= B (Slope) ± .0038939
= R2
= R (Correlation)
= Residual Variance
= S
(t.025)
L-PB1C64
Width:
9
Mem<
ory
271
-------
Data and Least Squares Fit
CONCENTRATION (ppm)
LEAST SQUARES
TOC
Cone x Ab
enter
enter
enter
enter
enter
enter
enter
enter
enter
enter
enter
enter
0
50
100
X
X
X
X
X
X
X
X
X
X
X
X
.34
39.8
82.9
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
enter Y
CAL_PB'.B66
Width: 9 Memory:
221
Analyst: ML Date: 6/1/92
X Y
3 3=Total entries
50 41.01333 = Mean
50 41.29337 = St. Dev. (Sample)
40.82483 33.71590 = St. Dev. (Pop.)
Y= A + B*X 95% confidence limits
-.266667 = A (Intercept) ± 12.90738
.8256 = B (Slope) ± .2668555
.9993525 = R2
.9996762 =R (Correlation)
2.208267 = Residual Variance
1.486024 = s
12.698 ~(t025)
P Form=COUNT (B6:B40)
Last Col/Row:I127
272
-------
11. COMBINED SEWER QUANTITY ANALYSES
As noted in Section 3.2.1, wet weather samples were collected at selected sewer locations
on two occasons. December 5, 1990 and August 9, 1991. This section summarizes the
precipitation and flow characteristics associated with the wet weather sampling. Additional
overflow observations for the various smple sites are summarized as are the obseved overflow data
for the Babcock St. automated sapmle site.
11.1. DECEMBER 5, 1990 SAMPLING
As reported at the NOAA weather station, Buffalo Airport, the period December 3-6, 1990
was fully overcast and precipitation occurred in the forms of rain and snow as follows: December
3: 30.5 mm water equivalent (rain and snow); December 4: 13.7 mm water equivalent (rain and
snow); and December 5: 1.8 mm water equivalent (snow). The Buffalo Sewer Authority (BSA)
rain guage in South Buffalo was not operating during this sampling period. The mean daily
temperatures at the airport for the same period were: December 3: +3.9°C; December 4: +2.2°C,
December 5: -2.2°C; and December 6: +1.1°C. The sampled runoff therefore was a mixture of
rainfall and snowmelt. As noted, sampling occurred at sites 3, 4, 5 and 8 (Figure 4; Hamburg St.,
St. Stephans PL, Babcock St. and Cazenovia Park, respectively). Flow velocity measurements
were taken within the overflow chamber at sites 3, 4 and 5 and immediately up-pipe of the outfall
mouth at site 8. The measurements were taken using a Montedoro-Whitney PVM-2A electronic
current meter and the mean of three, 10-second time averaged samples were:
Hamburg St., - 2.20 m s'1
St. Stephans PI. - 0.90 m S'1
Babcock St., - 0.45 m s'1
Cazenovia Park - 0.35 m s"1
In addition, the width and depth of flow were measured at sites 3 and 8 and the flowrate at these
sites therefore is calculated as:
Hamburg St., - 0.077 mV
Cazenovia Park - 0.00262 mV1
11.2. August 9, 1991 Sampling
Precipitation on August 8, 1992 at the Bufalo Airport totaled 17.8 mm, with only a trace on
August 9, 1992. As noted hi Section 3.2.1, sampling occurred at sites 3 and 4 (Hamburg St. and
St. Stephans PL resectively). Flow velocity measurements were taken within the overflow
chamber at both sites using a Montedoro-Whitney PVM-2A Electronic current meter. The width
and depth of flow also were measured and the flowrate at the two sites therefore was calculated as
0.0213 mV1 for the Hamburg St. site and 0.00116 mV1 for the St. Stephans PL site.
273
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11.3. Additional Overflow Observations
A moderately intense rainfall occurred in South Buffalo on July 17, 1992 and field
personnel from SUNY college at Buffalo made a visual inspection of the selected outfall sample
sites (Figure 4) during the event. The rainfall characteristics measured at the BSA South Buffalo
Pump Station gauge are summarized in Table 67 and a summary of the field observations is
provided in Table 68. The total rainfall depth recorded at the South Buffalo Pump Station gauge
during the period of field observation was 21.3 mm (0.84 hi). By comparison, the Buffalo Airport
received 26.7 mm (1.05 in). Calocerinos and Spnia (1989) analyzed rainfall data from the Buffalo
Airport for the period 1948 to 1986 and found that rainfall events having depths of 1.02 hi (25.9
mm) had a return period of 1 1/2 months. The probable frequency of overflow events is discussed
in more detail by Irvine et al, (1993b).
274
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TABLE 63 Rainfall Intensity, South buffalo Pump Station Gauge, Storm of July 17, 1992
Time
7:10
7:15
7:20
7:25
7:30
7:35
7:40
7:45
7:50
7:55
8:00
8:05
Intensity, mm hr "'
15.2
24.4
6.1
6.1
6.1
6.1
3.0
3.0
6.1
3.0
3.0
3.0
Time
8:10
8:15-9:30
9:35
9:40
9:45
9:50-11;25
11:30
11:35
11:40
11:45
11:50
11:55
Intensity, mm hr "'
3.0
0.0
33.5
33.5
36.6
0.0
42.7
6.1
6.1
6.1
3.0
0.0
275
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TABLE 64 Summary of Overflow Observations for the Storm of July 17, 1992
TIME
11:40
11:30
11:40
12:00
12:15
12:20
12:30
SITE NAME
Babcock St.
Bailey Ave.
Tamarack St.
Boone St.
Smith St.
Hamburg St.
Dead Man's
Cr.
SITE NO.
5
10
7
6
3
2
OBSERVATIONS
overflow observed but
just started
from debris, overflow
appeared to have
occurred recently, but
had stopped
no overflow, did not
appear to have
overflowed recently
from debris, overflow
appeared to have
occurred recently, but
had stopped
full overflow to the
river observed
overflow observed
overflow observed
11.4 Babcock St. Automated Station
A total of 8 overflow events were observed during the 1990 field season and 9 overflow events
were observed during the 1991 field season at the babcock St. automated station. An overflow "event"
arbitrarily was defined as a period of overflow separated from other overflows by a minimum of 2 hours.
k Overflow event characteristics are summarized in Table 69 and corresponding rainfall characteristics are
summarized hi Table 70. The BSA had removed all rain gauges prior to the December 3, 1990 event and
rainfall data from the Buffalo Airport therefore are substituted. Rainfall data for the storms of May 29
and September 26, 1991 also are from the Buffalo Airport.
A personal computer version of the Stormwater Management Model (PCSWMM3.2) was
calibrated for a total of 8 of the overflow events observed during the 1990-1991 period. The average
(absolute) prediction error of overflow volume for the 8 events was 4% and the average (absolute
prediction error of peak overflow rate was 24%. These calibration results compare favorably with those
reported hi the literature (e.g. Warwick and Tadepalli, 1991; Nix et al, 1991; Zaghloul and Al-Shurbaji,
1990). The details of the model calibration procedure for the Babcock St. sewershed are presented hi
Irvine et al. (1993b).
276
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TABLE 65 Overflow Characteristics - Babcock St. Sewershed
Event Date
Jul 9, 1990
Aug 13, 1990
Aug 28, 1990
Sep 5, 1990; event "a"
Sep 5, 1990; event "b"
Sep 7, 1990
Oct 11, 1990
Dec 3, 1990
Apr 19, 1991
Apr 20, 1991
Apr 21, 1991
Apr 22, 1991
May 29, 1991
Jul 4, 1991
Jul 7, 1991
Jul 8, 1991
Sep 26, 1991
Event Volume, m3
3021
5245
933
1020
1716
1306
815
11817
1667
3218
3417
10554
0.018
4060
597
32
578
Peak Overflow
Rate, mV
0.458
0.471
0.298
0.393
0.429
0.349
0.327
0.671
0.490
0.507
0.456
0.472
0.00005
1.11
0.224
0.066
0.174
Event Duration, hr
2.6
4.8
1.6
1.3
1.75
1.6
1.2
10.5
1.4
2.4
3.2
9.2
0.25
2.8
1
0.3
1.5
277
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TABLE 66 Rainfall Characteristics for Babcock Overflow Dates
Event Date
Jul 9, 1990
Aug 13, 1990
Aug 28, 1990
Sept 5, 1990;
event "a"
Sep 7, 1990
Oct 11, 1990
Dec 3, 1990
Apr 19, 1991
Apr 20, 1991
Apr 21, 1991
Apr 22, 1991
May 29, 1991
Jul 4, 1991
Jul 7, 1991
Jul 8, 1991
Sep 26, 1991
Event Depth, mm
24.6
35.3
23.1
23.9
16.0
17.5
30.5
15.2
10.0
10.1
16.7
46.8
14.1
no data*
29.7
localized storm - rainfall reported at the I
for the BSA guage.
Peak 5 Min
Intensity, mm hr'1
48.8
51.8
61.0
94.5
24.4
6.1
-
9.1
6.1
3.0
3.0
61.0
42.7
-
Peak 15 Min
Intensity, mm hr"1
38.6
21.3
46.8
44.7
19.3
5.1
-
9.1
5,1
3.0
3.0
45.7
26.4
-
Event
Duration, hr
3
11.6
2.6
1
3.2
9.4
9
3.25
4.1
4.1
10.0
2.2
2.2
10.0
iufalo Airport totaled only 0.25 mm and data were unavailable
278
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12. COMBINED SEWER QUALITY ANALYSES
The levels of total PCBs, PAHs and pesticides in the particulate and dissolved phases for the wet
weather samples from the various combined sewer sites are summarized in Tables 71 through 73. The
levels of conventional parameters and Pb for the wet weather samples of August 9, 1991 at the St.
Stephans PI. and Hamburg St. sites are summarized in Tble 74.
Levels of total PCBs hi the dissolved phase typically were below the method detection limit of
2.085 ng r1. The single detection at Hamburg St. (12/5/90) exceeded the guidelines (0.001 ug lu)
proposed by the NYSDEC (1989) tor protect wildlife from the toxic effects of eating contaminated fish.
The levels of total PCBs were higher hi the particulate phase for the sample results summarized hi Table
71, a finding consistent with the additional data reported below for the Babcock St. automated sampling
station. Based on sampled influent to the Buffalo Sewage Treatment plant the NYSDEC (1989) had
concluded that combined sewer overflows were not a source of PCB s to the river.
Levels of PAHs hi the dissolved phase exceeded state guidance values for class A rivers (0.0012
ug T1 for Benzo(a)Pyrene; 0.002 uT1 for the other PAHs; values represent a "total" concentration) hi 21 of
the 30 tests presented in Table 72. In addition, particulate phase concentrations were higher than the
dissolved phase hi 22 of the 30 tests, indicating that the total sample concentration would have a greater
probability of exceeding guidance values. It appears that the Cazenovia Park site generally has lower
levels of PAHs than the other sites, although more data would be required to confirm this observation.
The lower concentrations may be related to landuse (the Cazenovia Park contributing area primarily is
residential and parkland), although Marsalek (1990) noted that recent studies have found the relationsips
between levels of various pollutants and landuse not to be statistically significant.
Pesticide levels (Table 73) typically were below detection or quantitation limits, although a greater
quantitation frequency was observed for the particulate phase. Sampling of the Buffalo Sewage
Treatment Plant influent (wet and dry weather samples) between 1985 and 1987 did not indicate the
presence of chlordane, while DDT was quantified at a level of 0.1 uT! hi one of seven samples
(NYSDEC, 1989).
12.1. Additional Quality Data for Babcock St. Sewershed
Several overflow samples obtained at the Babcock St. site during the 1990-91 field seasons were
analyzed for total PCBs and Cu. These samples were not analyzed according to the QAPP for the
project, but the data are presented here for reference.
279
-------
TABLE 67 Total PCBs, Particulate and Dissolved Phases, Wet Weather Combined Sewage
Site
Babcock
Hamburg
St. Stephans PL
Cazenovia
St. Stephans PL
Hamburg
Date
12/05/90
12/05/90
12/05/90
12/05/90
8/9/91
8/9/91
Dissolved Phase, ng I"1
(PPt)
BMDL*
23.3
BMDL
BMDL
BMDL
BMDL
Particulate Phase,
ngl'1 (ppt)
20.83
152.66
99.03
3.96
18.80
22.56
Below Method Detection Limit
280
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TABLE 68 PAHs, Particulate and Dissolved Phases, Wet Weather Combined Sewage
Site
Babcock
Hamburg
St. Stephans PI.
Cazenovia
St. Stephans PI.
Hamburg
Date
12/5/90
12/5/90
12/5/90
12/5/90
8/9/91
8/9/91
Dissolved Phase, ngl"1
(PPt)
B(a)A 5.94
Chrysene 4.59
B(b)F 8.07
B(k)F 1.32
B(a)P 1.80
B(a)A 20.46
Chrysene 4.52
B(b)F 8.85
B(k)F 2.02
B(a)P 1.92
B(a)A 1.57
Chiysene 1.70
B(b)F BQL
B(k)F BQL
B(a)P BQL
B(a)A 3.65
Chrysene 2.67
B(b)F 1.72
B(k)F 0.37
B(a)P 0.39
B(a)A 22.79
Chrysene 14.26
B(b)F 9.60
B(k)F 2.27
B(a)P 2.33
B(a)A 46.37
Chiysene 28.85
B(b)F 19.91
B(k)F 3.34
B(a)P 4.51
Particulate Phase,
ngl'1 (ppt)
B(a)A 7.45
Chiysene 9.86
B(b)F 10.21
B(k)F 3.45
B(a)P 5.46
B(a)A 1.87
Chrysene 4.26
B(b)F 1.89
B(k)F 0.60
B(a)P 0.62
B(a)A 134.83
Chrysene 182.06
B(b)F 144.20
B(k)F 68.16
B(a)P 147.14
B(a)A 3.54
Chiysene 5.05
B(b)F 6.17
B(k)F 2.16
B(a)P 3.59
B(a)A 34.04
Chrysene 34.34
B(b)F 29.41
B(k)F 20.54
B(a)P 43.21
B(a)A 17.29
Chiysene 22.15
B(b)F 21.29
B(k)F 5.24
B(a)P 6.91
Abbreviations: B(a)A - Benzo(a)Anthracene; B(b)F - Benzo(b)Fluoranthene; B(k)F -
Benzo(k)Fluoranthene; B(a)P - Benzo(a)Pyrene; BQL - Below Quantitation Limit
281
-------
TABLE 69 Pesticides, Participate and Dissolved Phases, Wet Weather Combined Sewage
Site
Babcock
Hamburg
St. Stephans PL
Cazenovia
St. Stephans PL
Hamburg
Date
12/5/90
12/5/90
12/5/90
12/5/90
8/9/91
8/9/91
Dissolved Phase, ngl"1
(Ppt)
G-CHL BQL
A-CHL BQL
Dieldrin BDL
DDT BDL
G-CHL BQL
A-CHL BQL
Dieldrin BDL
DDT BQL
G-CHL BQL
A-CHL BQL
Dieldrin BDL
DDT BDL
G-CHL BQL
A-CHL BDL
Dieldrin BDL
DDT BDL
G-CHL 0.25
A-CHL 0.18
Dieldrin BQL
DDT BQL
G-CHL 0.10
A-CHL 0.10
Dieldrin BQL
DDT BQL
Particulate Phase,
ngl'1 (ppt)
G-CHL 0.15
A-CHL 0.14
Dieldrin BDL
DDT BDL
G-CHL 0.09
A-CHL 0.09
Dieldrin BDL
DDT 0.23
G-CHL 0.68
A-CHL 0.71
Dieldrin BDL
DDT 4.95
G-CHL BQL
A-CHL BQL
Dieldrin BDL
DDT BDL
G-CHL 0.06
A-CHL BQL
Dieldrin BQL
DDT BDL
G-CHL 0.04
A-CHL BQL
Dieldrin 1.41
DDT 0.24
Abbreviations: G-CHL - Gamma-chlordane; A-CHL - Alpha-chlordane; DDT - 4,4' -DDT; DBL - Below
Detection Limit; BQL - Below Quantitation Limit
282
-------
TABLE 70 Conventional Parameter and Metals Levels (ppm), Wet Weather Sewer Sampling,
August 9, 1991
Site
St.
Stephans
Hamburg
Alkalinity
158
332
Chloride
53.3
52.0
Total
Suspended
Solids
36
27
Sulfides
1.82
1.02
Total
Organic
Carbon
159.1
119.8
Dissolved
Organic
Carbon
128.5
105.7
Pb
0.028
0.004
note: data for Cu, Fe and Mg were not received from Alfred Analytical Laboratory
283
-------
The levels of Cu were determined using short-lived instrumental neutron activation analysis
(INAA) at the McMaster Nuclear Reactor, Hamilton, Ontario. The overflow samples were wet-filtered
using Millipore filters (minimum pore size of 0.45 um) to separately determine Cu levels associated with
the particulate and dissolved phases. The dry mass of filtered sediment used in the analyses ranged
between 0.001 and 0.155 gm, while 5 ml of filtrate was analyzed. No pre- or post-irradiation chemistry
was required. Irradiation, delay and count times, details of the reactor flux and characteristics of the
detector used for the analyses are provided by Vermette et at. (1987) and Irvine (1989). The efficacy of
INAA for the analysis of these types of samples is discussed by Irvine t al.
(1992b). In general, INAA results for water and sediment samples are comparable to more frequently
used analytical methods such as atomic absorption and inductively cooled plasma.
Total PCBs also were analyzed hi the dissolved and particulate phases of the CSO samples
following the procedures described hi the Federal Register (1984) and Loganathan et al. (1990), with
some modifications. Approximately 1 L of sample was filtered through 0.45
jam Whatmann Glass Fiber filters using Millipore filter systems to separate the dissolved and particulate
phases. The dissolved phase was extracted thrice (60 ml each time) using methylene chloride hi a
separatory funnel. The extract was passed through anhydrous sodium sulfate and collected hi an
Erhlenmeyer flask. The volume of the extract was brought down to 10 ml using K-D concentrator and
transferred to hexane. The sample extract was treated with 5% filming H2SO4 in concentrated sulfuric
acid and washed with hexane-washed water. The extract was concentrated to 1 ml and an aliquot of this
extract was injected into a gas chromatograph.
The particulate phase was soxhlet extracted for 16 ours using methylene chloride. The methylene
choride extract wa K=D concentrated and transferred to hexane. The extract was subjected to silicagel
chromatography for separation of PCBs from pesticides. The fraction containing PCBs was K-D
concentrated and the extract was treated with 5% fuming H2SO4 in concentrated sulfuric acid and washed
with hexane-washed water. The extract was concentrated to 1 ml using nitrogen gas and injected into a
gas chromatograph.
A gas chromatograph (Varian model GC-3400) equipped with a 63Ni electron capture detector and
automatic sampler (Varian model 8100) was used for quantittation of PCBs. A capillary column, DBS
(J&W Scientific) having dimensions of 30m x 0.25mm I.D. and 0.25
um film thickness was used. The temperature was programmed from 160°C and 230°C at a rate of 2°C
nun -1 with initial and final hold times of 10 minutes, respectively. The injector and detector temperatures
were kept at 250°C and 300°C, respectively. Nitrogen was used both as carrier and makeup gas. PCBs
were quantitaied using individually resolved peaks with corresponding standard peaks. PCBs standards
containing 1:1:1:1 mixture of 1242, 1248, 1254 and 1260 were used for PCBs quantitation.
The dissolved, particulate phases and blanks were spiked with surrogate standards (2,4,5,6-
tetrachloro-/H-xylene and 2,2',3,4,4',5.6,6' -octachlorobiphenyl) hi order to check
284
-------
the efficiency of the analytical procedure. Hexane-washed distilled water was used as blank. Recoveries
of the surrogate standard were 1 jQ ± 20%. Analytical results were not corrected for the surrogate
standard recoveries.
The additional analytical results at the Babcock St. site are available for three overflow "periods".
The first overflow period represents the overflow events that occurred on August 28, September 5 and
September 7, 1990. The events were composited in one sample since the birth of Gordon William Irvine
(September 3, 1990; 7 Ibs. 4 ox.) precluded a field visit to reset the system between events. The second
overflow period represents four overflow events that occurred between April 20 and April 22, 1991. The
third overflow period represents the event of July 4, 1991. The analytical results are presented in Table
75.
TABLE 71 Levels of Cu and Total PCBs in Sampled Overflows, Babcock St. Sewershed
Period
Sep 1990
Apr 1991
July 4, 1991
not determined for t
Cu, particulate
phase, ppm
414
ND*
478
Cu, dissolved
phase, ppm
0.131
ND
ND
Total PCBs,
particulate
phase, ng T1
400
ND
970
Total PCBs,
dissolved
phase, ng I"1
30
20
38
he event
12.2. ADDITIONAL QUALITY DATA FOR BAILEY AVENUE OUTFALL (SITE 10)
A single grab sample was collected immediately up-pipe of the Bailey Avenue outfall mouth
during an overflow event on October 20, 1989. The grab sample was taken using a Van Doren sampler.
The sample was processed and analyzed for the particulate Cu level using the same methodology as
described for the Babcock St. samples. The particulate Cu level for the sample was 342 ppm, which is in
the same general range as the levels observed for the Babcock St. site.
285
-------
13. RESULTS
13.1. Total PCB Concentrations in Buffalo River Water Samples - Fall 1990
Analysis of water samples during six surveys at six sites in the Buffalo River (fig. 5 and Tables 2,3)
revealed that the concentrations of total PCBs were below the method detection limit (MDL, = 2ng/L)
except for the sample collected on October 18, 1990 at site 2 (BR10102WID). The concentration
recorded was 4.28 +/-0.4 ng/L. (Table 15).
13.1.1. Total PCB Concentrations in Buffalo River Water Sample-soring 1992
Three surveys conducted at the sites 1,3 and 6 (Fig. 5 and Table 4) in the Buffalo River during the spring
of 1992 also showed the dissolved phase concentrations are below the method detection limit (1.5)ng/L).
13.1.2.Total PCB levels in Buffalo River suspended sediments - Fall 1990
Unlike water column samples, particulate phase (or suspended sediments) of the buffalo River samples
(fig. 5; Tables 2 and 3) indicated several of the samples had total PCB concentrations ranged from MDL
to 8.0+/-0.42 ng/L )parts per trillion). Note: The values were calculated based on the volume of water
filtered - Table 21). Majority o the detects were less than 5 ng/L. Among the six surveys conducted,
survey 1, (October 22, 1990), 2 (October 27, 1990) and 4 (November 5, 1990) recorded more detects in at
least three sites. Sites 3,4,5 and 6 recorded detectable levels of total PCBs at least hi surveyed 1,2 and 4.
Table 24 presents total PCB concentrations in the suspended sediments on mg/Kg basis. The
concentrations - mg/Kg values were calculated based on the TSS data obtained from MDL to 1.68 ppm.
the highest concentration (1.65 +/-0.20 mg/Kg) was recorded at the site 1 of the survey 4. Most of the
detects were less than 0.3 ppm. Survey 1,2 and 4 recorded detectable PCB levels in almost all sites.
Survey 2,5 and 6, most of the sampling sites revealed the concentrations less than the method detection
limit. Table 25 gives the PCB concentrations in suspended sediments as ng/L and mg/Kg for quick
comparison purposes.
13.1.2.1.Total PCBs in the Buffalo River Suspended sediments - Soring 1992
Unlike the Fall 1990 suspended sediment samples, spring even samples collected during the Spring 1992,
exhibited relatively more detects. Almost all samples showed detectable concentrations of PCBs, except
at Site 1 of the spring even survey 2 (SBR2). Among the detects the concentrations ranged from 0.52 to
8.42 +/-0.16 ng/L (based on ng?L basis) or 0.013 to 0.33 +/-0.006 ppm (mg/Kg). The highest PCB
concentration was recorded at site 6 of the survey 1. Lowest concentration (0.52 +/-0.15 ng/L) was
recorded at site 3 during the survey 2. Whereas, when the data is presented on mg/Kg basis, site 1 or
survey 1 showed the lowest concentration (0.013 +/-0.001
13.2. Pesticide Concentrations in the Buffalo River Water. Fall 1990
Chlorinated hydrocarbon pesticides such as gamma-Chlordane, alpha-Chlordane, Dieldrin and 4,4'-DDT
were also analyzed in the water and suspended sediments collected during the fall 1990 and spring even
samples (Spring 1992) from the Buffalo River.
286
-------
Table 28 presents the detection limits for the above pesticides and the concentrations of the same in
buffalo River water and CSO dissolved phase collected during the fall 1990. Among the four analytes
only chlordane (gamma and alpha) were detected hi a few water samples. The concentrations detected
were also very low. Only four samples (Site 4 of Survey 3; Site 5 of Survey 3; Site 2 of Survey 5; and
Site 3 or survey 6). The concentrations were ranged from 0.03 and 0.44 ng/L).
The detectable concentrations of alpha-Chlordane was recorded in six samples. The site and survey
numbers are as follows:
Site 1 of Survey 1; Site 2 of Survey 1; Site 4 of Survey 1; Site 6 of Survey 1; Site 1 of Survey 2 and Site
3 of Survey 6. The concentrations were ranged from 0.025 ng/L to 0.068 ng/L.
13.2.1.Pesticide Concentrations in Buffalo River Water Spring Even Samples
The pesticide analytes measured hi spring even samples are the same as the pesticides measured hi fall
1990 samples. Table 31 gives the detection limits of the pesticides and the analyte concentrations in
various samples collected during this period. Among the three sites (Site 1,3 and 6) and three surveys
(SBR1, SBR2 and SBR3) at each site, only 3 samples viz. Site 1 of survey 1; Site 6 of Survey 1 and Site
3 of survey 3 showed detectable concentrations of apha-Chlordane. The concentrations ranged from 0.05
ng/L to 0.06 ng/L. None of the other pesticides were detected hi these spring even samples.
13.2.2.Pesticide concentrations in Buffalo River Suspended Sediments - Fall 1990
Unlike water samples, suspended sediments (fall 1990) showed relatively many analytes at detectable
concentrations hi comparatively larger number of samples. Except dieldrin, gamma-Chlordane, alpha-
Chlordane and 4,4'-DDT were detected. Table 34 presents the detection limits for the pesticides and the
analytes data are presented hi both ng/L and mg/Kg basis. Among the four pesticide analytes, Chlordane
(gamma-Chlordane and alpha-chlordane) compounds were relatively more frequently found detectable
concentrations in suspended sediment samples. Apha-Chlordane was consistently higher concentration
than gamma-Chlordane hi almost all samples detected. Survey 4 and 5 revealed more detectable
concentrations (hi most of the sites) of chlordane than other surveys. The concentrations of gamma-
Chlordane ranged from 0.014ng/L (Site 1 or Survey 5) to 0.048 ng/L (Site 6 of Survey 5). Based on
mg/Kg, the concentration ranges were 0.005 mg/Kg (site 1 of Survey 1 and 5) to 0.012 mg/Kg (Site 1 or
Survey 4).
The concentrations of apha-Chlordane ranged between 0.0148ng/L (Site 1 of Survey 5) and 0.053 ng/L
(Site 6 of Survey 5). On the mg/Kg basis, the concentration range was 0.0005 mg/Kg (Site 1 of Survey
5) and 0.02 mg/Kg (Site 6 of Survey 3 and Site 1 of Survey 4). Many samples revealed the presence of
chlordane, but they were below the quantitation limit (BQL), but above the limit of detection (LOD).
Among 36 samples (6 sites and 6 surveys), only four sites showed the detectable concentrations of
4,4'=DDT (Table 34). They are:
Site 1 of Survey 2 (0.07 ng/L / 0.026 mg/Kg)
Site 3 of Survey 2 (0.086 ng/L / 0.022 mg/Kg)
Site 1 of Survey 4 (0.086 ng/L / 0.043 mg/Kg)
Site 3 of Survey 6 (0.107 ng/L / 0.0067 mg/Kg)
13.2.2.1.Pesticide Concentrations in Buffalo River Suspended sediments - soring 1992
287
-------
Spring even samples (Three surveys at Sites 1,3 and 6) also revealed that the pesticide concentrations in
suspended sediments are very low. Table 37 gives the pesticide concentration in each of the samples. As
observed in the suspended sediments of the Fall 1990, the present sample sets showed comparatively
more detects than of chlordane compounds are evident. Also the concentrations recorded were higher
than the concentrations found hi fall 1990 samples. Among the detectable concentrations, gamma-
Chlordane concentration ranged from 0.038 ng/L (Site 1 of Survey 3) and 0.092 ng/L QSite 6 of Survey
3). On mg/Kg basis the range was between 0.001 mg/Kg (Site 1 of Survey 1; Site 3 of Survey 1; Site 1
of Survey 3) and 0.005 mg/Kg (Site 6 of Survey 3).
13.3. PAHs Concentrations in Buffalo River Water and suspended sediment Samples - Fall 1990
and Spring 1992
During the fall of 1990, six selected sites (Fig. 5 and Tables 2 and 3) in the Buffalo River area of concern
were surveyed six times hi each of the sites for water and suspended sediments and the samples were
analyzed for five select PAHs hi addition to PCBs and pesticides. Since there were no storm events
during this sampling period, event samples were collected during spring 1992 from sites 1, 3 and 6.
PAHs concentrations hi the fall and spring event samples are presented hi Table 41 to 51 and figures 24
to 31. Unlike PCBs and pesticides, PAHs are detected hi both dissolved and particulate phases of non-
event (fall 1990) and even (spring 1992) samples. Results of individual PAHs concentrations in dissolved
and particulate phases of each of the surveys and sites during non-event and even samples are presented.
13.3.1. PAHs Concentrations in Water Samples of Buffalo River
13.3.1.1. Benzo(a)anthracene (B(a)A)
Concentrations of B[a]A hi six sites during six surveys ranged from the method detection limit (0.1 ng/L)
to 26.6 ng/L (site 3 during survey 4). No clear trend was observed for B[a]A between the sites and
surveys. In three surveys conducted during spring events, the concentration of B[a]A was very low (only
site 1 exhibited detectable concentrations while sites 3 and 6 in all three surveys show below the method
detection limit) in comparison with the fall 1990 at sites 1, 3 and 6. Notable concentrations of 23.63
ng/L of B[a]A were observed hi survey 1 of site 1 during the spring, 1992.
13.3.1.2 Chrvsene
Chrysene concentrations also comparable with B[a]A were detected in most of the sites during the six
surveys of fall, 1990. The concentrations ranged from below the method detection limit to 15.67 ng/L
(site 3 of survey 4). No specific trend can be discerned for site to site and survey to survey chrysene
levels except for the highest concentration recorded at the site mentioned above. In contrast to B[a]A,
more detects were found hi spring event samples. The highest concentration recorded was 11.25 ng/L at
site 6 hi the spring survey #2.
13.3.1.3. Benzofb]fluoranthene
B[b]F concentrations during the six surveys at six sites were < 3 ng/L for most samples. Only three
samples contained concentrations > 10 ng/L. The highest concentration was 15.34 ng/L during survey #5
at site 4. However, the concentration of B[b]F was below the method detection limit at the same site
during survey #4. No remarkable different in the B[b]F concentrations was observed in the spring event
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samples in comparison with the fall 1990 samples. The highest concentration of this compound during
the spring even was 6.2 ng/L during the spring survey 1 of site 1.
13.3.1.4. Benzo fkl fluoranthene
No site to site and survey to survey variation could be observed for B[b]F, since the concentrations in the
dissolved phase were very low. In most samples, the concentration was < 0.5 ng/L. The highest
concentration was 3.0 ng/L at site 3 of survey 4. Similarly, spring even sample concentration was also
low in almost all samples (< 1 ng/L). The highest concentration of spring even sampling was 1.35 ng/L
at site 1 of spring survey 1. This may be attributable to the dilution of these PAHs due to storm events.
13.3.1.5. Benzofolpvrene
B[a]P concentrations in dissolved phase were also very low as observed for B[k]F. In most of the
samples, the concentrations observed were < 1 ng/L. The highest concentration was 3.37 ng/L at site 4 of
survey #5. B[a]P concentration in spring even samples were also in the same range (below the method
detection limit to 2.2 ng/L) as observed for fall 1990 samples. No clear trend could be explained for
these concentrations in dissolved phase between the sites and/or surveys due to the same low
concentration ranges.
13.3.2. PAHs Concentrations in the Buffalo River Suspended Sediment Samples Fall 1990 and
Soring 1992
Unlike the dissolved phase, suspended sediment PAHs concentrations were relatively higher (ppb and
ppm) and exhibited clear differences in the concentrations for non-event (Fall 1990) and spring even
(Spring 1992) samples (Tables 47 to 51). The results of individual (selected) PAHS are as follows:
13.3.2.1. Benzo [a] anthracene (BfalA) Concentrations in Suspended Sediments
B[a]A concentrations in suspended sediments ranged from the method detection limit to 1.45 ug/g; ppm
(site 1, survey 4). At most sites during the six surveys, the concentrations were < 0.5 ug/g (Tables 47 -
50). No distinct pattern of concentrations of B[a]A was evident for the surveys or the sites for the
samples collected in the Fall 1990. However, remarkably high concentrations of B[a]A were found in the
spring even survey 1 at sites 1 and 6. The concentrations were 0.36 ug/g (55.05 ng/L) and 5.3 ug/g
(135.5 ng/L) respectively and survey 2 at site 6 3.02 ug/g (90.6 ng/L). Table 51 and Fig. 27.
13.3.2.2. Chrvsene Concentrations in Suspended Sediments
Chrysene concentrations in suspended sediments were also in the same range (p.l ug/g to 4.25 ug/g) as
observed for B[a]A. In most of the samples (from all six sites during six surveys) concentrations were <
0.5 ug/g. As observed for B[a]A, spring event samples contained comparatively higher concentrations of
chrysene. The chrysene concentrations ranged from 0.27 ug/g (20.0 ng/L) to 3.62 ug/g (90.6 ng/L) at
sites 3 and 6 of spring event surveys 3 and 1 respectively. Table 51 and Fig. 28.
13.3.3.3. Benzo[b1fluoranthene (BfbJF) concentrations in Suspended Sediments
No distinct site to site and survey to survey trend is observed for B[b]F in the suspended sediments
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collected during fall 1990. The B[b]F concentrations ranged from below the method detection limit to
4110 ug/g (site 1 or survey #4). Most sample concentrations (all sites and all surveys in the Fall 1990)
were < 1 ug/g.
A Distinct difference in the concentrations of B[b]F in spring event suspended sediment samples were
observed in comparison with fall 1990 suspended sediment samples (Fig. 29; ng/L basis). Based on ng/L
basis, almost all samples (except site and 3 of spring event survey 2), the concentrations of B[b]F was on
an order of magnitude higher than fall samples of the same site. Based on an ug/g basis, the
concentrations of B[b]F ranged from 0.96 ug/g (18.21 ng/L) to 3.4 ug/g (86.92 ng/L) Table 51.
13.3.3.4. Benzofk]fluoranthene (B[k]F) concentrations in Suspended Sediments
Unlike other PAH analytes (B[a]A, Chrysene, B[b]F, Benzo[k]fluoranthene concentrations were
comparatively lower in most of the suspended sediment samples in the Fall of 199 and spring event
samples (Tables 47 to 51 and Fig. 30). The concentration ranges observed for Fall suspended sediments
are < MDL to 1.32 ug/g (site 6 , survey 3). Most of the fall 1990 samples were < 0.3 ug/g. spring event
suspended sediment concentrations ranged from 0.22 ug/g (33.4 ng/L) to 1.42 ug/g (36 ng/L) at sites 1
and 6 of spring even survey 1 (Fig.30)
13.3.3.5. Benzofajpvrene (B[a]P) Concentrations in Suspended Sediments
In general, both B[k]F and B[a]P concentrations ranges were almost similar in both fall and spring event
samples, with slight higher concentrations of B[a]P in a few samples in both sampling events (Table 47 -
51, Figs. 30,31). In the Fall 1990, survey 1 revealed below method detection limits for al six sites for
both B[k]F and B[a]P. This indicated a clear pattern and possibly a different source for these compounds
in the Buffalo River AOC. The highest concentrations of 3.15 ug/g of B[a]P was observed in site 1 of
survey 4. In almost all sites during all surveys the B[a]P concentrations in suspended sediment were < 1
Unlike the fall 1990 suspended sediment samples, spring 1992 (spring event) suspended sediments
contained detectable amounts of B[a]P. The concentrations ranged from 0.12 ug/g (8.84 ng/L) at site 1 of
spring survey 1 and 1.7 ug/g (43.16 ng/L).
14. Summary
14.1. Total PCBs
i) Total PCB levels hi buffalo River water samples (i.e. dissolved phase) collected in fall of 1990,
and spring of 1992 were extremely low (below the detection limit Ippt*). The levels do not
exceed the NYSDEC target limit on total PCBs hi water (i.e. 1 ng/L Ippt) which is a standard set
to protect wildlife from toxic effects by these chemicals.
*MDL = method detection limit; MDL is > 3 times the standard deviation of the background
(blank) level. The MDL for the spring samples is 1 ppt, however, because the fall samples were
extracted two tunes, the MDL is 2 ppt.
ii) Total PCB concentrations hi suspended sediment ranged from detection limit to 8 ng/L (8 ppt).
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Due to very low concentrations in many samples, it is difficult to quantitatively determine a trend
using these data. However, comparison of PCB concentrations in suspended sediments collected at
sites 1,3 and 6 during the fall 1990 and the Spring 1992 revealed that most of the Spring 1992
samples were above detection limit. This may be due to resuspension of bottom sediments and/or
contribution from runoff.
iii) among the four CSO sampling sites (Babcock, St., Stephens PL, Hamburg and Cazenovia) the
St. Stephans PL and Hamburg sites exhibited the highest levels of total PCBs. It appears that
CSOs may be a source of these contaminants to the Buffalo River.
14.2. Pesticides
i) Chlordane, Dieldrin and 4,4'-DDT in Buffalo River water and suspended sediments were below
the detection limit in most of the samples collected during the fall of 1990.
ii) DDT concentrations in the Buffalo river were extremely low. They did not exceed the 1 ppt
chronic toxicity criterion established by the EPA for protection of freshwater aquatic biota.
iii) comparison of concentrations of pesticides in the fall 1990 and spring 1992 samples showed
more detects in the latter, indicating the influence of spring events on pesticide concentration.
iv) Pesticide levels in suspended sediments at the CSO sites are higher than those in buffalo River
water and suspended sediments, thus indicating the possible contribution of these contaminants to
the river by CSOs.
14.3. PAHs
i) In general, the concentrations of five selected PAHs in the Buffalo River hi water and
sediments were higher than both total PCBs and pesticides. Therefore, the concentrations of
organic contaminants hi the buffalo River suspended sediments are in the following order:
PAHs > PCBs > Pesticides
ii) Unlike PCBs and pesticides, PAHs were detected in both water and suspended sediment
samples collected during the fall 1990 and spring 9921992 sample periods.
iii) Although PAHs were detected at all the sites, the PAHs levels in suspended sediments
collected at sites 3, 4, 5, and 6 were higher than those at sites 1 and 2.
iv) PAHs concentrations were 5 to 10 times higher hi spring even samples than the fall 1990
samples indicating the influence of storm events.
v) CSO samples exhibited the highest concentrations of PAHs in comparison with the Buffalo
River water and suspended sediments. Therefore, CSO may be one of the important sources of
these contaminants to the River (in particular the St. Stevens PL and Hamburg Street sites).
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14.4. METALS
1.) The total concentrations (i.e. unfiltered samples) of Cu and Fe exceeded IJC ambient
water quality criteria in 100% of the samples collected from the Buffalo River during
event (spring, 1992) and inter-event periods (fall, 1990). The total concentrations of Pb
exceeded the IJC criteria in 40% of the samples collected from the Buffalo River during
event and inter-event periods. The absolute concentrations of Cu, Fe and Pb reported
here must be regarded with some caution. When compared with data from other
agencies (NYSDEC, USGS), Drs. J. Atkinson and J. DePinto (University at Buffalo) felt
that our reported concentrations were too high. A detailed review of analytical methods,
and possibly, additional sampling should be done to resolve discrepancies in the data.
2.) A large amount of variability in metals concentrations was observed between samples,
making it difficult to identify trends given the relatively small data set. In general,
statistical testing indicated no significant differences (a = 0.05) was detected in the
concentrations between different sample sites for both event and inter-event samples.
3.) Particulaterdissolved ratios for Fe were greater during the sampled spring events. This
suggests that the runoff diluted the dissolved concentrations and the particulate
concentrations may have been elevated due to resuspension of bed and bank material.
The particulate:dissolved ratios for Cu were greater during the fall inter-event sample
period. This suggests that there may be sources of particulate Cu other than
resuspension of bed and bank material.
292 - i
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