&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
                                                13

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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
                                        14

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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:
                                             15

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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

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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

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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

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                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

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              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

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(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

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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

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       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

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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

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       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

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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

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                                                                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

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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

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      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

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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

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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

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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

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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

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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

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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

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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

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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

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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

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       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

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 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

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 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
                                                 289

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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).
                                                290

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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).
                                                291

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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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