United States
Environmental Protection
Agency
Great Lakes National
Program Office
536 South Clark Street
Chicago, Illinois 606005
EPA-905/4-85-002
February 1985 /
C/
Investigation of
Polycyclic Aromatic
Hydrocarbon Discharges
To Water in the Vicinity
Of Buffalo, New York
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EPA-905/4-85-002
February 1985
INVESTIGATION OF POLYCYCLIC AROMATIC HYDROCARBON DISCHARGES
TO WATER IN THE VICINITY OF BUFFALO, NEW YORK
By
Edward J. Kuzia
New York State
Department of Environmental Conservation
Albany, New York 12233
and
John J. Black
New York State
Department of Health
Roswell Park Memorial Institute
Buffalo, New York
Grant No. R00556610-01
Projector Officer
Vacys J. Saulys
Great Lakes National Program Office
United States Environmental Protection Agency
536 South Clark Street
Chicago, Illinois 60605
U.S. Environmental Protection Agency
J&teglqn y.,Ubj-ary
230 'South Dea>boW9«r»ti?vn3 % y
Chicago, Illinois 60604
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DISCLAIMER
This report has been reviewed by the Great Lakes National Program Office,
U.S. Environmental Protection Agency, and approved for publication. Approval
does not signify that the contents necessarily reflect the views and policies
of the U.S. Environmental Protection Agency, nor does mention of trade names
or commericial products constitute endorsement or recommendation for use.
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FOREWORD
The Great Lakes National Program Office (GLNPO) of the United States
Environmental Protection Agency was established in Region V, Chicago,
to focus attention on the significant and complex natural resources
represented by the Great Lakes.
GLNPO implements a multi-media environmental management program drawing
on a wide range of expertise represented by universities, private firms,
State, Federal, and Canadian governmental agencies, and the International
Joint Commission. The goal of the GLNPO program is to develop programs,
practices and technology necessary for a better understanding of the
Great Lakes Basin ecosystem, and to eliminate or reduce to the maximum
extent practicable the discharge of pollutants into the Great Lakes sys-
tem. GLNPO also coordinates U.S. actions in fulfillment of the Agreement
between Canada and the United States of America on Great Lakes Water
Quality of 1978.
This investigation was funded in partial support of the binational study
of the Niagara River toxic contaminant problems.
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TABLE OF CONTENTS
ABSTRACT vi
LIST OF FIGURES vii
LIST OF TABLES vlii
INTRODUCTION 1
MATERIALS AND METHODS 3
ANALYTICAL METHODS 3
Solvents and Standards 3
Polypropylene Substrates 3
Sediments 6
Aqueous Samples 7
QUANTITATIVE HPLC ANALYSES FOR SEDIMENTS AND
AQUEOUS SAMPLES 8
FIELD SAMPLING 11
STATISTICAL TREATMENT 11
RESULTS AND DISCUSSION 13
PRELIMINARY SURVEY 13
VERIFICATION SAMPLING 17
Buffalo Sewer Authority 28
Buffalo River 28
Smoke Creek and Union and Lackawanna Canals 37
Two Mile Creek 43
COMPARISION OF PAH TYPES AMONG SITES 52
CONCLUSIONS 54
RECOMMENDATIONS 56
LITERATURE CITED 57
IV
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APPENDIX
A. PAH CHROMATOGRAMS OF ARTIFICIAL SUBSTRATE
SAMPLING OF PRELIMINARY SURVEY SITES 59
B. PAH SEDIMENT CONCENTRATIONS 67
C. SITE DESCRIPTIONS 98
D. QUALITY CONTROL MEASURES 103
v
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ABSTRACT
Eastern Lake Erie and the upper Niagara River basin were sampled for
polycyclic aromatic hydrocarbons (PAH) to assess their distribution and
sources. Twenty-five sites were sampled using polypropylene substrates.
Five areas were identified as having relatively high PAH contamination.
These were Lake Erie at the mouth of Smoke Creek, the Union and
Lackawanna Ship Canals, the Buffalo River, Two Mile Creek, and the
Buffalo Sewer Authority. Subsequent sampling and analyses of sediments,
water, and polypropylene substrates confirmed the preliminary findings.
The sources of the PAH were attributed to steel manufacturing operations
(Lake Erie at the mouth of Smoke Creek and Union and Lackawanna Ship
Canals) and oil storage facilities (Two Mile Creek). The Buffalo Sewer
Authority was sampled directly in the outfall, and the analytical results
identified it as a source of PAH to the Niagara River. The Buffalo River
had several PAH inputs near the South Park Bridge. In addition to the
areas identified as having high PAH contamination, there was a
generalized PAH contamination throughout the study area.
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LIST OF FIGURES
Fig. 1* Preliminary Artificial Substrate Sampling
Sites and Relative Total PAH Concentration 14
Fig. 2* PAH Sediment Sampling Sites. Buffalo River
with Relative Total PAH Concentration 18
Fig. 3* PAH Sediment Sampling Sites. Smoke Creek
Transect in Lake Erie with Relative Total
PAH Concentration 19
Fig. 4* PAH Sediment Satnling Sites at Union and
Lackawanna Canals with Relative PAH
Concentration 20
Fig. 5* PAH Sediment Sampling Sites at Two Mile Creek
with Relative PAH Concentration 21
Fig. 6* Total PAH Sediment Concentrations and Corresponding
Artificial Substrate Total PAH Group for Similar
Stations 27
Fig. 7* Artificial Substrate Sampling Sites in Buffalo River.. 31
Fig. 8 Buffalo River Artificial Substrate Sampling Sites
Near South Park Bridge and Total PAH 34
Fig. 9 Percent Composition of Total PAH Compounds in
Sediment at Buffalo River Sites 5 and 6 36
Fig. 10* Artificial Substrate Sampling Sites at Smoke Creek
and the Union and Lackawanna Canals 38
Fig. 11* Cluster Map of Association of Sediment Sampling
Sites Based on Their PAH Composition 41
Fig. 12* Two Mile Creek Artificial Substrate Sampling Sites 44
Fig. 13 Percent Composition of Total PAH in Two Mile Creek
Artificial Substrate Sites 49
Fig. 14 Percent Composition of Total PAH Compounds in
Sediment 51
* Detailed site description for these figures are presented
in Appendix C
vii
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LIST OF TABLES
Page
Table 1 PAH Screening Results 15
Table 2 PAH Concentrations in Water Samples from Smoke
Creek, Bethlehem Steel Outfalls to Smoke Creek
and the Lackawannna Sewage Treatment Plant 23
Table 3 PAH Concentrations in Water from Buffalo Color
Water Outfalls and Intake 24
Table 4 PAH Concentrations in Water from Allied Chemical
Outfalls to Buffalo River 25
Table 5 PAH Concentrations in Buffalo Sewer Authority
Outfall Water 26
Table 6 PAH Concentration Artificial Substrates from
Buffalo River 29
Table 7 PAH Sediment Concentrations at Buffalo River
Sites 5 and 6 33
Table 8 PAH Concentrations in Artificial Substrates
Smoke Creek and Union and Lackawanna Canals 39
Table 9 PAH Percent Composition of Clusters from Cluster
Map of Site Association 42
Table 10 PAH Concentrations in Artificial Substrates from
Two Mile Creek 45
Table 11 PAH Sediment Concentration from Two Mile Creek 47
viii
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INTRODUCTION
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INTRODUCTION
Anthropogenic polynuclear aromatic hydrocarbons (PAH) are
contaminants of aquatic ecosystems. These compounds have been reported
in fish (Neff, 1982), invertebrates (Eadie et^ a^, 1982), sediment (Heit
e_t^ al. , 1981), and water (Basu1 and Saxena, 1978). PAH can enter the
aquatic environment from various sources, which include airborne
deposition into water from anthropogenic and natural combustion processes
(Hert et^ al_., 1981), runoff from urban areas and roadways (Wong, 1981),
and municipal or industrial effluents (Baum, 1978). Because incomplete
combustion of organic material can result in PAH production, in
particular combustion of fossil fuels, there is a potential for eventual
dispersal of these compounds throughout aquatic ecosystems.
The potential for pollution of the aquatic ecosystem with these
compounds presents a significant problem due to the potent
carcinogenicity of compounds such as dibenzanthracene and benzo(a)pyrene.
PAH produce skin tumors in mice and have been associated with
occupational cancers (USEPA, 1980). Black (1983) has demonstrated a
relationship between tumors in fish and PAH contaminated sediments.
Therefore, these compounds are not only carcinogens of humans, but may
also produce cancers in feral fish.
The study described here had three major objectives: 1) development
of source identification techniques for PAH in ambient waters, 2)
localization of sources of PAH in eastern Lake Erie and the Upper Niagara
River, and 3) determination of the distribution, type, and concentrations
of PAH in eastern Lake Erie and the upper Niagara River. The development
of source identification techniques centered around the use of an
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artificial substrate which is the same material used for containing oil
spills (3 M Brand Oil Sorbent Type 151). In addition to development of
artificial substrates, conventional media (water and sediment) were also
analyzed for PAH. These analyses not only identified the distribution
and relative contamination with PAH in the study area, but, they also
were used to assist in source identification and the evaluation of the
artificial substrate as a PAH monitoring tool.
The general strategy employed to identify PAH sources was deployment
of artificial substrates throughout the area under study. Sites for the
preliminary survey were selected by staff from the New York State
Department of Environmental Conservation (DEC) and the contractor. Sites
were also selected where PAH input was not suspected. Results of this
preliminary survey were reviewed by the same group and subsequent
sampling was designed to verify inputs of PAH where high levels were
identified in the preliminary sampling. Analyses of water and sediment
were also done to confirm the results of artificial substrate sampling.
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MATERIALS AND METHODS
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ANALYTICAL METHODS
Solvents and Standards
All solvents were redistilled in glass from technical grade solvents
using a reflux-type condenser (Fisher Scientific #07-748).
Acetonitrile (Fisher Scientific, pesticide grade) and dimethyl sulfoxide
(Me?SO) were used without further purification.
Potassium hydroxide and sodium sulfate were reagent grade
(Fisher Scientific). Florisil (J.T. Baker, 60-100 mesh) was
washed to remove fines and then activated by heating overnight to
o
180 C and after cooling, partially deactivated by addition of 2.5%
distilled water by weight of Florisil.
PAH standards were obtained from Supelco, PAH mixture 610-M,
and as Standard Reference Material #1647 (National Bureau of
Standards). 2-methylphenanthrene, 2-methylanthracene, and perylene
were supplied by Dr. Fred Block, Roswell Park Memorial Institute,
Buffalo, N.Y.
Polypropylene Substrates
Polypropylene substrates measuring 5.0 cm x 10.0 cm were cut from
sheets of a commercially available oil-absorbent cloth (3M Brand Oil
Sorbent Type 151) . Substrates were wrapped in foil to avoid
contamination prior to use. The buoyant artificial substrates were
attached to an anchored wooden float by a short nylon line and allowed to
trail freely in the current. Spring-loaded metal clips facilitated rapid
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substrate installation and removal under field conditions. After
exposure periods of 96 h, substrates were removed, immediately wrapped in
o
foil, and returned to the laboratory where they were stored at -10 C
prior to extraction and analysis.
Substrates were placed in 43 mm x 123 mm cellulose thimbles
(Whatman) and extracted with 95% ethanol in a Soxhlet apparatus for 4 h
(approximately 16 cycles). The ethanol extract (250 ml) was transferred
to a separatory funnel containing 230 ml of water and 250 ml of
cyclohexane,1 and a nonpolar fraction was isolated by liquid-liquid
partitioning. After solvent exchange of the cyclohexane for dimethyl
sulfoxide (Me2SO), a PAH-containing fraction was isolated by Me2SO
partitioning and back-extraction procedures as those utilized by Dunn
(1979) for isolation of PAH from marine organisms.
Following Dunn, the solvent exchanged Me2SO was transferred along
with a 5ml Me.SO rinse from the evaporation flask to a separatory
funnel containing 10 ml of hexane. After vigorous shaking, the Me2SO
hypophase was transferred to a second separatory funnel. The hexane
phase in the first funnel was extracted a second time with a fresh 10 ml
volume of Me2SO, and this was also added to the second separatory
funnel. Following addition of 40 ml of water and 20 ml of cyclohexane to
the second funnel, the PAH was back-extracted into the cyclohexane. The
aqueous Me2SO phase was drained into a third funnel and extracted again
with 20 ml of cyclohexane. The -two cyclohexane phases were combined and
washed with distilled water.
This fraction, containing the bulk of the PAH, was reduced in volume
to approximately 3 ml and transferred to a conical tube where the
hydrocarbons contained in the fraction were concentrated into an
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accurately measured volume of Me2SO (0.5-1 ml) by evaporating off the
cyclohexane. The resulting analytical fractions were transferred to
septum-covered injection vials (Varian Associates) and stored in the dark
prior to analysis.
The PAH content of artificial substrate derived analytical fractions
was characterized using reverse phase gradient elution HPLC. Analyses
were performed on a Perkin-Elmer Series 3 Liquid Chromatograph using
acetonitrile and water as the elution solvent system. In
characterizations of some initial samples, an in-house repacked column
(2.1 mm i.d. x 250 mm, Vydac TP201, 10 uM ODS packing material) was
employed. All other samples were analyzed us,ing a commercially available
column (Perkin-Elmer HC-ODS). Chromatographic conditions were varied to
accomodate column characteristics. Eluted compounds were detected by UV
absorbance (254 nM) using a Perkin-Elmer LC-15 fixed wavelength detector.
Peak identifications were assigned on the basis of retentions relative to
an internal reference compound (chrysene) and by trace enrichment with a
mixture of PAH standards.
Gradient programs:
In house repacked column: TP201, 10 uM ODS, flow 0.6 ml/min
TL - isocratic, 2.5 min, 55% acetonitrile/H20
T2 - 25 min linear to 99.9%, 55% acetonitrile/H20
T3 - 20 min hold at " , " " "
T purge - 5 min, 99.9%, " " ", flow rate 2.0
mis/min
T equilibrate - 20 min 55% acetonitrile/H20, flow rate 0.6
ml/min
Perkin-Elmer SIL HC-ODS, flow 0.9 ml/min
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T. - isocratic, 1.5 min, 55% acetonitrile/H20
T2 - 15 min liner to 99.9% acetonitrile/H20
T3 - 10 min hold at " " "
T purge - 5 min 99.9% acetonitrile/H20, flow rate 2.0 ml/min
T equilibrate - 15 min, 55% acetonitrile/H20, flow rate 0.9
ml/min
Sediments
To compensate for variable sediment composition, concentrations
were expressed in terms of wet weight, dry weight, and the weight of
organic matter in the sample. Paired sub-samples were used with one
taken through extraction and analysis and the other dried to constant
o o
weight at 60 C followed by combustion at 500 C for 24 hours. The
organic weight was the loss in weight between 60°C and 500°C.
Methods of sample extraction and PAH prefractionation were similar
to those employed by Dunn (1979). Samples of wet sediment (2-20 gms)
were digested in boiling ethanol/potassium hydroxide by liquid-liquid
extraction. The cyclohexane phase was concentrated and a PAH containing
fraction isolated by chromatography on Florisil.
A 22 x 400 mm column was dry-packed with 25 gms of partially
deactivated (2.5% wt/vol) 60-100 mesh Florisil topped with 20 gms of
sodium sulfate. Following a hexane prewash, the cyclohexane phase was
percolated into the column. This fraction, contaminated with aliphatics,
was discarded. The PAH fraction was eluted from the column with three 50
ml washes of 50% methylene chloride/hexane. This fraction was
concentrated into 5 ml of Me?SO by flash evaporation.
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Additional aliphatics were removed by partitioning of the PAH
between Me.SO and hexane. After adding water, the aromatic
hydrocarbons were back extracted from the Me_SO into a fresh volume of
cyclohexane. The PAH were concentrated into an accurately measured
volume of Me~SO by evaporating off the cyclohexane using a gentle
stream of warm air. Aliquots of from 1 to 20 ul were injected for HPLC
analysis.
Aqueous Samples
A simple "trapping" technique was applied to aqueous samples.
Aqueous effluents were sampled by vacuum aspiration (1500 - 1800 mis)
through a commercial reversed phase cartridg-e, J.T. Baker, 6.0 ml
reversed phase, octyl and octadecyl, extraction columns. To prevent
cartridges from rapid plugging by coarse particulates, a small amount of
glass wool was placed in the cartridge. Following collection of the
sample, the column was eluted with a 10 ml volume of 90% acetonitrile/10%
methanol. A simple liquid-liquid partitioning scheme was employed for
sample clean up. Following elution of the extraction columns/cartridge,
20 mis of distilled water and 10 mis of hexane were added to the 10 ml
sample in 90% acetonitrile/10% methanol in a 125 ml separatory funnel.
This aqueous solution was extracted by the hexane. The aqueous phase was
discarded and the hydrocarbon solvent was reduced in volume to
approximately 1 ml in a conical 2 ml test tube. A carefully measured
volume (usually 50 ul) of Me SO was added to the PAH containing
fraction and the remaining hexane removed by evaportation under a gentle
stream of warm air. Samples of 1- 10 ul were injected into the HPLC for
analysis of PAH. This procedure assures only a semi-quantitative result
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due to low recoveries. Average PAH recoveries ranged from 25% for the
octadecyl cartridge to 50% for the octyl cartridge.
QUANTITATIVE HPLC ANALYSES FOR SEDIMENTS AND AQUEOUS SAMPLES
The PAH content of analytical fractions was estimated by using
reverse phase gradient elution HPLC. Analyses were performed using a
Perkin-Elmer series 3B liquid chromatograph and acetonitrile/water as the
eluting solvent system. Although solvent gradients were varied to
accommodate column characteristics, flow rates of 1.0 to 1.5 mls/min and
linear solvent gradients from 40% to 100% (15 to 40 minutes in length
depending on column characteristics) gave satisfactory results.
Although several commercial brands of PAH selective columns were
employed (Supelco, Supelcosil LC-PAH; Perkin-Elmer PAH ; and Vydac
201TP 54.6), most samples were analyzed on the Vydac column. In the
absence of interfering compounds, all three brands were capable of
completely resolving all 16 EPA priority PAH. At the first signs of loss
of column resolution or selectivity, the column was either reversed or
replaced to restore the effectiveness of the separation.
The column was connected in series to an absorbance detector
(Perkin-Elmer LC-75 spectrophotometer equipped with an autocontrol for
scanning of spectra) and a fluorescence detector (Perkin-Elmer 650-10S
fluorospectrophotometer equipped with a by-pass valve enabling the flow
cell to be taken offline for spectral scanning). In this arrangement,
low molecular weight PAH compounds were detected by their absorbance at
254 nM and higher molecular weight PAH compounds were detected by their
fluorescence signals. An exciting wavelength of 295 nM and an emission
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wavelength of 405 nM, using a slit width of 10 nM (both excitation and
emission monochrometers) were used.
Absorbance data were quantified using a Spectra-Physics 4100
computing integrator. Peaks detected by their fluorescence were
quantitated using a Hewlett-Packard 3390A integrator. All PAH compounds
were quantitated on the basis of peak areas and individual response
factors.
Gradient program
Column: Vydac 201TP 54.6, C10; flow rate 1.5 ml/min; initial
1 o
solvent 40% acetonitrile/H20
TI - 40 min linear to 99.9% acetonitrile/H20
T2 - 22 min hold at " " "
T3 - 2.5 min linear return to 50% acetonitrile/H 0
T equilibrate - 10 min at 40% acetonitrile/H20
Although all components present in PAH containing analytical
fractions were not identified, 16 components were identified as PAH
compounds. Peaks were identified on the basis of relative retention
times and co-chromatography with available PAH standards. Internal
reference peaks used were phenanthrene and chrysene(absorbance
chromatograms) and benzanthracene, benzo(k)fluoranthene, and
3,4-benzo(a)pyrene (fluorescence chromatograms). Chrysene was added as
an internal reference compound by co-injecting a volume equal to 25 ng
along with the sample. In addition, seven compounds were confirmed (in
selected samples) on the basis of spectral characteristics identifiable
to the compound of interest. Although compounds were not routinely
confirmed spectroscopically, most sediment samples exhibited similar peak
distributions characteristic of a PAH "fingerprint". The compounds
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carbazol, naphthylene, acenaphthylene, and acenaphthene may have been
present in most samples. The volatility and solubility characteristics
of these compounds interfered with their quantitative recovery in the
Florisil chromatography and clean up procedures.
The following compounds usually appear to be well resolved by the
chromatographic conditions employed: phenanthrene, anthracene,
benzanthracene, chrysene, benzo(k)fluoranthene, and benzo(a)pyrene.
Mesurements of these PAH (in the samples analyzed for the present
project) usually reflect a high degree of accuracy. Other PAH, including
fluoranthene, methylphenanthrene, pyrene, methylanthracene, and
benzofluorene, were variably resolved from neighboring peaks and
therefore data for these compounds reflect a lower degree of
accuracy. Data for these PAH should be useful for comparison
purposes within the study areas as well as providing
semi-quantitative data for external comparison. Two compounds,
dibenz(a,h)anthracene and benzo(g,h,i)perylene, although potentially
well resolved by the fluorescence detection method, are generally
present at only trace levels (relative to the amounts of other PAH)
and the routine measurements of these two PAH may exhibit a variable
degree of certainty depending upon the concentrations of these
compunds relative to fluorescence background materials in the high
molecular PAH region of the chromatogram. Two more compounds,
perylene and benzo(b)fluoranthene, appear to co-elute. In this
situation the peak(s) is quantitated as perylene by UV absorbaance
and as benzo(b)fluoranthene by fluorescence. Thus, data represent
maximal estimates for these two compounds.
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FIELD SAMPLING
Polypropylene substrates were used exclusively in a preliminary
sampling survey which was done in Fall 1980 and Spring 1981 at 25 sites
(Fig. 1) from the mouth of Smoke Creek north to the mouth of Tonawanda
Creek on the Niagara River. Verification sampling was done in 1981 and
1982 at areas indicated to have high PAH concentration by the preliminary
survey. This sampling was done to confirm the preliminary sampling
results and narrow the area of suspected PAH input. Analyzed media
included water, polypropylene substrates, and sediment.
Grab or composite water samples were taken for PAH analyses. Two
liter grab samples were taken on two subsequent days from Smoke Creek.
Allied Chemical, Buffalo Color, Bethlehem Steel, and the Lackawanna Sewer
Treatment Plant outfalls were sampled with an ISCO toxics sampler. Water
samples were composited in a 10 L bottle at a rate of 100 ml/15 min. over
a 24 h period. The Buffalo Sewer Authority outfall was also sampled with
an ISCO toxics sampler at the rate of 200 ml/15 min. over a 24 hr.
period. Samples were composited into a 20 L container. Sediment samples
were taken by Ponar Dredge.
STATISTICAL TREATMENT
Relative proportions of PAH were used to characterize sediment
sampling sites. The degree of similarity among sites was calculated with
n-space Euclidean geometry where n is the number of different PAH
compounds analyzed. Small n-space distances indicate similarity among
sites based on the relative proportions of PAH. The computer software
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used to generate the distances produces a cluster map that shows the
clusters of sites and, therefore, which sites are more closely associated
based on the relative PAH composition.
Cluster analyses of PAH distribution in sediments were done using
the SAS (SAS 1979) cluster analysis program. Eighteen PAH compounds were
quantified in sediment analyses, but only PAH with low solubility that
would be expected to be retained in sediment were used in the cluster
analyses. These were benzo(e)pyrene, chrysene, perylene, benzo(a)pyrene
and dibenzo(a.h)anthracene. Cluster analyses were performed on the
relative percentage of these five PAH's and they identified differences
in PAH composition among sites studied. The cluster analysis is based on
2 22
the following equation: x = (a. - bj + (a~ - b ) (a - b ) ,
where a is the percent of total PAH composition of a specific PAH at
one site and b is the percent of total PAH composition of the same
n
compound at another site. Small values of x should therefore indicate a
similarity in PAH composition between sites, while relatively large
values of x indicate a dissimilarity in PAH composition between sites.
The SAS program carries out a multistep process. It begins by forming
one cluster for each observation in the analysis. The two closest
clusters are then combined into one cluster, then the two new closest
clusters are combined into a single cluster, and so on until all
observations are in a single cluster. This process is depicted on a
cluster map (see Fig. 11) by lines of asterisks joining each cluster as
it is formed starting from the top of the page and reading down. Sites
which have a similar PAH composition should cluster together at an early
stage in this analysis.
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RESULTS AND DISCUSSION
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PRELIMINARY SURVEY
The twenty-five sites sampled by artificial substrate in Spring
1981, including 13 sites which were sampled in Fall 1980, are shown in
Fig. 1. Chromatograms of extracts were ranked qualitatively for total
PAH concentration (Table 1; Appendix A). Five broad groupings were
established: neglible, low, medium, medium high, and high. Each
grouping has an approximate tenfold difference in total PAH accumulation
from its adjacent group. Unless otherwise indicated, no attempt was made
to quantify PAH accumulation in artificial substrates throughout this
investigation. The distribution of sites so grouped is indicated in
Figure 1. The site ranking of the 13 identical sites sampled in 1980
versus 1981 is similar with the exception of Two Mile Creek. On the
basis of the preliminary sampling data, five areas which had medium to
high PAH accumulation during at least one sampling period were considered
for further investigation. These were: 1) Two Mile Creek, 2) Buffalo
Sewer Authority, 3) Buffalo River, 4) Lackawanna-Union Canals, and 5)
Smoke Creek.
The five sampling sites identified by the preliminary survey as
having significant PAH inputs were in areas that had potential
anthropogenic sources of these compounds such as iron and steel
manufacturing operations (Smoke Creek, Union and Lackawanna Ship Canals,
and Buffalo River), oil storage facilities (Two Mile Creek), municipal
wastewater treatment facilities (Buffalo Sewer Authority) or other
industrial activities (Buffalo River). Four areas identified as having
PAH inputs in the preliminary survey - Buffalo River, Smoke Creek, Union
and Lackawanna Ship Canals, and Two Mile Creek were subsequently sampled
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Q
Tonawanda Creek
Black
Creek
HIGH I
MEDIUM HIGH,
MEDIUM I
LOW
NEGLIGIBLE
Scajaquada Creek
Buffalo River
9 Q 2
TOTAL PAH
Spring Fall
81 80
B
Q
D
Lake Erie
Srnoke Creek
FIGURE 1: PRELIMINARY ARTIFICIAL SUBSTRATE SAMPLING SITES AND RELATIVE
TOTAL PAH CONCENTRATION DETAILED SITE DESCRIPTION FOR THIS
FIGURE IS PRESENTED IN APPENDIX C.
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TABLE 1. PAH SCREENING RESULTS (RANK-GROUP)
SAMPLE SITE Fall 5/81 5/81 6/81 6/81 6/81
"80" wk. 2 wk. 4 wk. 1 wk. 2 wk. 3
1. Smokes Creek 6-M 2-MH
2. Union Canal 3-MH 1-M 3-MH
3. Lackawanna Canal (Mouth) 19-L
4. Lackawanna Canal 2-MH 8-H 9-M
5. Small Boat Harbor A 27-N
6. Small Boat Harbor B 4-L 26-N
7. Buffalo River A (Breakwall) 10-N 20-N 25-N
8. Buffalo River B (Naval Park) 5-L 12-M 5-M
9. Allied Chemical (L bank below) 7-M
10. Allied Chemical (R bank below) 10-M
11. Republic Steel 11-M
12. Buffalo Color 15-L
13. Scajaquada A 6-L 16-L
14. Scajaquada B 9-N
15. Buffalo Sewer Authority 4-MH
16. Sheridan Drive (foot of) 11-N 13-L
17. Niagara Mohawk 7-L 18-L
18. Two Mile Creek A 1-H 23-N
19. Two Mile Creek B 24-N
20. Tonawanda Creek A 22-N
21. Tonawanda Creek B 8-L
22. Frenchman's Creek A 21-N
23. Frenchman's Creek B 12-N 17-L
24. Black Creek A 13-N
25. Black Creek B 19-L
H - High
MH - Medium High
M - Medium
L - Low
N - Negligible
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with artificial substrates, or water and sediment samples were taken for
PAH analyses to assist in source identification. This verification
sampling was planned in conjunction with Region 9 NYSDEC staff, Central
Office NYSDEC staff, and the contractor. The Buffalo Sewer Authority was
monitored directly in the discharge and, therefore, no further source
identification was required. However, water samples were taken to assess
PAH concentrations in the discharge. These sites will be discussed in
detail under verification sampling.
The criteria for selecting a site from the preliminary survey for
further investigation was based on a ranking of medium to high during a
minimum of one sampling period by artificial.substrate. Artificial
substrates were consistent in the accumulation of total PAH in the
preliminary survey with the exception of those at the Buffalo River at
Naval Park and Two Mile Creek. The Buffalo River at Naval Park (Fig. 1)
artificial substrate samples gave a reading of low and medium during two
different sampling periods. At this location in the Buffalo River, there
is a characteristic flow reversal which may account for low PAH level in
the artificial substrate on one occasion and a medium reading on another
occasion, because the PAH contamination from upstream may not be
consistently carried downstream as would be expected in most riverine
systems. The Two Mile Creek substrate results of a high and a negligible
level in artificial substrates may result from the extremly intermittent
nature of the sources of PAH in this drainage. These results will be
discussed in detail under the verification sampling.
The results from the preliminary survey indicate that artificial
substrates were effective in screening large areas for PAH inputs. These
substrates have several advantages for ambient monitoring over
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-17-
conventional environmental samples. These are 1) ability to place them
almost anywhere in an aquatic environment, 2) integration of contaminant
exposure over time, and 3) identification of the presence of PAH in the
water column. The use of an artifical substrate offers an alternative to
monitoring of water, sediment, or biota that can overcome some of the
problems involved with contaminant monitoring of these strata. Water
sample monitoring may miss occasional, but significant discharges of PAH.
Sediment sampling may reflect old discharges which may not have any
significance to environmental or human health, because the contaminants
are bound to the sediments. Conversely, leaching of PAH from sediments
into the surface waters can be detected by use of the artificial
substrates. Sampling biota may provide integration of contaminant
exposure over time, however contaminant monitoring is complicated by the
mobility of the organisms being monitored. The artificial substrates
overcome these problems in water, biological, and sediment monitoring.
VERIFICATION SAMPLING
Following the preliminary survey, site specific sampling was carried
out for those areas having medium to high total PAH concentrations as
indicated by the preliminary survey. These areas were the Buffalo Sewer
Authority, Buffalo River, Smoke Creek, the Union and Lackawanna Ship
Canals, and Two Mile Creek. This sampling included additional sampling
with artificial substrates, water, or sediment collections. Artificial
substrates were used to focus more clearly on the area of suspected
discharge. Sampling of sediment and water was used to suggest or confirm
sources of PAH. PAH sediment sampling locations are shown in Figs. 2-5.
-------
-18-
N
50000
25000
Total PAH pg/gm
wet weight
Al 1ied Chemical
Buffalo Color
. Park bridge
Republi c Steel
1 23^5678910
SITE
FIGURE 2: PAH SEDIMENT SAMPLING SITES. BUFFALO RIVER WITH RELATIVE
TOTAL PAH CONCENTRATION. DETAILED SITE DESCRIPTION FOR
THIS FIGURE IS PRESENTED IN APPENDIX C.
-------
-19-
LAKE ERIE
I
100000-
Total PAH ng/gm
wet weight
50000-
1 2 3 A 5 6 7 8
V
FIGURE 3: PAH SEDIMENT SAMPLING STIES. SMOKE CREEK TRANSECT IN
LAKE ERIE WITH RELATIVE TOTAL PAH CONCENTRATION
DETAILED SITE DESCRIPTION FOR THIS FIGURE IS PRESENTED
IN APPENDIX C.
-------
-20-
J
i
Total PAH ng/cim
wet weight
500004
LAKE ERIE
Union Canal
Lackawanna Canal
FIGURE A: PAH SEDIMENT SAMPLING SITES AT UNION AND LACKAWANNA CANALS
WITH RELATIVE PAH CONCENTRATION.. DETAILED SITE DESCRIPTION
FOR THIS FIGURE IS PRESENTED IN APPENDIX C.
-------
-21-
Total PAH ng/gm
wet weight
100000-
50000-
FIGURE 5: PAH SEDIMENT SAMPLING SITES AT TWO MILE CREEK WITH
RELATIVE PAH CONCENTRATION. DETAILED SITE DESCRIPTION
FOR THIS FIGURE IS PRESENTED IN APPENDIX C.
-------
-22-
In addition to these sites, sediment samples were taken at the junctions
of Frenchmans and Black Creeks with the Niagara River in Canada and in
Tonawanda Creek (U.S.A.). one quarter mile upstream from its confluence
with the Niagara River. Individual PAH sediment concentrations for all
locations are shown in Appendix B (Tables 1-7). Concentrations of
phenanthrene, benzanthracene and benzo(a)pyrene are summarized in
Appendix D (Table 8) for all sites to allow comparison of a 3-ringed
(phenanthrene), 4-ringed (benzanthracene) and 5-ringed (benzo(a)pyrene)
compound at all sediment sampling sites. Water samples were taken from
discharges to confirm the presence of PAH in effluents. PAH
concentrations in unfiltered water are reported for the following
locations: Bethlehem Steel/Smoke Creek (Table 2), Buffalo Color/Buffalo
River (Table 3), Allied Chemical/Buffalo River (Table 4) and the Buffalo
Sewer Authority outfall (Table 5). Verification sampling with artificial
substrates and associated sediment and water analyses for PAH
consistently demonstrated contamination with these compounds.
Sediment sampling for PAH contamination corroborated the PAH
contamination indicated by the substrates. This relationship between
relative grouping of sites and sediment contamination of PAH for 10 sites
having preliminary artificial substrate sampling and verification
sediment sampling locations in common is shown in Fig. 6. Sites ranking
medium to high by artificial substrate determinations tended to have
higher concentrations of PAH in sediment. Conversely, sites ranking low
or negligible by artificial substrates tended to have lower
concentrations in sediment. Tonawanda Creek is an exception to this
overall pattern. PAH concentrations in sediment at Tonawanda Creek,
which artificial substrate sampling indicated had low concentrations of
-------
H
3
H W O
*
a
o
a
o
o
n>
O
Q
W
K3
N3
O
O
O
O NJ I—•
UJ
o
-O
K>
O
-P-
o
O
Bethlehem Steel
Outfall
217
oo
oo
o
o
o
O
O
-~l ^-J O
O O O
^J OJ (^
Ln O O
o o a a o
o o o o o
O
O
O
Bethlehem Steel
Outfall
225
o
o
OO
(sJ
o\
o
u>
Ul
Lackawanna
STP Outfall
tjJ
Ln
O
WO
Smoke Creek
Downstream of South
Return Trench
o
o
M O CO i—
.p~ ON O <-n
OO
OO
O
Return Trench
South of Mouth of
Smokes Creek
(S3 O OJ H-• IjJ
a • • • • • a
Oi-n^—JhO-P^4>-O
Smoke Creek
Immediately Upstream
of Bethlehem Steel
-ez-
-------
-24-
TABLE 3. PAH CONCENTRATIONS IN WATER FROM BUFFALO COLOR WATER OUTFALLS
AND INTAKE
COMPOUND
Intake
Concentration (ng/L)
Outfall
006
Outfall
Oil
FLUORENE ND*
PHENANTHRENE ND
ANTHRACENE ND
FLUORANTHENE 1.3
MePHENANTHRENE ND
PYRENE 4.2
MeANTHRACENE ND
BENZOFLUORENE ND
BENZANTHRACENE 0.2
CHRYSENE 0.4
BENZO(e)PYRENE ND
PERYLENE ND
BENZO(b)FLUORANTHENE 0.3
BENZO(k)FLUORANTHENE 0.2
BENZO(a)PYRENE 0.8
DI.BENZO(g,h,i)PERYLENE 0.2
BENZO(g,h,i)PERYLENE 0.3
INDENO(1,2,3-c,d)PYRENE ND
TOTAL 7.9
ND
ND
ND
5.4
ND
5.2
ND
ND
0.3
0.4
ND
ND
0.3
0.2
0.7
0.1
13
ND
25
ND
ND
ND
6.0
ND
43
ND
ND
0.6
1.1
ND
ND
0.6
0.3
0.9
0.
0.
1
4
ND
53
*ND - Not Detected
-------
-25-
TABLE 4. PAH CONCENTRATIONS IN WATER FROM ALLIED CHEMICAL OUTFALLS TO
BUFFALO RIVER
Concentration (ng/L)
COMPOUND
FLUORENE
PHENANTHRENE
ANTHRACENE
FLUORANTHENE
McPHENANTHRENE
PYRENE
MeANTHRACENE
BENZOFLUORENE
BENZANTHRACENE
CHRYSENE
BENZO(e)PYRENE
PERYLENE
BENZO(b)FLUORANTHENE
BENZO(k)FLUORANTHENE
BENZO(a)PYRENE
DIBENZ(a,h)ANTHRACENE
BENZO(g,h,i)PERYLENE
INDENO(1,2,3-c,d)PYRENE
TOTAL
Outfall
001
ND*
ND
ND
ND
ND
2.1
ND
ND
0.2
0.3
ND
ND
0.2
0.1
0.5
0.1
0.2
ND
3.7
Outfall
003
ND
ND
ND
1.2
ND
1.1
ND
ND
0.1
ND
ND
ND
0.6
ND
0.5
ND
0.1
ND
3.6
Outfall
004
ND
ND
ND
5.4
ND
2.0
ND
ND
0.1
0.6
ND
ND
0.
0.
0.7
0.7
7.5
ND
17
*ND - Not Detected
-------
-26-
TABLE 5. PAH CONCENTRATIONS IN BUFFALO SEWER AUTHORITY OUTFALL WATER
(ng/L)
COMPOUND CONCENTRATION
FLUORENE ND*
PHENANTHRENE ND
ANTHRACENE ND
FLUORANTHENE 5.7
MePHENANTHRENE ND
PYRENE 9.2
MeANTHRACENE ND
BENZOFLUORENE ND
BENZATHRACENE 0.5
CHRYSENE 5.5
BENZO(e)PYRENE ND
PERYLENE ND
BENZO(b)FLUORANTHENE 0.7
BENZO(k)FLUORANTHENE 0.3
BENZO(a)PYRENE 0.8
DIBENZ(a,h)ANTHRACENE 0.1
BENZO(g,h,i)PERYLENE 0.5
INDENO(1,2,3-c,d)PYRENE ND
Total PAH Concentration 23
*ND - Not Detected
-------
-27-
Scdimnt
Total PAH
ng/gm x 10*
wet Might
• 7
•6
-o2
"°1
-• 10
-05
MH
Artificial Substrate Group
Figure 6: Total PAH Sediment Concentrations (wet weight) and
Corresponding Artificial Substrate Total PAH
Group for Similar Stations. (Only ten stations appear
because sediments were not available or taken from the
other substrate sampling stations. If two substrate
samples were taken at the same site the mean of the groups
is indicated by a filled in circle.). DETAILED SITE
DESCRIPTION FOR THIS FIGURE IS PRESENTED IN APPENDIX C.
Key
1. - Mouth of Black Creek
2. - Mouth of Frenchman's Creek
3. - Mouth of Tonawanda Creek
1*. - Buffalo River at South Park Bridge
5. - Buffalo River at Naval Park
6. - Buffalo River at Republic Steel
7. - Buffalo River at Buffalo Color
8. - Lackawanna Canal
9. - Union Canal
10.- Two Mile Creek
-------
-28-
PAH, had sediment concentrations similar to those sites ranked medium by
artificial substrate sampling. This may indicate that PAH in sediments
of Tonawanda Creek are not entering the water column, and therefore are
not available to be accumulated in artificial substrates.
The results from the verification sampling of the five areas
identified as having suspected PAH discharges are discussed below.
Buffalo Sewer Authority
No further source identification was required at this site because
artificial substrates were placed directly in the discharge. A water
sample from this discharge was taken for analysis. The total PAH
concentration of 23 ng/L (Table 5) was a relatively low value compared to
those for PAH in wastewater treatment effluents as summarized by Neff
(1979). This would amount to a loading of 17 gm of total PAH to the
river per day. Although this is a relatively small amount of PAH, there
may be considerable variation in the PAH burden of the wastewater from
day to day. Consequently, the Buffalo Sewer Authority may require
additional water sampling to determine the PAH load to the Niagara River.
Buffalo River
Eleven sites were sampled by artificial substrates in the Buffalo
River (Fig. 7). All sites sampled had evidence of PAH contamination
(Table 6). Sites 4 and 7 gave high values that suggested point source
contributions. Sites 4 and 7 are near effluents from Allied Chemical,
Buffalo Color, and Republic Steel. They were subsequently targeted for a
further study which is described below.
Artificial substrates were placed near the two Allied Chemical
effluents, Buffalo Color, and the two Republic Steel effluents. There
appeared to be a strong PAH source near the South Park bridge (Fig. 8).
-------
TABLE 6. PAH CONCENTRATIONS
ARTIFICIAL SUBSTRATES FROM BUFFALO RIVER
Site
Site
Site
Site
Site
Site
Site
Site
Site
Site
Site
1
2
3
4
5
6
7
8
9
10
11
.c
4J
C
a
c
0)
.c
PM
151
17
14
6.82
10
12
13
14
12
12
15
01
c
0)
o
ra
u
j=
4J
•*
1.9
2.8
1.9
1.8
0.9
1.8
3.1
3.4
2.0
1.5
2.2
JC
4J
c
to
H
s
rH
fH
54
95
74
220
3.7
77
140
110
72
29
40
JC
4J
C
to
c
01
x
Q-i
01
SS
9.9
16
13
27
7.4
13
22
16
13
4.3
7.8
,
X
4J
5
01
S
8.4
12
12
24
20
13.5
37
19
13
3.3
7.7
^i
o
3
rH
tM
O
N
C
1>
PQ
8.1
22
28
150
26
27
78
37
28
2.5
9.8
.c
4-J
C
M
N
C
01
pa
12
17
36.6
200
38
32
130
36
36
1.1
_
,
M
(U
P-.
23
10
22
59
4.8
14
84
17
22
8.7
16
£_
D.
s^
N
C
01
PO
6.7
5.5
6.4
4.6
-
2.8
38
8.1
4.0
9.6
11
•=„
n)
^^
N
C
11
•H
Q
3.3
2.3
5.4
6.2
-
-
17
2.4
0.4
-
2.4
eg
Q) <}
C p i
11
C iH
o rt
V^ 4J
o o
CJ H
1 1
180 {^
1
232
270
LP 960x5
135
250
LP 777
333
259
91
146
1 All concentrations are in nanograms per substrate
2 1 ul injected - multiply by 5 for equivalent values ie. 4781.0
3 based on identified peaks only
LP significant peak in this area
-------
-30-
A second artificial substrate sampling was done one month later to
supplement results of previous investigations. Artificial substrates
were tiered in relation to a probable downstream flow from the South Park
Bridge area, and an upstream flow from Republic Steel to distinguish
between a possible erroneous analysis resulting from upstream movement of
PAH from downstream sources due to flow reversal. Results of these
analyses are shown in Fig. 8. The distribution of PAH contamination at
this site indicates that it is unlikely that the high levels associated
with the South Park bridge are due to upstream movement of PAH from other
effluents. However, the possibility of pooling of PAH at this site
should also be considered as a possible reason for the consistently high
result.
PAH sediment samples were taken throughout the Buffalo River
(Fig. 2) in addition to artificial substrate samples (Fig. 7). Sediment
samples had their highest PAH concentrations immediately downstream from
the South Park bridge (Fig. 2) which corroborates the source of PAH
indicated by the high accumulation of PAH by artificial substrates at
this location (Table 6).
Water samples from outfalls of two dischargers in this area had PAH
in their water samples (Table 3). Buffalo Color outfall Oil was
approximately 1000 yds. upstream from the south Park Bridge. This
discharge had PAH concentrations seven times higher than intake water.
This outfall may be one point source of the high PAH concentrations found
in the area of the South Park Bridge. Although most PAH compounds were
not found in Buffalo Color outfalls (Table 3), pyrene exhibited the
highest concentration of any PAH from the outfalls sampled in this area
(Tables 3 & 4). The highest concentration of pyrene found in Buffalo
-------
- 31 -
Allied Chemical
Buffalo Color
BUFFALO RIVER
South Park Bridge
Republic Steel
7
8
FIGURE 7: ARTIFICIAL SUBSTRATE SAMPLING SITES IN BUFFALO
RIVER. DETAILED SITE DESCRIPTION FOR THIS FIGURE
IS PRESENTED IN APPENDIX C.
-------
-32-
River sediment was also at this location. Allied Chemical outfalls did
not exhibit high concentrations of pyrene (Table 4). Allied Chemical or
Buffalo Color discharges have not been conclusively proven to be the
dischargers of the high PAH concentrations observed in this area of the
Buffalo River. However, it is clear that a significant source of PAH is
present near the South Park bridge. As can be seen from Fig. 2, total
PAH concentrations in sediment decrease in subsequent downstream
stations. Artificial substrate sampling also suggested inputs of PAH in
the vicinity of Republic Steel discharges, however, direct effluent
sampling was not done because these discharges were not in operation at
the time of planned sampling. Although the present evidence indicates a
point source in the Buffalo River at the South Park bridge, further
effluent water and sediment monitoring would be required to pinpoint the
cause of the extremely high total PAH concentrations in sediment.
Although there are industrial facilities in this area, release of high
concentrations of PAH from the type of chemical manufacturing or dye
operations that are present here is not to be expected (US EPA, 1979).
Another potential source of PAH at this location may be from groundwater
leachates to the Buffalo River.
The percentages of constituent PAH compounds in sediment vary
considerably between those taken at sediment sampling site 5
(Table 7, Fig. 9), which was near the South Park bridge, and sampling
site 6 (Table 7). Benzo(e)pyrene was not detected in sediment near the
South Park bridge but was found in the vicinity of the Republic Steel
outfalls (Site 6, Table 7) to this area at concentrations of 130 ng/gm
organic weight. An outfall of Donner-Hanna Coke also discharges at this
location. Benzo(a)pyrene concentrations approximately double at site 6
-------
-33-
TABLE 7. PAH SEDIMENT CONCENTRATIONS (ORGANIC WEIGHT ng/mg) AT BUFFALO
RIVER SITES 5 and 6
CONCENTRATION
COMPOUND
FLUORENE
PHENANTHRENE
ANTHRACENE
FLUORANTHENE
MePHENANTHRENE
PYRENE
MeANTHRACENE
BENZOFLUORENE
BENZANTHRACENE
CHRYSENE
BENZO(e)PYRENE
PERYLENE
BENZO(b)FLUORANTHENE
BENZO(k)FLUORANTHENE
BENZO(a)PYRENE
DIBENZ(a,h)ANTHRACENE
BENZO(g,h,i)PERYLENE
INDENO(1,2,2-c,d)PYRENE
TOTAL
Site 5
13
200
70
210
29
450
20
190
42
7
ND*
280
ND
18
39
130
14
16
1700
Site 6
20
110
42
100
28
220
17
180
80
54
130
240
62
36
79
14
73
51
1500
*ND - Not Detected
-------
-34-
Buffalo
Color
Buffalo
Color
Total PAH
10-81 11-81
HIGH £ •
MEDIUM HIGH ^ Q
MEDIUM Q Q
LOW O D
OUTFALLS A
RepublIc Steel
FIGURE 8: BUFFALO RIVER ARTIFICIAL SUBSTRATE SAMPLING SITES
NEAR SOUTH PARK BRIDGE AND TOTAL PAH
-------
-35-
as compared to 5 (Table 7; Fig. 9) even though total PAH concentrations
decrease. However, artificial substrates do not reflect this increase in
benzo(a)pyrene and benzo(e)pyrene concentrations (Table 6). High
concentrations of benzo(a)pyrene have been associated with foundry
(Schimberg ej^ a^l. , 1980) and coking operations (Lao e_t a_l. , 1975).
Benzo(e)pyrene has also been reported in air samples from foundries.
Therefore, the increase of these two compounds in the sediments could be
expected. The operations at the Republic Steel and Donner-Hanna Coke
facilities have been curtailed and consequently the presence of PAH
presumably attributable to these facilities may represent old inputs.
The absence of increases of benzo(a)pyrene and benzo(e)pyrene
concentrations in substrates placed at the South Park bridge and at Site
6 may be due to the absence of ongoing discharges from Donner-Hanna and
Republic Steel. Chrysene concentrations also significantly increase in
concentration from 7 ng/gm organic weight to 54 ng/gm (Table 7) from
sediment sampling sites 5 to 6. Chrysene has been reported at extremely
high concentrations in raw wastewater of foundries and iron and steel
manufacturers. Maximum concentrations for foundries and iron and steel
manufacturing were reported as 1,300 ug/L and 2,200 ug/L respectively
with mean values of 1,100 ug/L and 94 ug/L (USEPA 1979).
The presence of elevated PAH concentrations in drainage basins of
highly urbanized areas such as the Buffalo River is not unusual (Herman
1981, Wong 1981). The PAH concentration in the sediments, however, are
extremely high. Eadie et al. (1982) reported sediment concentrations of
total PAH of up to 770 ug/kg in western Lake Erie associated with a power
plant while the total PAH concentrations in Buffalo River sediments were
I
as high as 44,000 ug/kg wet weight.
-------
KCT
A«%
20
Percent
of
Total PAH
10
1 1
li
II
PI
Ph
An
Fla
MeP
Py
M«A
BeP
B«A
Ch
BeP
Pery
BbF
BKF
B«P
D1A
Fluortnc
Phenanthren*
Anthracene
Fluoranthen*
Methyl
phenanthrene
Pyrene
Me anthracene
Benzof luorene
Bencanthracm*
Chryaene
Benzo(e)pyrent
Perylene
Bento(b) f luoranthene
Benco(K) f luoranthene
Bento(a)pyrene
Pibent(a,h)anthrccen«
B(ghl)P - Bcnco(|
1 1
1
1
In P
i ,i i
.h.Dperylene
Indano(If2,3>c.d)pyrcn*
I |
Fl Pfr An Flo MtP Pjr McA BtF BeA Ch BeP Ptry BbF BkF JBoP Of A BghIP
|
biP
CO
i
PAH
Figure 9: Present Composition of Total PAH Compounds in Sediment
(Organic Weight) at Buffalo River Sites 5 and 6.
First Line of Pair is Site 5.
-------
-37-
Smoke Creek and Union and Lackawanna Canals
Smoke Creek and the Union and Lackawanna Canal areas are treated
together because the suspected source of the PAH pollution of this area
is the same for both.
PAH concentrations in the artificial substrates placed in the south
branch of Smoke Creek were considerably higher than in those in the north
branch (Fig. 10, Table 8). A heavy rain had fallen and the source of PAH
may have been a sewer overflow discharging to the south branch of
Smoke Creek. However, another DEC sampling program for contaminants
(Spring 1982) in sewer overflows did not find high PAH concentrations in
this sewer overflow. PAH concentrations at the mouth of Smoke Creek were
higher than those at any other station except the south branch station,
and this suggests an input of PAH from the Bethlehem Steel property.
A strong contribution of PAH was apparent in the area of the
Lackawanna and Union Ship Canals (Fig. 10), however an artificial
substrate placed directly in the Union Canal had a relatively low PAH
concentration (Table 8).
PAH analyses of water samples from Bethlehem Steel outfalls and in
the portion of Smokes Creek running through Bethlehem Steel property
revealed the highest PAH concentrations in water found in this study
(Table 2). Fluoranthene occurred in the highest concentration in all
water samples while pyrene occurred in the second highest concentration.
Compounds such as fluoranthene, chrysene, and benzo(a)pyrene, all present
in Bethlehem Steel outfall samples, have been reported from other foundry
and ferrous metal manufacturing operations (USEPA, 1979) . The
concentration of total PAH (organic weight) at Lake Erie site 8 exhibits
an approximate four fold increase in concentration over total PAH
-------
-38-
LAKE
ERIE
V
FIGURE 10: ARTIFICIAL SUBSTRATE SAMPLING SITES AT SMOKE
CREEK AND THE UNION AND LACKAWANNA CANALS.
DETAILED SITE DESCRIPTION FOR THIS FIGURE IS
PRESENTED IN APPENDIX C.
-------
-39-
TABLE 8. PAH CONCENTRATIONS IN ARTIFICIAL SUBSTRATES
SMOKE CREEK AND UNION AND LACKAWANNA CANALS
(ng/SUBSTRATE)
Total PAH
Site 1 190
Site 2 150
Site 3 330
Site 4 61
Site 5 78
Site 6 56
Site UL1 110
Site UL2 7600
-------
-40-
reported from Lake Erie site 1 (Fig. 3). The individual PAH reported in
Bethlehem Steel outfalls approximate this increase at Lake Erie from site
1 to site 8 by an approximate four to seven fold increase depending on
the individual PAH compound. Sediment samples from the Union and
Lackawanna Canals exhibit a marked decrease in total PAH concentration
with distance away from the canal entrances (Fig. 4). The sediment PAH
composition exhibits relatively high concentrations of fluoranthene,
pyrene, chrysene, benzoanthracene, and other PAH compounds also found in
water samples from Bethlehem Steel outfalls (Table 2), but compounds
such as fluoranthene, pyrene, and chrysene were found in relatively high
concentrations in sediment from other locations in the study area. Smoke
Creek and Union and Lackawanna sediment sampling locations exhibited an
association in the cluster analyses (Fig. 11 - Cluster 2, Table 9).
However, the cluster analyses suggest similarities in relative PAH
distribution between sites associated with the Bethlehem Steel operation
and areas far removed from this location such as Tonawanda Creek, Two
Mile Creek, and two locations on the Canadian side of the Niagara River,
Frenchman's Creek, and Black Creek (Fig. 11). This may be due to the most
common source of PAH contamination, air deposition of products of
combustion. Because of the ubiquitous nature of combustive PAH
production it is not suprising that diverse areas have similar PAH
constituents. Laflamme and Kites (1980) indicate that qualitative and
quantitative similarities in PAH compounds in sediments from diverse
areas result from combustive processes. It is therefore not unexpected
that a steel manufacturing operation employing various combustive
processes for manufacturing would have similar PAH composition in its
-------
SAMPLE
NUMBER OF
CLUSTERS
3D
Z9
£9
£7
2*
29
£4
23
22
£1
20
19
IB
17
1*
J3
14
S3
13
II
10
7
t
5
4
3
e
t
1 89 10 2 8
0
I
2
S
N
2
S •
N II
3 5
I
R
• B
M R
3 7
U
L
I
U S
L N
5 8
T
0
N
S T
N N
5 I
U
L
*
U
L
6
S S
N N
7 I
T U
N L
2 3
r
R
I
• S
L N
I *
S
N
6
T
N
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I
Cluster 1 Cluster 2
FIGURE 11: CLUSTER MAP OF ASSOCIATION OF SEDIMENT SAMPLING
SITES BASED ON THEIR PAH COMPOSITION-.
Cluster 3
B R
S N
U L
T M
B L
F R
Ton
-10 - Buffalo River (Fig. 2)
-8 - Lake Erie Transect Across the Mouth of Smokes Creek (Fig. 3)
-6 - Union and Lackawanna Canals (Fig. 4)
-3 - Two Mile Creek 1-3 (Fig. S)
Black Creek Houth at Niagara River
Frenchman* Creek Mouth at Niagara River
Tonawanda Creek Mouth at Niagara River
-------
TABLE 9. PAH PERCENT COMPOSITION OF CLUSTERS FROM CLUSTER MAP OF SITE ASSOCIATION
Percent of Each PAH
Benzo(e)pyrene Chrysene Perylene Benzo(a)pyrene Dibenzo(a,h)anthracene
Cluster 1
Cluster 2
Cluster 3
Buffalo River 3 & 4
Buffalo River 5 8 4 56 8 26 ^
Cluster 1 includes the following sites: Buffalo River Sites 1-6, 8-10 (Fig. 2), Smoke Creek
Transect Sites 2-3 (Fig. 3).Union and Lackawanna Site 2.
Cluster 2 includes the following sites: Buffalo River 7 (Fig. 2), Union-Lackawanna 1, 3-6, Smoke Creek 1, 4-8
(Fig. 3), Two Mile Creek 1 and 2 (Fig. 5).
Cluster 3 is made up of one site: Two Mile Creek 3 (Fig. 5).
15
21
80
9
8
9
17
2
4
4
58
36
0
79
56
13
21
13
6
8
5
5
5
2
26
-------
-43-
immediate area to distant areas presumably receiving PAH contamination
from other combustion sources. Heit et al., 1980 report high
concentrations of fluoranthene, pyrene, and a number of other PAH
compounds from upper sediments (0-4 cm) of Adirondack Lakes without
nearby sources of PAH which they attribute to combustive sources. The
proportional and actual concentrations of these PAH compounds decrease
markedly in deep sediments with the exception of perylene which has been
attributed to natural sources.
Two Mile Creek
Three artificial substrates were placed in Two Mile Creek (Fig. 12).
PAH concentrations in artificial substrates are presented in Table 11.
All substrates analyzed accumulated PAH, however concentrations of PAH
were considerably higher at the mouth of Two Mile Creek than at the other
two locations (Table 10).
Although artificial substrate sampling suggested that the highest
concentrations of PAH were at the mouth of Two Mile Creek, field
investigation suggested that a source of PAH might be upstream. PAH
contaminated sediment from upstream could settle near the mouth and
subsequent leaching from these contaminated sediments may have produced
the high PAH concentrations in the artificial substrate. Further field
inspections resulted in the discovery of an oil containment boom at an
intermittent tributary of Two Mile Creek which entered the creek
approximtely 1/2 mile from its-j-unction with the Niagara River.
Substrates downstream from this intermittent tributary and upstream from
the junction of this tributary had medium high and high concentrations of
PAH respectively. A second substrate sampling was done. Artificial
-------
-44-
GRAND ISLAND
FIGURE 12: TWO MILE CREEK ARTIFICIAL SUBSTRATE SAMPLING SITES
DETAILED SITL DESCRIPTION FOR THIS FIGURE IS PRESENTED
IN APPENDIX C.
-------
TABLE 10. PAH CONCENTRATIONS IN ARTIFICIAL SUBSTRATES FROM TWO MILE CREEK (ng/substrate)
Site 1
Site 2
Site 3
a
b
b
4)
X
o.
240
20
19
c
<
50
3.0
4.3
2
LL.
950
70
92
t
£
210
14
20
<
^
170
12
15
5
to
260
17
23
c
CD
460
29
27
_£
o
600
44
61
£
m
500
38
47
4)
a.
460
35
40
c
O3
380
31
38
£
a
160
21
22
•w
o
H
440
330
408
-------
-46-
substrates were placed directly in the intermittent tributary immediately
downstream from the oil boom. Two other substrates were placed in Two
Mile Creek immediately upstream and downstream from the intermittent
tributary. The substrate in the intermittent tributary exhibited the
highest PAH accumulation, while the substrate upstream from the junction
of the intermediate tributary exhibited a moderate PAH accumulation and
the downstream substrate exhibited the lowest PAH accumulation.
Sediment from different sites in the Two Mile Creek drainage did not
appear to be similar in their relative PAH compound composition. At
Site 3 (Fig. 5, Table 11) which was the furthest upstream in the
intermittent tributary, the more soluble PAH compounds such as
fluoranthene, pyrene, phenanthrene, and methyl phenanthrene were in a
greater proportion to less soluble compounds than when compared to Site 1
(Fig. 5, Table 11) at the mouth of Two Mile Creek. However,
benzofluorene, which has a relatively low solubility (Mackay and Yinz
Shiu, 1977), is in relatively high concentrations at both sites
1 and 3. At site 1 perylene, benzo(e)pyrene, benzo(a)pyrene, chrysene
and other similar low solubility PAH compound comprise most of the total
PAH composition (Table 11, Fig. 5). Because of the intermittent nature
of the tributary at site 3 the more soluble PAH may tend to remain in the
sediment while at site 1 the more soluble PAH are subject to constant
leaching.
The presence of petroleum storage facilities in the uppermost
sections of the intermittent tributary to Two Mile Creek with a history
of 12 petroleum spills to this drainage since 1976 (NYS DEC records)
suggest that this is a source of PAH pollution to Two Mile Creek.
Although an attempt was made to compare PAH patterns in Two Mile Creek
-------
-47-
TABLE 11. PAH SEDIMENT CONCENTRATION FROM TWO MILE CREEK
(ORGANIC WEIGHT ng/mg)
CONCENTRATION
COMPOUND
FLUORENE
PHENANTHRENE
ANTHRACENE
FLUORANTHENE
MePHENANTHRENE
PYRENE
MeANTHRACENE
BENZOFLUORENE
BENZANTHRACENE
CHRYSENE
BENZO(e)PYRENE
PERYLENE
BENZO(b)FLUORANTHENE
BENZO(k)FLUORANTHENE
BENZO(a)PYRENE
DIBENZ(a,h)ANTHRACENE
BENZO(g.h.i)PERYLENE
INDENO(1,2,3-c,d)PYRENE
TOTAL
Site 1
River Rd. Bridge
ND*
5
ND
66
2
11
2
81
49
51
51
120
61
30
61
30
52
56
730
Site 3
Intermittent Tributary
13
65
17
260
34
760
45
200
21
1
46
ND
7
3
4
1
5
4
1500
*ND - Not Detected
-------
-48-
with known PAH patterns in various petroleum products, Neff (1979)
indicates that a high degree of variability exists in the PAH composition
of these products. This variability prevents a comparison of PAH
distributions in a contaminated area with a given petroleum product. In
addition, the physical, chemical, and biological processes acting upon
PAH in the aquatic environment as described by Herbes et_ al. (1980) can
alter the relative composition of PAH compounds in the aquatic
environment substantially.
Artificial substrate sampling in Two Mile Creek showed remarkably
similar PAH compositions (Fig. 13, Table 11), with the highest
concentration in substrates at the mouth of Two Mile Creek. The
relatively high PAH accumulation of a substrate placed upstream from the
junction of Two Mile Creek and the intermittent tributary suggested
another upstream source of PAH in addition to the sources associated with
the intermittent tributary. Sediments from four storm sewers entering
Two Mile Creek between Sheridan Drive and the Youngman Expressway,
approximately 1.5 miles upstream from the junction of Two Mile Creek and
the intermittent tributary identified as having one source of PAH
pollution, were sampled in 1982 by DEC. Acenaphthene, anthracene,
benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene,
benzo(g,h,i)fluoranthene, chrysene, dibenzo(a,h)anthracene, fluoranthene,
fluorene, indeno(l,2,3-cd)pyrene, napthalene, phenanthrene and pyrene
were present at concentrations of less than or equal to 2-8.7 ug/gm dry
weight. Eight of the PAH compounds present were at concentrations over 2
ug/gm. The following PAH compounds were quantified on a dry weight
basis:Anthracene (8 ug/gm), Benzo(a)anthracene (2.4 ug/gm),
Benzo(a)pyrene (2.5 ug/gm), Chrysene (3.5 ug/gm), and Pyrene (8.7 ug/gm).
-------
KEY
Percent
of
Total PAH
_LL
Fl - Fluorene
Ph - Phenanthrene
An - Anthracene
Fla - Fluoranthene
MeP - Methyl phenanthrene
Py - Pyrene
MeA - Me anthracene
BeF - Benzofluorene
BeA - Benzanthracene
Ch - Chrysene
EeP - Benzo(e)pyrene
Pery - Perylene
BbF - Benzo(b)fluoranthene
BKF - Benzo(K)fluoranthene
BaP - Benzo(a)pyrene
DiA - Dlbenz(a,h)anthracene
B(ghi)P - Benzo(g,h,i)perylene
In P - Indeno(l,2,3-c,d)pyrene
Ph An Flo MeP MeA BeF BeA BaP Pery BaP DiA
PA H
FIGURE 13: PERCENT COMPOSITION OF TOTAL PAH IN TWO MILE CREEK
ARTIFICIAL SUBSTRATES SITES 1, 2, AND 3 (FIG. 12).
FIRST, SECOND, AND THIRD LINES ARE SITES I, 2, AND 3
RESPECTIVELY.
-------
-50-
Fluorene and phenanthrene were not detected in sediments from the mouth
of Two Mile Creek. However, the remainder of the compounds quantified in
the storm sewer sediment were at concentrations within the same order of
magnitude as those occurring in sediments at the mouth of Two Mile Creek.
The PAH contamination identified in the storm sewers may represent
another significant source of PAH to Two Mile Creek. Storm sewers have
been identified as routes of PAH contamination to the aquatic environment
(Herman, 1981).
Comparison of proportions of PAH compound composition among 2 Two
Mile Creek sites and a Buffalo River and Lake Erie sediment sampling
sites which apparently receive their PAH input ultimately from combustive
sources reveal differences in their PAH composition. Two Mile Creek
sediment at Site 3 (Fig. 14, Table 11), which is probably receiving its
PAH contamination from petroleum spills, exhibits a substantial
percentage of pyrene which is 51% of the total PAH at this site.
Perylene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene,
dibenzo(a,h)anthracene, benzo(g,h,i)perylene, and indeno(l,2,3,c,d)pyrene
are at extremely low relative concentrations, or not present at this
location as compared to the Buffalo River and Lake Erie, which have PAH
contamination which is presumably derived from combustive sources.
-------
KEY
20
Percent
of
Total PAH
10
11
Fl
Ph An
Flo
_i_
51
1
J
^>
MeP Py
MeA BaF
BeA
Ch
Fl
Ph
An
Fla
MeP
Py
MeA
Be?
BeA
Ch
EeP
Pery
BbF
BKF
BaP
D1A
B(ghi)P
In
P
1
Fluorene
- Phenanthrene
- Anthracene
- Fluoranthene
Methyl phenanthrene
- Pyrene
- Me anthracene
- Benzof luorene
- Benzanthracene
- Chrysene
Benzo(e)pyrene
- Perylene
- Benzo(b)f luoranthene
- Benzo(K)f luoranthene
Benzo(a)pyrene
- I)lbenz(a,h)anthracene
- Benzo(g,h,l)perylene
Indeno(l,2,
1
BeP Ptry BbF BkF BaP
3-c,d)pyrene
OiA BahIP InP
PAH
FIGURE \k: PERCENT COMPOSITION OF TOTAL PAH COMPOUNDS IN SEDIMENT. THE FOUR LOCATIONS IN EACH
GROUP ARE SMOKE CREEK TRANSECT SITE 8 (FIG. 3), BUFFALO RIVER SITE 6 (FIG. 2), TWO
MILE CREEK SITE I (FIG. 5)f AND Two M|LE CREEK SITE 3 (FIG. 5) RESPECTIVELY.
-------
-52-
COMPARISON OF PAH AMONG SITES
Although localized sources of PAH were identified in this study,
cluster analyses suggested similarities in PAH composition among sites.
The cluster analysis of sediment PAH concentrations (Fig. 11) produced
two major clusters of sampling sites and a single site which appeared to
have PAH composition unrelated to the other sites (Two Mile Creek 3, Fig.
5). Cluster 1 is composed primarily of Buffalo River sites. Cluster 2
has the greatest variety of sampling sites which include Union and
Lackawanna Canals, Smoke Creek mouth transect sites (Lake Erie), Two Mile
Creek sites, Tonawanda Creek, and two Canadian sampling sites ,
Frenchman's Creek, and Black Creek. Cluster 1 had relatively high
percentages of perylene. Benzo(e)pyrene and benzo(a)pyrene relative
concentrations were approximately equal. Within this cluster, three
Buffalo River sites (Sites 3, 4, and 5) appeared to be different in PAH
composition from other Buffalo River sites. Sites 3 and 4 were most
similar to one another. The relative benzo(a)pyrene and benzo(e)pyrene
concentrations were lower than the mean of cluster 1 (Table 9). Buffalo
River Site 5 was not as strongly associated with any other Buffalo River
sites in this cluster. This location had the highest sediment PAH
contamination (Fig. 2). Furthermore, artificial substrate sampling
demonstrated consistently high PAH accumulation in the vicinity of this
site. The variety of sites having similar distributions in cluster 2 may
be indicative of the widespread PAH contamination of water due to
widespread deposition of combustive products of PAH from air into water.
Cluster 2 sites had higher relative proportions of benzo(e)pyrene and
-------
-53-
benzo(a)pyrene and almost twice the proportion of chrysene in cluster 1
sites. These types of PAH compounds are characteristic contaminants
associated with iron and steel manufacturing operations. This type of
industry is associated with some of the sites located in cluster 2. The
Two Mile Creek site 3 appears to have a unique PAH composition based on
the cluster analysis. Extremely high proportions of benzo(e)pyrene were
present in sediment at this location and no perylene was detected in
sediment at this site. Perylene was at the highest concentration of the
five PAH compounds in the other two clusters. This location was the only
site that had high PAH contamination which could be attributed to oil
pollution.
-------
CONCLUSIONS AND RECOMMENDATIONS
-------
-54-
CONCLUSIONS
Artificial substrates were useful tools for identifying areas of PAH
input in the study area. Furthermore, once an area was identified by
these substrates as having PAH contamination, substrates could be used to
further isolate the input area of PAH. It is deemed significant that
areas identified as having PAH contamination by artificial substrates
generally had high PAH concentrations in sediment.
The Buffalo River and the aquatic environment surrounding the
Bethlehem Steel property are grossly contaminated by PAH compounds. A
major input area of PAH in the Buffalo River is in the area of the South
Park Bridge. Discharge sampling identified elevated PAH levels in one
Buffalo Color discharge; however, other sources of PAH may occur in this
area. It is possible that the PAH accumulated by artificial substrates
came from contaminanted sediment leaching PAH into the water column.
Therefore, contaminated sediment cannot be eliminated as a source to the
water column. It is clear from discharge sampling that Bethlehem Steel
is a source of PAH to Smoke Creek. The increase in sediment PAH levels
in Lake Erie from south to north paralleling the Bethlehem Steel property
and the high degree of sediment PAH contamination in the Union and
Lackawanna Canals point to Bethlehem Steel as the source of PAH
contamination in this area.
The PAH contamination of Two Mile Creek is likely to be high because
it is a small body of water with at least two sources of PAH. It is
apparent that the petroleum storage facilities present a continuing PAH
input to this creek. A second input to this drainage appears to be storm
sewers in Two Mile Creek upstream from the area contaminated by petroleum
-------
-55-
spills.
The Buffalo Sewer Authority is a source of PAH to the Niagara River
but the magnitude of PAH input appears to be small. However, in a
facility of this type it is expected that PAH discharges may vary
considerably due to the variety of municipal, commercial, and storm sewer
discharges to the Buffalo Sewer Authority.
Superimposed upon the specific areas of high PAH contamination is a
generalized PAH contamination of the study area.
-------
RECOMMENDATIONS
The sources of PAH in the Buffalo River require further
verification. The Buffalo Color and Allied Chemical discharges should be
resampled to confirm the identified discharge of PAH from the Buffalo
Color outfall and eliminate the other outfalls as sources of PAH. The
major source of PAH to the Buffalo River water may be from previously
contaminated sediments. If ongoing discharges are not the primary PAH
source then a study to identify the impact of transfer to the water
column upon biota should be initiated.
A PAH monitoring program is recommended for the area surrounding
Bethlehem Steel. Operations at this facility have been greatly reduced
and therefore PAH levels should drop. Monitoring should be done to test
this hypothesis.
The oil storage facilities at the upstream area of the intermittent
tributary to Two Mile Creek should better contain their spillage. The
sources of PAH found in the storm sewers discharging to Two Mile Creek
should be identified.
The PAH input to the Niagara River from the Buffalo Sewer Authority
requires further investigation. Water and artificial substrate sampling
were not done at the same time and consequently the concentrations of PAH
in water leading to accumulations in artificial substrates may have been
considerably higher than those that were measured in the water sample.
If PAH concentrations in the Buffalo Sewer Authority discharge are found
to be high upon repetitive sampling then the sources of those inputs to
the Authority should be identified.
-56-
-------
LITERATURE CITED
Basu, D. K. and J. Saxena. 1978. J. Environ. Sci and Technol. 12.
795-798.
?• Baum, E. J. 1978. Polycyclic Aromatic Hydrocarbons and Cancer Vol. 1.
Gelboin and Ts'o Eds. Academic Press, pp. 45-70.
Black, J. J. 1983. Epidermal hyperplasia and neoplasia in brown
bullheads Ictalurus nebulosus in response to repeated application of
PAH contaminated extract of polluted river sediment in Polynuclear
Aromatic Hydrocarbons: Formation Metabolism and Measurements.
Battelle Press, Columbus, pp. 99-111.
Calocerinos and Spina Consulting Engineers 1982. Buffalo River Combined
Sewer Overflow Study. Interim Report on Water Quality. 47 pp.
Dunn, B. P. 1979. In Polynuclear Aromatic Hydrocarbons: Chemistry and
Biological Effects; Biorseth, A., and A. J. Dennis, Eds. Columbus,
p. 367-377.
Eadie, B. J., W. Faust, W. S. Gardner and T. Nalepa. 1982. Chemosph. l}_
(2): 185-191.
Heit, M., Y. Tarn, C. Klusek and J. C. Burke. 1981. Water, Air, and
Soil Pollution J_5, 441-464.
Herbes, S. E., G. R. Southworth, D. L. Schaeffer, W. L. Griest, and M. P.
Moskarinec. 1980. The Scientific Basis of Toxicity Assessment.
H. Witschi Ed. Elsevier/North Holland Biomedical Press.
Herman, R. 1981. Water, Air, and Soil Pollution 16, 445-467.
* Lao, R. C., R. S. Thomas and J. L. Monkman (1975). J. Chromatog. 112:
681-700. in Neff. J. M. 1979. Polycyclic Aromatic Hydrocarbons in
the Aquatic Environment: Sources, Fates, and Biological Effects.
Applied Science Publishers LTD. London. 262 pp.
Laflamme, R. E. and R. A. Kites 1978. Geochimica et Cosmochimica Acta.
42_, 289-303.
Mackay, D. and W. Y. Shiu. 1977. J. Chem. and Engr. Data. 22(4),
399-402.
^Neff, J. M. 1979. Polycyclic Aromatic Hydrocarbons in the Aquatic
Environment: Sources, Fates, and Biological Effects. Applied
Science Publishers Ltd. London. 262 pp.
SAS 1979. SAS Users Guide. Helwig and Council Eds. SAS Institute.
North Carolina. 494 pp.
-57-
-------
-58-
Schimberg, R. W., P. Pfaffli, and A. Tossavainen, 1980. J.
Toxicol. and Environ. Hlth. £, (5-6), 1187-1194.
USEPA. 1980. Ambient Water Quality Criteria for Polynuclear Aromatic
Hydrocarbons. EPA 440/5-80-069.USEPA. 1979. Treatability Manual.
Vol I. Treatability Data.
Wong, J. 1981. Persistent Toxic Substances in Runoff from the City of
Cornwall. 1978 Canada-U.S. Great Lakes Water Quality Agreement
Project No. 1502.
-------
APPENDIX A
-------
-59-
Chromatograms of PAH Screens from Artificial Substrates from Preliminary
Survey. (The region of the chromatogram that reflects the presence of
PAH starts about 1 cm from the left margin and continues to the right.
The peak marked C is a chrysene reference standard. Chromatograms are
presented in order of decreasing rank. Sites correspond to map of
preliminary survey locations on fig. 1)
-------
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-------
APPENDIX B
-------
-67-
PAH Sediment Concentrations for All Sampling Sites (site locations
correspond to sediment sampling sites in text for Buffalo River, Smoke
Creek Transect in Lake Erie, Union and Lackawanna Canals, and Two Mile
Creek)
-------
-68-
TABLE 1. BUFFALO RIVER: SITE 1. BUFFALO RIVER DOWNSTREAM FROM
CONFLUENCE OF NORTH AND SOUTH BRANCHES. PAH SEDIMENT
CONCENTRATIONS
CONCENTRATIONS
COMPOUND WET ng/gm DRY ng/gm ORGANIC ng/mg
FLUORENE ND* ND ND
PHENANTHRENE 380 760 20
ANTHRACENE 100 190 5
FLUORANTHENE 1700 3400 86
MePHENANTHRENE 150 300 7
PYRENE 1000 2000 51
MeANTHRACENE ND ND ND
BENZOFLUORENE 400 800 20
BENZANTHRACENE 300 600 15
CHRYSENE 250 500 13
BENZO(e)PYRENE 940 1800 48
PERYLENE 1300 2500 64
BENZO(b)FLUORANTHENE 470 940 24
BENZO(k)FLUORANTHENE 200 400 10
BENZO(a)PYRENE 320 630 16
DIBENZ(a,h)ANTHRACENE 84 170 4
BENZO(g,h,i)PERYLENE 380 750 19
INDENO(1,2,3-c,d)PYRENE 410 800 21
TOTAL 8400 16500 420
*ND - Not Detected
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-69-
TABLE 1 CONT'D.
SITE 2. BUFFALO RIVER AT DOWNSTREAM BOUNDARY OF MOBIL
TANK FARM. PAH SEDIMENT CONCENTRATIONS
COMPOUND WET ng/gm
FLUORENE 73
PHENANTHRENE 360
ANTHRACENE 73
FLUORANTHENE 1400
MePHENANTHRENE 150
PYRENE 740
MeANTHRACENE 100
BENZOFLUORENE 520
BENZANTHRACENE 270
CHRYSENE 150
BENZO(e)PYRENE 360
PERYLENE 890
BENZO(b)FLUORANTHENE 370
BENZO(k)FLUORANTHENE 170
BENZO(a)PYRENE 290
DIBENZ(a,h)ANTHRACENE 60
BENZO(g,h,i)PERYLENE 270
INDENO(1,2,3-c,d)PYRENE 260
CONCENTRATIONS
DRY ng/gm
170
840
170
3300
350
1700
240
1200
640
360
850
2100
860
400
670
150
640
620
ORGANIC ng/mg
3
14
3
56
6
29
4
21
11
6
14
35
15
7
11
2
11
10
TOTAL
6500
15000
260
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-70-
TABLE 1 CONT'D.
SITE 3. BUFFALO RIVER 200 YDS. UPSTREAM OF SOUTH PARK
BRIDGE. PAH SEDIMENT CONCENTRATIONS.
COMPOUND WET ng/gm
FLUORENE 61
PHENANTHRENE 330
ANTHRACENE 99
FLUORANTHENE 1200
MePHENANTHRENE 160
PYRENE 660
MeANTHRACENE 110
BENZOFLUORENE 600
BENZANTHRACENE 220
CHRYSENE 110
BENZO(e)PYRENE 1300
PERYLENE 2400
BENZO(b)FLUORANTHENE 310
BENZO(k)FLUORANTHENE 150
BENZO(a)PYRENE 220
DIBENZ(a,h)ANTHRACENE 57
BENZO(g,h,i)PERYLENE 340
INDENO(1,2,3-c,d)PYRENE 420
CONCENTRATIONS
DRY ng/gm
130
700
210
2500
350
1400
240
1300
460
240
2800
5100
660
320
470
120
720
890
ORGANIC ng/mg
2
13
3
46
6
26
4
24
8
4
52
95
12
6
9
2
13
17
TOTAL
8700
1900
340
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-71-
TABLE 1 CONT'D. SITE 4. BUFFALO RIVER AT SOUTH PARK BRIDGE. PAH
SEDIMENT CONCENTRATIONS
CONCENTRATIONS
COMPOUND WET ng/gm DRY ng/gm ORGANIC ng/mg
FLUORENE ND* ND ND
PHENANTHRENE 980 2300 43
ANTHRACENE 250 500 11
FLUORANTHENE 1700 4000 76
MePHENANTHRENE 230 520 10
PYRENE 2400 5500 100
MeANTHRACENE 180 400 8
BENZOFLUORENE 1500 3500 66
BENZANTHRACENE 340 790 14
CHRYSENE 150 340 7
BENZO(e)PYRENE 1900 4500 84
PERYLENE 2100 4800 91
BENZO(b)FLUORANTHENE 2400 5500 100
BENZO(k)FLUORANTHENE 290 660 12
BENZO(a)PYRENE 94 220 4
DIBENZ(a,h)ANTHRACENE 61 140 3
BENZO(g.h.i)PERYLENE 92 210 4
INDENO(1,2,3-c,d)PYRENE 880 2000 39
TOTAL 15600 36000 670
*ND - Not Detected
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-72-
TABLE 1. SITE 5. BUFFALO RIVER AT BUFFALO COLOR. PAH SEDIMENT
CONCENTRATIONS
CONCENTRATIONS
COMPOUND WET ng/gm DRY ng/gm ORGANIC ng/mg
FLUORENE 330 640 13
PHENANTHRENE 5000 9600 200
ANTHRACENE 1800 3400 70
FLUORANTHENE 5200 10000 210
MePHENANTHRENE 740 1400 29
PYRENE 11000 22000 450
MeANTHRACENE 520 1000 20
BENZOFLUORENE 4800 9200 190
BENZANTHRACENE 1100 2100 42
CHRYSENE 200 390 7
BENZO(e) PYRENE ND* ND ND
PERYLENE 7100 14000 280
BENZO(b)FLUORANTHENE ND ND ND
BENZO(k)FLUORANTHENE 460 900 18
BENZO(a)PYRENE 990 1900 39
DIBENZ(a,h)ANTHRACENE 3300 6300 130
BENZO(g.h.i)PERYLENE 1100 2100 14
INDENO(1,2,3-c,d)PYRENE 410 800 16
TOTAL 44000 86000 1700
*ND - Not Detected
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-73-
TABLE 1 CONT'D. SITE 6. BUFFALO RIVER 600 YDS. DOWNSTREAM FROM SOUTH
PARK BRIDGE. PAH SEDIMENT CONCENTRATIONS
CONCENTRATIONS
COMPOUND WET ng/gm DRY ng/gm ORGANIC ng/mg
FLUORENE 320 630 20
PHENANTHRENE 1800 3600 100
ANTHRACENE 690 1400 42
FLUORANTHENE 1600 3200 100
MePHENANTHRENE 460 900 28
PYRENE 3600 7100 220
MeANTHRACENE 280 540 17
BENZOFLUORENE 3000 5900 180
BENZANTHRACENE 1300 2600 80
CHRYSENE 890 1800 54
BENZO(e)PYRENE 2100 4200 130
PERYLENE 4000 7900 240
BENZO(b)FLUORANTHENE 1000 2000 62
BENZO(k)FLUORANTHENE 580 1200 36
BENZO(a)PYRENE 1300 2500 79
DIBENZ(a,h)ANTHRACENE 230 450 14
BENZO(g,h,i)PERYLENE 1200 2400 73
INDENO(1,2,3-c,d)PYRENE 840 1700 51
TOTAL 2500 5000 1500
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-74-
TABLE 1 CONT'D.
SITE 7. BUFFALO RIVER 900 YDS. DOWNSTREAM FROM SOUTH
PARK BRIDGE. PAH SEDIMENT CONCENTRATIONS
COMPOUND WET ng/gm
FLUORENE 120
PHENANTHRENE 1300
ANTHRACENE 420
FLUORANTHENE 3400
MePHENANTHRENE 540
PYRENE 2800
MeANTHRACENE 360
BENZOFLUORENE 3500
BENZANTHRACENE 1200
CHRYSENE 940
BENZO(e)PYRENE 2100
PERYLENE 3000
BENZO(b)FLUORANTHENE 1300
BENZO(k)FLUORANTHENE 590
BENZO(a)PYRENE 1200
DIBENZ(a,h)ANTHRACENE 270
BENZO(g,h,i)PERYLENE 1400
INDENO(1,2,3-c,d)PYRENE 880
CONCENTRATIONS
DRY ng/gm
240
2500
800
6400
1000
5300
670
6600
2300
1800
3900
5600
2500
1100
2200
500
2600
1700
ORGANIC ng/mg
6
61
20
160
25
130
17
160
57
44
96
140
62
27
55
12
64
41
TOTAL
25000
48000
1200
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-75-
TABLE 1 CONT'D.
SITE 8. BUFFALO RIVER IMMEDIATELY UPSTREAM FROM TURNING
BASIN. PAH SEDIMENT CONCENTRATIONS
COMPOUND WET ng/gm
FLUORENE 76
PHENANTHRENE 820
ANTHRACENE 400
FLUORANTHENE 2400
MePHENANTHRENE 570
PYRENE 2100
MeANTHRACENE 440
BENZOFLUORENE 3700
BENZANTHRACENE 940
CHRYSENE 740
BENZO(e)PYRENE 2600
PERYLENE 3700
BENZO(b)FLUORANTHENE 930
BENZO(k)FLUORANTHENE 370
BENZO(a)PYRENE 750
DIBENZ(a,h)ANTHRACENE 160
BENZO(g,h,i)PERYLENE 780
INDENO(1,2,3-c,d)PYRENE 160
CONCENTRATIONS
DRY ng/gm
130
1400
700
4100
990
3600
760
6400
1600
1300
4500
6400
1600
640
1300
270
1300
2800
ORGANIC ng/mg
4
44
22
130
31
110
24
200
51
40
140
200
50
20
40
9
42
87
TOTAL
23000
40000
1200
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-76-
TABLE 1 CONT'D.
SITE 9. BUFFALO RIVER AT OHIO ST. BRIDGE.
CONCENTRATIONS
PAH SEDIMENT
COMPOUND WET ng/gm
FLUORENE 140
PHENANTHRENE 900
ANTHRACENE 300
FLUORANTHENE 2400
MePHENANTHRENE 300
PYRENE 1500
MeANTHRACENE 220
BENZOFLUORENE 2200
BENZANTHRACENE 560
CHRYSENE 350
BENZO(e)PYRENE 1900
PERYLENE 2400
BENZO(b)FLUORANTHENE 750
BENZO(k)FLUORANTHENE 300
BENZO(a)PYRENE 560
DIBENZ(a,h)ANTHRACENE 160
BENZO(g,h,i)PERYLENE 780
INDENO(1,2,3-c,d)PYRENE 1100
CONCENTRATIONS
DRY ng/gm
260
1700
560
4400
560
2700
400
4100
100
650
3500
4500
1400
540
1000
290
1400
2000
ORGANIC ng/mg
8
51
17
140
17
84
12
130
32
20
100
140
42
17
32
9
44
63
TOTAL
17000
31000
960
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-77-
TABLE 1 CONT'D.
SITE 10. BUFFALO RIVER AT NAVAL PARK PAH SEDIMENT
CONCENTRATIONS
COMPOUND WET ng/gm
FLUORENE 86
PHENANTHRENE 880
ANTHRACENE 300
FLUORANTHENE 2700
MePHENANTHRENE 320
PYRENE 1800
MeANTHRACENE 110
BENZOFLUORENE 2100
BENZANTHRACENE 650
CHRYSENE 360
BENZO(e)PYRENE 2000
PERYLENE 2500
BENZO(b)FLUORANTHENE 840
BENZO(k)FLUORANTHENE 380
BENZO(a)PYRENE 670
DIBENZ(a,h)ANTHRACENE 150
BENZO(g,h,i)PERYLENE 700
INDENO(1,2,3-c,d)PYRENE 1100
CONCENTRATIONS
DRY ng/gm
170
1700
600
5300
610
3400
220
4000
1200
700
4000
4900
1600
730
1300
280
1400
2100
ORGANIC ng/mg
5
49
17
150
17
97
6
110
36
20
110
140
47
21
37
8
39
60
TOTAL
18000
34000
970
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-78-
TABLE 2. LAKE ERIE: SITE 1. 300 YDS. OFFSHORE - 3 MILES SOUTH OF SMOKE
CREEK MOUTH. PAH SEDIMENT CONCENTRATIONS
COMPOUND WET ng/gm
FLUORENE 39
PHENANTHRENE 280
ANTHRACENE 64
FLUORANTHENE 300
MePHENANTHRENE 45
PYRENE 190
MeANTHRACENE 25
BENZOFLUORENE 130
BENZANTHRACENE 89
CHRYSENE 72
BENZO(e)PYRENE 27
PERYLENE 130
BENZO(b)FLUORANTHENE 67
BENZO(k)FLUORANTHENE 43
BENZO(a)PYRENE 75
DIBENZ(a,h)ANTHRACENE 14
BENZO(g,h,i)PERYLENE 50
INDENO(1,2,3-c,d)PYRENE 51
CONCENTRATIONS
DRY ng/gm
48
340
77
370
55
230
30
150
110
87
33
160
81
52
91
17
60
62
ORGANIC ng/mg
3
21
5
22
3
14
2
9
7
5
2
10
5
3
6
1
4
4
TOTAL
1700
2100
130
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-79-
TABLE 2 CONT'D.
SITE 2. LAKE ERIE 300 YDS. OFFSHORE - 2 MILES SOUTH
OF THE MOUTH OF SMOKE CREEK. PAH SEDIMENT
CONCENTRATIONS
COMPOUND WET ng/gm
FLUORENE 27
PHENANTHRENE 210
ANTHRACENE 38
FLUORANTHENE 440
MePHENANTHRENE 63
PYRENE 270
MeANTHRACENE 13
BENZOFLUORENE 89
BENZANTHRACENE 93
CHRYSENE 38
BENZO(e)PYRENE 45
PERYLENE 200
BENZO(b)FLUORANTHENE 74
BENZO(k)FLUORANTHENE 48
BENZO(a)PYRENE 75
DIBENZ(a,h)ANTHRACENE 14
BENZO(g,h,i)PERYLENE 54
INDENO(1,2,3-c,d)PYRENE 68
CONCENTRATIONS
DRY ng/gm
39
310
55
640
92
390
19
130
130
55
64
280
110
69
110
21
79
98
ORGANIC ng/mg
1
10
2
21
3
13
1
4
4
2
2
9
3
2
4
1
3
3
TOTAL
1900
2700
90
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-80-
TABLE 2 CONT'D.
SITE 3. LAKE ERIE 300 YDS. OFFSHORE - 2 MILES
OF THE MOUTH OF SMOKE CREEK. PAH SEDIMENT
CONCENTRATIONS
SOUTH
COMPOUND WET ng/gm
FLUORENE 16
PHENANTHRENE 120
ANTHRACENE 15
FLUORANTHENE 270
MePHENANTHRENE 42
PYRENE 130
MeANTHRACENE 13
BENZOFLUORENE 78
BENZANTHRACENE 39
CHRYSENE 13
BENZO(e)PYRENE 25
PERYLENE 93
BENZO(b)FLUORANTHENE 38
BENZO(k)FLUORANTHENE 22
BENZO(a)PYRENE 32
DIBENZ(a,h)ANTHRACENE 7
BENZO(g,h,i)PERYLENE 29
INDENO(1,2,3-c,d)PYRENE 32
CONCENTRATIONS
DRY ng/gm
21
160
20
350
55
170
17
100
51
17
33
120
50
29
42
9
38
42
ORGANIC ng/mg
2
14
2
30
5
14
1
9
4
1
3
10
4
2
4
1
3
4
TOTAL
1000
1300
110
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-81-
TABLE 2 CONT'D.
SITE 4. LAKE ERIE 300 YDS. OFFSHORE - 3/4 MILES SOUTH
OF MOUTH OF SMOKE CREEK. PAH SEDIMENT CONCENTRATIONS
COMPOUND
FLUORENE
PHENANTHRENE
ANTHRACENE
FLUORANTHENE
MePHENANTHRENE
PYRENE
MeANTHRACENE
BENZOFLUORENE
BENZANTHRACENE
CHRYSENE
BENZO(e)PYRENE
PERYLENE
BENZO(b)FLUORANTHENE
BENZO(k)FLUORANTHENE
BENZO(a)PYRENE
DIBENZ(a,h)ANTHRACENE
BENZO(g,h,i)PERYLENE
INDENO(1,2,3-c,d)PYRENE
TOTAL
WET ng/gm
68
550
91
920
120
460
35
190
190
ND*
160
300
220
110
130
33
120
140
3800
CONCENTRATIONS
DRY ng/gm
100
850
140
1400
190
710
53
290
290
ND
250
460
340
160
200
51
180
220
5900
ORGANIC rig/rag
3
27
4
44
5
22
2
9
9
ND
8
14
11
5
6
2
6
7
180
*ND - Not Detected
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-82-
TABLE 2 CONT'D. SITE 5. 300 YDS. OFFSHORE - WEST OF MOUTH OF SMOKE
CREEK. PAH SEDIMENT CONCENTRATIONS
CONCENTRATIONS
COMPOUND WET ng/gm DRY ng/gm ORGANIC ng/mg
FLUORENE 200 320 6
PHENANTHRENE 1500 2400 43
ANTHRACENE 330 530 10
FLUORANTHENE 1400 2200 41
MePHENANTHRENE 380 620 11
PYRENE 1400 2300 42
MeANTHRACENE 200 320 6
BENZOFLUORENE 1100 1800 34
BENZANTHRACENE 660 1100 19
CHRYSENE 630 1000 18
BENZO(e)PYRENE 410 660 12
PERYLENE 1600 2600 48
BENZO(b)FLUORANTHENE 600 970 18
BENZO(k)FLUORANTHENE 370 600 11
BENZO(a)PYRENE 740 1190 22
DIBENZ(a,h)ANTHRACENE 150 250 5
BENZO(g,h,i)PERYLENE 560 900 16
INDENO(1,2,3-c,d)PYRENE 610 980 18
TOTAL 13000 21000 380
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-83-
TABLE 2 CONT'D.
SITE 6. 300 YDS. OFFSHORE
OF SMOKE CREEK
-1/2 MILE NORTH OF MOUTH
COMPOUND
FLUORENE
PHENANTHRENE
ANTHRACENE
FLUORANTHENE
MePHENANTHRENE
PYRENE
MeANTHRACENE
BENZOFLUORENE
BENZANTHRACENE
CHRYSENE
BENZO(e)PYRENE
PERYLENE
BENZO(b)FLUORANTHENE
BENZO(k)FLUORANTHENE
BENZO(a)PYRENE
DIBENZ(a,h)ANTHRACENE
BENZO(g,h,i)PERYLENE
INDENO(1,2,3-c,d)PYRENE
WET ng/gm
71
590
89
1000
150
620
71
200
300
870
44
360
380
170
320
39
140
180
CONCENTRATIONS
DRY ng/gm
110
920
140
1600
240
960
110
310
460
1400
68
560
600
270
510
62
210
280
ORGANIC ng/mg
3
21
3
37
5
22
3
7
11
31
2
13
14
6
12
1
5
7
TOTAL
5600
8800
200
-------
-84-
TABLE 2 CONT'D. SITE 7. 300 YDS. OFFSHORE - 1 MILE NORTH OF MOUTH OF
SMOKE CREEK. PAH SEDIMENT CONCENTRATIONS
CONCENTRATIONS
COMPOUND WET ng/gm DRY ng/gm ORGANIC ng/mg
FLUORENE 150 200 10
PHENANTHRENE 990 1300 69
ANTHRACENE 310 420 22
FLUORANTHENE 1000 1400 71
MePHENANTHRENE 220 290 15
PYRENE 880 1200 61
MeANTHRACENE 180 240 13
BENZOFLUORENE 1100 1500 76
BENZANTHRACENE 280 380 20
CHRYSENE 200 270 14
BENZO(e)PYRENE 440 590 31
PERYLENE 420 560 29
BENZO(b)FLUORANTHENE 230 310 16
BENZO(k)FLUORANTHENE 130 180 9
BENZO(a)PYRENE 230 300 16
DIBENZ(a,h)ANTHRACENE 40 53 3
BENZO(g,h,i)PERYLENE 150 200 10
INDENO(1,2,3-c,d)PYRENE 180 240 12
TOTAL 7100 9600 500
-------
-85-
TABLE 2 CONT'D.
SITE 8. 11/2 MILES NORTH OF MOUTH OF SMOKE CREEK
50 YDS. WEST OF POINT CF SOUTH HARBOR ENTRANCE
BREAKWALL. PAH SEDIMENT CONCENTRATION
COMPOUND WET ng/gm
FLUORENE 120
PHENANTHRENE 890
ANTHRACENE 220
FLUORANTHENE 1500
MePHENANTHRENE 210
PYRENE 830
MeANTHRACENE 110
BENZOFLUORENE 820
BENZANTHRACENE 550
CHRYSENE 440
BENZO(e)PYRENE 470
PERYLENE 1100
BENZO(b)FLUORANTHENE 490
BENZO(k)FLUORANTHENE 320
BENZO(a)PYRENE 610
DIBENZ(a,h)ANTHRACENE 97
BENZO(g,h,i)PERYLENE 250
INDENO(1,2,3-c,d)PYRENE 410
CONCENTRATIONS
DRY ng/gm
170
1300
310
2100
300
1200
160
1200
780
630
670
1600
700
460
870
140
360
590
ORGANIC ng/mg
8
56
14
92
13
52
7
52
35
28
30
72
31
20
38
6
16
26
TOTAL
9400
13500
596
-------
-86-
TABLE 3. BETHLEHEM STEEL: SITE 1. 200 YDS. EAST OF ENTRANCE TO UNION
CANAL. PAH SEDIMENT CONCENTRATIONS
COMPOUND
FLUORENE
PHENANTHRENE
ANTHRACENE
FLUORANTHENE
MePHENANTHRENE
PYRENE
MeANTHRACENE
BENZOFLUORENE
BENZANTHRACENE
CHRYSENE
BENZO(e)PYRENE
PERYLENE
BENZO(b)FLUORANTHENE
BENZO(k)FLUORANTHENE
BENZO(a)PYRENE
DIBENZ(a,h)ANTHRACENE
BENZO(g,h,i)PERYLENE
INDENO(1,2,3-c,d)PYRENE
WET ng/gm
2800
12000
4300
18000
2000
11000
1500
7800
3900
2300
2500
7600
2300
1600
3200
710
1800
2600
CONCENTRATIONS
DRY ng/gm
5600
23000
8600
36000
4000
21000
2900
15000
7700
4600
5000
15000
4600
3100
6200
1400
3500
5100
ORGANIC ng/mg
37
160
57
240
27
140
19
100
51
31
33
99
31
21
42
9
23
33
TOTAL
88000
172000
1200
-------
-87-
TABLE 3 CONT'D.
SITE 2. ENTRANCE TO UNION CANAL.
CONCENTRATIONS
PAH SEDIMENT
COMPOUND WET ng/gm
FLUORENE 1500
PHENANTHRENE 7100
ANTHRACENE 3000
FLUORANTHENE 13000
MePHENANTHRENE 1400
PYRENE 6800
MeANTHRACENE 960
BENZOFLUORENE 5100
BENZANTHRACENE 2900
CHRYSENE 2300
BENZO(e)PYRENE 2800
PERYLENE 7900
BENZO(b)FLUORANTHENE 1900
BENZO(k)FLUORANTHENE 1300
BENZO(a)PYRENE 2300
DIBENZ(a,h)ANTHRACENE 530
BENZO(g,h,i)PERYLENE 1400
INDENO(l,2,3-c,d)PYRENE 1600
CONCENTRATIONS
DRY ng/gm
2700
13000
5500
23000
2500
1300
1800
9400
5400
4300
5200
15000
3500
2400
4300
990
2500
3100
ORGANIC ng/mg
20
96
40
170
19
92
13
69
39
32
38
110
26
18
32
7
19
22
TOTAL
64000
110000
860
-------
-88-
TABLE 3 CONT'D. SITE 3. ENTRANCE TO LACKAWANNA CANAL. PAH SEDIMENT
CONCENTRATIONS
CONCENTRATIONS
COMPOUND WET ng/gm DRY ng/gm ORGANIC ng/mg
FLUORENE 1300 1900 26
PHENANTHRENE 5800 8600 120
ANTHRACENE 2200 3200 45
FLUORANTHENE 9400 14000 190
MePHENANTHRENE 930 1400 19
PYRENE 9200 14000 190
MeANTHRACENE 710 1100 15
BENZOFLUORENE 2800 4200 58
BENZANTHRACENE 3100 4500 63
CHRYSENE 3500 5200 72
BENZO(e)PYRENE 1900 2700 38
PERYLENE 3300 4900 69
BENZO(b)FLUORANTHENE 1800 2700 38
BENZO(k)FLUORANTHENE 1100 1600 23
BENZO(a)PYRENE 2700 40000 56
DIBENZ(a,h)ANTHRACENE 450 670 1
BENZO(g,h,i)PERYLENE 2100 3000 42
INDENO(1,2,3-c,d)PYRENE 1300 1900 26
TOTAL 54000 80000 1100
-------
-89-
TABLE 3 CONT'D.
SITE 4. 1/8 MILE NORTH OF ENTRANCE TO LACKAWANNA CANAL.
PAH SEDIENT CONCENTRATIONS
COMPOUND WET ng/gm
FLUORENE 240
PHENANTHRENE 1800
ANTHRACENE 560
FLUORANTHENE 3400
MePHENANTHRENE 320
PYRENE 2100
MeANTHRACENE 180
BENZOFLUORENE 980
BENZANTHRACENE 960
CHRYSENE 650
BENZO(e)PYRENE 750
PERYLENE 1400
BENZO(b)FLUORANTHENE 730
BENZO(k)FLUORANTHENE 500
BENZO(a)PYRENE 850
DIBENZ(a,h)ANTHRACENE 170
BENZO(g,h,i)PERYLENE 590
INDENO(1,2,3-c,d)PYRENE 770
CONCENTRATIONS
DRY ng/gm
400
2900
940
5600
530
3500
290
1600
1600
1100
1200
2400
1200
820
1400
290
980
1300
ORGANIC ng/mg
5
34
11
64
6
40
3
19
18
12
14
27
14
9
16
3
11
15
TOTAL
17000
28000
320
-------
-90-
TABLE 3 CONT'D.
SITE 5. 1/4 MILE NORTH OF ENTRANCE TO LACKAWANNA CANAL.
PAH SEDIMENT CONCENTRATIONS
COMPOUND WET ng/gm
FLUORENE 270
PHENANTHRENE 1800
ANTHRACENE 520
FLUORANTHENE 3400
MePHENANTHRENE 530
PYRENE 2100
MeANTHRACENE 2300
BENZOFLUORENE 1400
BENZANTHRACENE 920
CHRYSENE 720
BENZO(e)PYRENE 150
PERYLENE 1700
BENZO(b)FLUORANTHENE 680
BENZO(k)FLUORANTHENE 490
BENZO(a)PYRENE 840
DIBENZ(a,h)ANTHRACENE 160
BENZO(g,h,i)PERYLENE 500
INDENO(1,2,3-c,d)PYRENE 730
CONCENTRATIONS
DRY ng/gm
570
3900
1100
7200
1100
4400
480
3000
2000
1500
320
3600
1500
1000
1800
350
1100
1600
ORGANIC ng/mg
5
32
9
59
9
36
4
25
16
13
3
29
12
9
15
3
9
13
TOTAL
17000
37000
300
-------
-91-
TABLE 3 CONT'D.
SITE 6: 3/8 MILE NORTH OF ENTRANCE TO LACKAWANNA CANAL.
PAH SEDIMENT CONCENTRATIONS
COMPOUND
FLUORENE
PHENANTHRENE
ANTHRACENE
FLUORANTHENE
MePHENANTHRENE
PYRENE
MeANTHRACENE
BENZOFLUORENE
BENZANTHRACENE
CHRYSENE
BENZO(e)PYRENE
PERYLENE
BENZO(b)FLUORANTHENE
BENZO(k)FLUORANTHENE
BENZO(a)PYRENE
DIBENZ(a,h)ANTHRACENE
BENZO(g,h,i)PERYLENE
INDENO(1,2,3-c,d)PYRENE
WET ng/gm
150
1300
340
2500
250
1400
150
980
720
540
600
1200
590
390
670
140
520
600
CONCENTRATIONS
DRY ng/gm
270
2300
610
4500
450
2500
260
1800
1300
990
1100
2100
1100
700
1200
250
940
1100
ORGANIC ng/mg
3
26
7
51
5
29
3
20
15
11
12
24
12
8
14
3
11
13
TOTAL
13000
23000
270
-------
-92-
TABLE 4.
TWO MILE CREEK:
CONCENTRATIONS
SITE 1. AT RIVER ROAD BRIDGE. PAH SEDIMENT
CONCENTRATIONS
COMPOUND
FLUORENE
PHENANTHRENE
ANTHRACENE
FLUORANTHENE
MePHENANTHRENE
PYRENE
MeANTHRACENE
BENZOFLUORENE
BENZANTHRACENE
CHRYSENE
BENZO(e)PYRENE
PERYLENE
BENZO(b)FLUORANTHENE
BENZO(k)FLUORANTHENE
BENZO(a)PYRENE
DIBENZ(a,h)ANTHRACENE
BENZO(g,h,i)PERYLENE
INDENO(1,2,3-c,d)PYRENE
TOTAL
WET ng/gtn
DRY ng/gm
ND
290
ND
3500
90
590
92
1700
2600
2800
2800
6600
3300
1600
3300
1600
2800
3000
ND
540
ND
6500
170
1100
170
3100
4900
5100
5100
12000
6000
3000
6000
3000
5200
5600
37000
6700
ORGANIC ng/mg
ND
5
ND
66
2
11
2
81
49
51
51
120
61
30
61
30
52
56
730
ND - Not Detected
-------
-93-
TABLE 4 CONT'D.
SITE 2. INTERMITTENT TRIBUTARY TO TWO MILE CREEK 1/4
MILE SOUTHWEST OF TWO MILE CREEK ROAD. PAH SEDIMENT
CONCENTRATIONS
COMPOUND WET ng/gm
FLUORENE 190
PHENANTHRENE 1300
ANTHRACENE 330
FLUORANTHENE 3600
MePHENANTHRENE 1400
PYRENE ND*
MeANTHRACENE 570
BENZOFLUORENE 570
BENZANTHRACENE 360
CHRYSENE 690
BENZO(e)PYRENE 480
PERYLENE 980
BENZO(b)FLUORANTHENE 310
BENZO(k)FLUORANTHENE 160
BENZO(a)PYRENE 300
DIBENZ(a,h)ANTHRACENE 80
BENZO(g,h,i)PERYLENE 410
INDENO(1,2,3-c,d)PYRENE 220
TOTAL 12000
CONCENTRATIONS
DRY ng/gm
350
2400
630
6900
2700
ND
1100
1100
700
1300
910
1900
590
300
590
150
790
430
23000
ORGANIC ng/mg
2
17
4
47
18
ND
7
7
5
9
6
13
4
2
4
1
5
3
150
ND - Not Detected
-------
-94-
TABLE 4 CONT'D.
SITE 3. INTERMITTENT TRIBUTARY TO TWO MILE CREEK 1/2
MILE SOUTHWEST OF TWO MILE CREEK ROAD. PAH SEDIMENT
CONCENTRATIONS
CONCENTRATIONS
COMPOUND
FLUORENE
PHENANTHRENE
ANTHRACENE
FLUORANTHENE
MePHENANTHRENE
PYRENE
MeANTHRACENE
BENZOFLUORENE
BENZANTHRACENE
CHRYSENE
BENZO(e)PYRENE
PERYLENE
BENZO(b)FLUORANTHENE
BENZO(k)FLUORANTHENE
BENZO(a)PYRENE
DIBENZ(a,h)ANTHRACENE
BENZO(g,h,i)PERYLENE
INDENO(1,2,3-c,d)PYRENE
TOTAL
WET ng/gm
DRY ng/gm
1100
5300
1400
2100
2800
62000
3700
16000
1700
43
3700
ND*
540
210
290
99
420
350
2200
11000
2800
43000
5700
130000
7400
33000
3500
88
7600
ND
1100
440
580
200
850
710
120000
250000
ORGANIC ng/mg
13
65
17
260
34
770
45
200
21
1
46
ND
7
3
4
1
5
4
1500
*ND - Not Detected
-------
-95-
TABLE 5. MOUTH OF FRENCHMAN'S CREEK, CANADA. PAH SEDIMENT CONCENTRATIONS
COMPOUND
FLUORENE
PHENANTHRENE
ANTHRACENE
FLUORANTHENE
MePHENANTHRENE
PYRENE
MeANTHRACENE
BENZOFLUORENE
BENZANTHRACENE
CHRYSENE
BENZO(e)PYRENE
PERYLENE
BENZO(b)FLUORANTHENE
BENZO(k)FLUORANTHENE
BENZO(a)PYRENE
DIBENZ(a,h)ANTHRACENE
BENZO(g,h,i)PERYLENE
INDENO(1,2,3-c,d)PYRENE
TOTAL
WET ng/gm
9
110
7
320
34
190
11
66
36
ND*
ND
43
130
26
46
8
31
43
1100
CONCENTRATIONS
DRY ng/gm
13
150
11
430
47
250
16
90
50
ND
ND
60
180
36
63
11
44
59
1500
ORGANIC ng/mg
0.7
7.1
0.5
21
2.3
12
0.8
4.4
2.5
ND
ND
2.9
8.8
1.7
3.1
0.5
2.1
2.9
74
*ND - Not Detected
-------
-96-
TABLE 6. MOUTH OF BLACK CREEK, CANADA. PAH SEDIMENT CONCENTRATIONS
COMPOUND
FLUORENE
PHENANTHRENE
ANTHRACENE
FLUORANTHENE
MePHENANTHRENE
PYRENE
MeANTHRACENE
BENZOFLUORENE
BENZANTHRACENE
CHRYSENE
BENZO(e)PYRENE
PERYLENE
BENZO(b)FLUORANTHENE
BENZO(k)FLUORANTHENE
BENZO(a)PYRENE
DIBENZ(a,h)ANTHRACENE
BENZO(g,h,i)PERYLENE
INDENO(1,2,3-c,d)PYRENE
TOTAL
WET ng/gm
14
40
19
120
20
7
6
40
11
ND*
ND
12
7.3
3.1
11.0
4.0
11.0
ND
330
CONCENTRATIONS
DRY ng/gm
21
60
30
180
29
11
9
60
16
ND
ND
17
11
4.6
17
6
17
ND
490
ORGANIC ng/mg
0.5
1.4
0.7
4.1
0.7
0.3
0.2
1.4
0.4
ND
ND
0.4
0.3
0.1
0.4
0.1
0.4
ND
11
*ND - Not Detected
-------
-97-
TABLE 7. TONAWANDA CREEK 1/4 MILE FROM CONFLUENCE WITH NIAGARA RIVER
PAH SEDIMENT CONCENTRATIONS
CONCENTRATIONS
COMPOUND WET ng/gm DRY ng/gm ORGANIC ng/mg
FLUORENE 57 140 3
PHENANTHRENE 1400 3400 67
ANTHRACENE 260 640 12
FLUORANTHENE 4500 11000 210
MePHENANTHRENE 280 700 14
PYRENE 2700 6700 130
MeANTHRACENE 150 360 7
BENZOFLUORENE 1000 2500 49
BENZANTHRACENE 920 2300 44
CHRYSENE 980 2400 47
BENZO(e)PYRENE 720 1800 34
PERYLENE 2600 6300 120
BENZO(b)FLUORANTHENE 1500 3700 73
BENZO(k)FLUORANTHENE 680 1700 32
BENZO(a)PYRENE 1000 2500 49
DIBENZ(a,h)ANTHRACENE 160 390 8
BENZO(g,h,i)PERYLENE 840 2100 40
INDEND(1,2,3-c,d)PYRENE 890 2200 42
TOTAL 21000 5100 1000
-------
APPENDIX C
-------
-98-
Appendix C
Site Descriptions of Sampling Sites in Text
(Site Descriptions for Figures Not Listed in Appendix Are Included in Text)
Figure 1
Site 1. Smoke Creek
Site 2. Union Canal
Site 3. Lackawanna Canal (mouth)
Site 4. Lackawanna Canal
Site 5. Small Boat Harbor A
Site 6. Small Boat Harbor B
Site 7. Buffalo River A (breakwall)
Site 8. Buffalo River B (Naval Park)
Site 9. Allied Chemical (downstream, left bank)
Site 10. Allied Chemical (downstream, right bank)
Site 11. Republic Steel
Site 12. Buffalo Color
Site 13. Scajaquada A
Site 14. Scajaquada B
Site 15. Buffalo Sewer Authority
Site 16. Sheridan Drive
Site 17. Niagara Mohawk
Site 18. Two Mile Creek A
Site 19. Two Mile Creek B
Site 20. Tonawanda Creek A
Site 21. Tonawanda Creek B
Site 22. Frenchman's Creek A
Site 23. Frenchman's Creek B
Site 24. Black Creek A
Site 25. Black Creek B
Figure 2
Site 1. Buffalo River downstream from confluence of N. and S. branches
Site 2. Buffalo River at downstream boundary of Mobil Tank Farm
Site 3. Buffalo River 200 yds. upstream of South Park Bridge
Site 4. Buffalo River at South Park Bridge
Site 5. Buffalo River at Buffalo Color
Site 6. Buffalo River 600 yds. downstream from South Park Bridge
Site 7. Buffalo River 900 yds. downstream from South Park Bridge
Site 8. Buffalo River immediately upstream from turning basin
Site 9. Buffalo River at Ohio Street Bridge
Site 10. Buffalo River at Naval Park
-------
-99-
Figure 3
Site 1.
Site 2.
Site 3.
Site 4.
Site 5.
Site 6.
Site 7.
Site 8.
Figure 4
Site 1.
Site 2.
Site 3.
Site 4.
Site 5.
Site 6.
Figure 5
Site 1.
Site 2.
300 yds. off shore - 3 miles south of the mouth of Smokes
Creek
300 yds. off shore - 2 miles south of the mouth of Smokes
Creek
300 yds. off shore - 1.5 miles south of the mouth of Smokes
Creek
300 yds. off shore - 3/4 miles south of Smokes Creek
300 yds. off shore - west of mouth of Smokes Creek
300 yds. off shore - 1/2 mile north of mouth of Smokes Creek
300 yds. off shore - 1 mile north of mouth of Smokes Creek
1 1/2 miles north of mouth of Smokes Creek - mouth 50 yds west
of point of South Harbor entrance breakwall
200 yds. east of entrance to Union Canal
Entrance to Union Canal
Entrance to Lackawanna Canal
1/8 mile north of entrance to Lackawanna Canal
1/4 mile north of entrance to Lackawanna Canal
3/8 mile north of entrance to Lackawanna Canal
Two Mile Creek at River Road Bridge
Intermittent Tributary to Two Mile Creek 1/4 Mile Southwest of
Two Mile Creek Road
Site 3. Intermittent Tributary to Two Mile Creek 1/2 Mile Southwest of
Two Mile Creek Road
Figure 6
Site 1. Mouth of Black Creek
Site 2. Mouth of Frenchmans Creek
Site 3. Mouth of Tonawanda Creek
Site 4. Buffalo River at South Park Bridge
Site 5. Buffalo River at Naval Park
Site 6. Buffalo River at Republic Steel
Site 7. Buffalo River at Buffalo Color
Site 8. Lackawanna Canal
Site 9. Union Canal
Site 10. Two Mile Creek
-------
-100-
Figure 7
Site 1. Second bridge This artificial substrate was anchored on the
downstream side of the second bridge on the left (easterly)
fork of the river.
Site 2. Second bridge This artificial substrate was anchored below
the second bridge on the right (westerly) branch of the river.
It was near the right bank (facing upstream) just below what
appears to be a storm sewer drain.
Site 3. Allied Chemical This artificial substrate was located
immediately below the effluents at Allied Chemical.
Site 4. South Park bridge This artificial substrate was approximately
20 yards below the South Park Avenue bridge along the Buffalo
Color plant wall (right bank) approximately 3 to 6 feet from
the shore.
Site 5. South Park bridge This artificial substrate was on the
opposite bank across from site 4.
Site 6. Buffalo Color This artificial substrate was anchored 5 to 10
yards below the effluent baffle about 6 to 10 feet from the
left bank.
Site 7. Republic Steel effluent This artificial substrate was
"swimming" directly in the effluent turbulence of the first
major effluent encountered downstream of the South Park bridge.
This is approximately 150 yards below the old Railroad bridge.
Site 8. River bend This artificial substrate was located along the
left bank (east side) at the bend below Buffalo Color.
Site 9. Republic Steel This artificial substrate was located about 20
yards below the second Republic Steel effluent almost directly
opposite site 11.
Site 10. R.R. bridge This artificial substrate was in midstream just
above the old railroad bridge.
Site 11. Second R.R. bridge This artificial substrate was just
upstream of the R.R. bridge approximately 1 mile from the site
13 bridge. It was located slightly to the west of the main
part of the channel.
-------
-101-
Figure 10
Site 1. Lake Erie This artificial substrate was just on the south
edge of the current from Smoke Creek flowing into Lake Erie
approximately 75 yards from shore.
Site 2. Lake Erie This artificial substrate was on the north edge
of the Smoke Creek current where it flows into Lake Erie
approximately 75 yards offshore.
Site 3. Sewer overflow This artificial substrate was located less
than 10 feet from the sewer opening at Roland and Front
Streets in Lackawanna in the edge of the heavy flows created
when the station operates.
Site 4. Seal Place bridge This artificial substrate was anchored 75
to 100 yards upstream of the bridge at Warsaw Street in
Lackawanna near the shore property of Mr. Ed Buczek.
Site 5. Pedestrian bridge This artificial substrate was anchored
about 50 feet downstream below a metal pedestrian bridge
located at a gravel road that runs behind the Buffalo
Railroad shop off Dona Street in Lackawanna. The artificial
substrate was near the north shore.
Site 6. Route 5 bridge This artificial substrate was located
approximately 6 feet from shore just upstream of the bridge.
Site 1UL Union Lackawanna 1 This artificial substrate was placed
approximately 10 yards from the north side of the canal,
directly opposite an effluent boom that is 40 to 50 yards
inside the canal.
2UL Union Lackawanna 2 There is an effluent grating located
just around the corner from the Union Chip Canal (southerly
direction). The artificial substrate was anchored within 6
feet of the wall and about 25 yards from the grating.
Figure 11
B R 1-10 - Buffalo River
S M 1-8 - Lake Erie Transect across the mouth of Smokes Creek
U L 1-6 - Union and Lackawanna Canals
T M 1-3 - Two Mile Creek 1-3
B L 1 - Black Creek mouth
F R 1 - Niagara River
F R 1 - Frenchman's Creek mouth at Niagara River
Ton - Tonawanda Creek mouth at Niagara River
-------
-102-
Figure 12
Site 1. River Road bridge This artificial substrate was anchored at
the mouth of Two Mile Creek near the River Road bridge.
Site 2. Two Mile Road conduit This artificial substrate was located 30
feet below the effluent pipe and a minor (intermittent)
tributary near Two Mile Road.
Site 3. Veterans Park This artificial substrate was anchored near a
storage facility above major and minor flows.
-------
APPENDIX D
-------
-103-
QUALITY CONTROL MEASURES
1. Solvents; Hydrocarbon solvents were redistilled from technical
grade solvents producing a high quality solvent at low cost. The
quality of the redistilled product from each new 5 gallon batch of
solvent was checked out by evaporating 30 mis of hydrocarbon solvent
into a lOOul volume of DMSO in a conical centrifuge tube. A lOul
aliquot was injected into the HPCL and the elution monitored at
0.016 AUF, 254 nM UV absorbance. This technique provides more than
a 600-fold comparative solvent concentration factor since most real
samples were analyzed at sensitivities of 0.04 AUF to 0.08 AUF, 254
nM. Typical chromatograms demonstrating the improvement in solvent
quality are shown in figures QC 1. and QC 2. Solvent quality
produced by the distillation appeared to be very uniform within each
solvent type regardless of the source or degree of pre-distillation
contamination. Differences in quality between commercially
redistilled solvents and those prepared using the Fisher refluxing
condenser were negligible relative to contamination as visualized by
HPLC/UV detection.
2. Peak resolution: Environmental samples contain certain complex
mixtures of biogenic and anthropogenic chemicals which are difficult
to separate by any chromatographic methods, the combinations of
alcoholic hydrolysis, solvent partitioning, and Florisil
chromatography generally produced fractions which exhibited a
characteristic peak distribution. Although many peaks were only
partly resolved from neighboring components, use of "in series"
-------
-104-
detection by absorbance at 254 nM followed by monochromatic
fluorescence detection (EX 295, EM 405) reduced the degree of
uncertainty associated with measurement of some PAH. Typical
chromatograms illustrating the character of the peak resolution in
analysis of sediment fractions are shown in Figure QC 3. This
figure shows absorbance chromatograms of sediment collected from the
Buffalo Harbor (sediment sample taken at the intersection of a line
from the Lackawanna Bethlehem Steel and Union ship canals near the
Bethlehem Steel Corporation) together with a companion chromatogram
of a spiked sample. Figure QC 4. shows the companion fluorescence
chromatograms produced by analysis of these same two fractions
(spiked and non-spiked).
3. Blanks; Although reagent blanks were not run for every new batch of
solvents (quality checked by the previously described procedure),
periodic reagent blanks using the technical grade redistilled
solvents exhibited very few artificial peaks (Figure QC 5.). At the
sensitivities and sample concentrations used in the present project,
trace amounts of phenanthrene (not exceeding 5.0 ng),
benzo(k)fluoranthene, and benzo(a)pyrene (not exceeding 0.5 ng)
could be found (see tabular data for typical blank results).
4. Replicates; Replicates of three injections each, were run on two
sediment samples (S-16-82) and (S-16-82 dup.). Standard deviation
for each PAH varied within and between samples but most were less
than 10% of the individual PAH concentration (see tabular values).
-------
-105-
5. Duplicates; Three sediment samples were run as paired duplicates.
Although individual PAH values varied in the range of 10% between
samples, overall there was a reasonable agreement between pairs of
duplicates (see tabular values for results of analysis of paired
duplicates).
6. Recovery rates; Recovery rates were calculated for two spiked
sediment samples (also run as duplicates). Recovery rates for one
sample averaged 90 - 100% (S-16-82) and 75 - 85% for the other
sample S-29-82 (see tabular values). Recovery rates were measured
for a water sample processed using a commercial C „ reversed phase
mini-column chromatography cartridge (J.T. Baker; 6ml capacity).
Recoveries of PAH compounds from these cartridges were in the low
range, i.e. 25 - 40% indicating the cartridge trapping technique
will significantly underestimate (by as much as 60 - 80%) the
concentrations/amounts of PAH in aqueous effluent. In this regard,
PAH values for effluent 225 should be compared as this effluent was
analyzed both by the cartridge trapping technique and by
conventional liquid extraction (dichloromethane extraction).
7. Polypropylene substrates; Polypropylene substrates were used as an
integrative indexing procedure for comparing relative amounts of PAH
adsorbed from water over a measured length of time. The technique
does not yield quantitative information in terms of effluent
concentrations, but aspects of the efficiency with which PAH can be
recovered from the substrates, as well as the reproducibility of the
technique, have been studied (see Black, Hart, and Black (1982).
Environ. Sci. Technol. 16: 247-250).
-------
-106-
8. Cleaning and Preparation of ISCO Sampling Devices;
Sampler tubing is cleaned as follows:
a) Wash with non-phosphate detergent in hot water
8. Cleaning and Preparation of ISCO Sampling Devices (continued)
b) Rinse with hot water
c) Remove stainless steel sampling probe from sampling tube
d) One liter of HC1 (one part distilled water; one part
concentrated HC1) is run through tubing
e) A rinse with hot tap water follows (12L)
f) Two liters of distilled water are run through tubing
Prior to collection of sample:
a) ISCO sampler is flushed continuously with water to be
sampled
b) Wastewater is collected in glass bottles
Grab Water Samples:
a) Stainless steel buckets are used (cleaning methods follow)
b) Prior to taking sample, bucket is rinsed 3 times with
sample water source
c) Water samples are taken with glass vials without any
visible air remaining in container
d) A cleaned bucket is used for each sample taken, and clean
buckets are used each day for grab samples
Sediment Samples:
a) Ponar or Eckman dredges are rinsed repeatedly in water at
each sediment sampling site. After a sediment sample is
obtained the dredges are scraped of visible residue and
repeatedly rinsed in water again.
-------
-107-
Cleaning of Sampling Containers for Water Samples:
a) Scrub with steel wool and acetone
b) Rinse with hot water
c) Wash with hot soapy water
d) Rinse with hot water
e) Rinse with distilled water
f) Acetone rinse with reagent grade acetone
Cleaning of Sampling Containers for Water Samples (continued)
g) Rinse with 100 ml of reagent grade ether
h) Rinse aluminum foil with petroleum grade ether and cover
buckets
Plastic bottles:
a) All plastic bottles are soap washed
b) Tap water rinsed
c) Nitric acid washed
d) Rinsed a minimum of 4 times with deionized water
All glass bottles are:
a) Soap washed
b) Tap water rinsed
c) Rinsed with pesticide grade ether
d) Rinsed a minimum of six times with deionized water
-------
-108-
FIGURE QC 1.
TECHNICAL GRADE
PREDISTIUATION
POSTDISTILLAT10N
-------
-109-
FIGURE QC 2.
ISO-OCTOE
PREDISTILLATION
-------
-110-
FIGURE QC 3.
ABSORBANCE CHROMATOGRAM
23 5
78 9 10
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Fluorene
Phenanthrene
Anthracene
Fluoranthene
MePhenanthrene
Pyrene
Me Anthracene
Benzof1uorene
Benzanthracene
Chrysene
Benzo(e)pyrene
Perylene
Benzo(a)pyrene
Dibenz(a,h)anthracene
Benzo(g,h,i)pe'"ylene
peaks associated with
Indeno(l,2,3-c,d)pyrene
-------
FIGURE QC 4.
FLUORESCENCE CHROMATOGRAM
10 Chrysene
11 Benzo(e)pyrene
12 Perylene
13 Benzo(a)pyrene
14 01benz(a,h)anthracene
15 Benzo(g,h,1)pery1ene
peaks associated with
** Benzo(b)fluoranthene
*** Benzo(k)fluoranthene
-------
FIGURE QC 5.
REAGENT BLANKS
A8SORBANCE
FLUORESCENCE
-------
PAH CONCENTRATIONS FOR AQUEOUS EFFLUENT 225 (rig/liter)
Liquid Ex. Dlchloromethane CIR
Sample name
Sample vol (ul)
Sample Inject (ul)
Wet wt (gin)
Dry wt (mg)
Organic wt (mg)
No. of compounds
1 Fluorene
Z Phenanthrene
3 Anthracene
4 Fluoranthene
5 MePhenanth
6 Pyrene
7 Me Anthracene
8 Benzofluor
9 Benzanth
W Chrysene
Henzo(e)pyr
12 Perylene
13 Benzo(b)f1uor
14 Benzo(k)f1uor
15 Benzo(a)pyr
16 D1benz(a,h)anth
17 Benzo(g,h,1)peryl
18 Indeno(l,2,3-c,d)pyr
Effluent 225
340
5
3420
IB
873.200
16,829.600
957.200
' 1.095. 600
6.098,800
3.989.600
834,200
2.230.200
3.712.400
4.202.200
0,635.200
2,085.800
4,510.000
1,471.400
1,498.200
404.200
2,704.400
Effluent 225
500
1.5
1679
18
0
0
0
56.298.004
0
15. 52?. 355
0
0
2.979.840
7,534.930
0
0
1,956.487
972.455
973.054
97.206
1,500.00
0
-------
REAGENT BLANK
ng/gm
VARIATION WITHIN SAMPLES
ng/gm
Sample name
Sample vol (ul)
Sample Inject (ul)
Wet wt (gin)
Dry wt (mg)
Organic wt (mg)
No. of compounds
1 Fluorene
2 Phenanthrene
3 Anthracene
4 Fluoranthene
5 MePhenanth
6 Pyrene
7 MeAnthracene
8 Benzofluor
9 Benzanth
10 Chrysene
11 Benzo(e)pyr
12 Perylene
13 Benzo(b)f1uor
14 Benzo(k)f1uor
15 Benzo(a)pyr
16 01benz(a,h)anth
17 Benzo(g,h,i)pery1
18 Indeno(l,2,3-c,d)pyr
Blank
1000
10
18
0
4.8
0
0
0
0
0
0
0
0
0
0
0
0.33
0.42
0
0
0
S-16-82
1000
2.5
5.0
18
249
1781
598
3499
323
2216
161
913
994
684
683
1483
759
483
872
161
587
734
St. dev.*
29.7
8.62
10.5
88.1
10.5
267.0
25.3
17.4
54.8
79.2
49.5
11.2
15.1
12.0
48.2
11.0
46.2
26.8
S-16-82 d
1000
2.5
5.0
255
1775
531
3214
318
2048
194
1043
916
609
642
1377
697
467
815
159
566
805
plicate
St. dev.*
32.5
47.0
12.4
45.8
39.7
552.0
11.5
14.0
72.8
35.2
22.9
67.1
21.0
37.5
42.6
3 5
34.0
14.6
* Based on 3 replicate Injections of each sample
-------
SEDIMENT DUPLICATES (ng/gm)
Sa.-ole name
Sample vol (ul)
Sample Inject (ul)
Wet Ht (gm)
Dry wt (ing)
Organic wt (mg)
No. of compounds
1 Fluorene
2 Phenanthrene
3 Anthracene
4 Fluoranthene
5 MePhenanth
6 Pyrene
7 MeAnthracene
8 Benzofluor
9 Benzanth
10 Chrysene
11 Benzo(e)pyr
12 Perylene
13 Benzo(b)f1uor
14 Benzo(k)f1uor
15 Benzo(a)pyr
16 Oibenz(a,h)anth
17 Benzo(g,h,1)pery1
18 Indeno(l,2,3-c,d)pyr
S-8-82
1000
10
5
3.250
115.361
18
3.816
28.J24
3.847
45.079
6.065
23.258
2.102
11.349
8.646
0
8.002
13.661
8.389
5.Q4Q
6.141
1.575
5.358
6.837
S-8-82 dup.
1000
10
5
3.248
90,915
18
2.969
26.987
5.244
46.490
5.986 j
22.979
1.364
7.594
10.296
0
8.082
16.145
13.352
gj.549
7.093
1.752
6.434
7.305
S-16-82
1000
2.5
5
3.016
263.417
18
2.904
22.256
7.481
43.745
4.032
27.709
2.008
11.412
12.430
8.550
10.680
18.533
9.494
6.033
10 896
2.015
7.338
9.183
S-16-82 dup.
1000
2.5
5
3.016
263.417
18
3.188
22.191
6.631
^40.169
3.977
25.608
2.422
13.035
11.451
7.610
8.029
17.217
8.768
6.352
10 436
2. 284
7.427
10.063
S-29-82
1000
4.5
10
5.420
177.180
18
5.753
40.381
14.910
111.323
14.350
71.438
9.755
99.112
24.292
17.177
85.420
112.536
33.380
13.003
73 ftffl.
5 B70
?9 959
50.202
S-29-82 dup.
1000
4.5
10
5.420
117.180
18
6.468
40.366
12.387
104.175
12.716
62.502
9.644
101.007
25.964
14.672
' 87.160
107.605
34.080
14.463
25.622
8.584
40.246
49.737
Ul
I
-------
SEDIMENT RECOVERIES (ng/gm)
Sample name
Sample vo1 (ul)
Sample Inject (ul)
Wet wt (gm)
Dry wt (mg)
Organic wt (mg)
No. of compounds
1 Fluorene
2 Phenanthrene
3 Anthracene
4 Fluoranthene
5 MePhenanth
6 Pyrene
7 Me Anthracene
8 Benzofluor
9 Benzanth
10 Chrysene
11 Benzo(e)pyr
12 °erylene
13 Benzo(b)fluor
14 Benzo(k)fluor
15 Benzo(a)pyr
16 D1benz{a,h)anth
17 Benzo(g,h,1)peryl
18 Indeno(l,2,3-c,d)pyr
S- 16-82
1000
2.5
5
3.016
263.417
18
2.904
22.256
7.481
43.745
4.032
27.709
2.008
11.412
12.430
8.550
10.680
18.533
9.494
6.033
10.896
2.015
7.338
9.183
S-16-82 dup.
1000
2.5
5
3.016
263.417
18
3.188
22.191
6.631
40.169
3.977
25.608
2.422
13.035
11.451
7.610
8.028
17.217
8.768
6.352
10.436
2.284
7.327
10.063
S-l6-82sp1ke
1000
2.5
5
3.016
263.417
18
27.621
50.265
33.227
74.412
32.095
54.478
27.877
39.593
36.607
32.288
47.160
43.589
9.723
.746
29.271
26.134
32.450
10.357
^Recovery
90.3
MOO.O
95.2
>100.0
>100.0
>100.0
98.7
>100.0
91.6
94.7
MOO.O
98.2
82.2
MOO.O
MOO.O
S-29-82
1000
4.5
10
5.42
177.18
18
5.753
40.381
14.910
111.323
14.350
71.438
9.755
99.112
24.292
17.177
85.420
112.536
33.380
23.670
5.670
29.959
50.202
5-29-82 dup.
1000
4.5
10
5.42
177.18
18
6.468
40.366
12.387
104.175
12.716
62.502
9.644
101.007
25.964
14.672
87.160
107.605
34.080
MAfii
26.622
8.584
40.246
49.737
S-29-82sp1ke
1000
4.5
10
5.42
177.18
18
27.750
46.864
38.958
91.156
36.477
69.074
33.563
90.661
36.011
35.715
50.161
95.385
18.289
8872
38.858
28.872
46.776
13.637
^Recovery
72.4
60.6
90.6 ,
60.6
82.8
89.9
86.8
74.4
59.6-
81.8
0
70.0
_ ~""^^ —
81.3
85.0
93.3
-------
(ng/Hter) WATER RECOVERIES Ci8 Mini column
Sample name
Sample vol (ul)
Sample Inject (ul )
Wet wt (gm)
Dry wt (mg)
Organic wt (mg)
No. of compounds
1 Fluorene
2 Phenanthrene
3 Anthracene
4 Fluoranthene
5 MePhenanth
6 Pyrene
7 MeAnt'iracene
8 Benzofluor
9 Benzanth
10 Chrysene
11 Benzo(e)pyr
12 Perylene
13 Benzo(b)f1uor
14 Benzo(k)f1uor
15 Benzo(a)pyr
16 01benz(a,h)anth
17 Benzo(g,h,i )peryl
18 Indeno(l,2,3-c,d)pyr
Hoover Cr.
50
28.790
12 640
0.868
1.297
1.084
0.265
1.332
Hoover Cr. D
50
98.084
75.064
48.295
37.892
18.158
17.762
16.786
JD.
% Recovery
14.9
4.8
26.2
24.1
28.0
10.7
11.6
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-905/4-85-002
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Investigation of Polycyclic Aromatic Hydrocarbon
Discharges to Water in the Vicinity of Buffalo
New York
5. REPORT DATE
February 1985
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Edward J. Kuzia and John J. Black
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
New York State Department of Environmental
Conservation
50 Wolf Road
Albany, New York 12233
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
R00556610-01
12. SPONSORING AGENCY NAME AND ADDRESS
U.S.Environmental Protection Agency
Great Lakes National Program Office
Chicago, Illinois 60605
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
Lakes National Program Office
USEPA, Region V
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Eastern Lake Erie and the upper Niagara River basin were sampled for polycyclic
aromatic hydrocarbons (PAH) to assess their distribution and sources. Twenty-
five sites were sampled using polypropylene substrates. Five areas were identified
as having relatively high PAH contamination. These were Lake Erie at the mouth of
Smoke Creek, the Union and Lackawanna Ship Canals, the Buffalo River, Two Mile
Creek, and the Buffalo Sewer Authority. Subsequent sampling and analyses of
sediments, water, and polypropylene substrates confirmed the preliminary findings.
The sources of the PAH were attributed to steel manufacturing operations (Lake
Erie at the mouth of Smoke Creek and Union and Lackawanna Ship Canals) and oil
storage facilities (Two Mile Creek). The Buffalo Sewer Authority was sampled
directly in the outfall, and the analytical results identified it as a source
of PAH to the Niagara River. The Buffalo River had several PAH inputs near the
South Park Bridge. In addition to the areas identified as having high PAH
contamination, there was a generalize PAH contamination throughout the study
area.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b..IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Polycyclic Aromatic
Contaminants
Sediments
Waters
Hydrocarbons
13. DISTRIBUTION STATEMENT
Document is available
to the public through the National
Technical Information Service
Springfield. Virginia 22151
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
144
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
US GOVERNMENT PRINTING OFFICE 1985—555-755/549
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