Tracking Sources of Contaminants in Cayuga Creek on the Niagara Falls Air Reserve Station, Niagara Falls, New York

Transcription

1 Tracking Sources of Contaminants in Cayuga Creek on the Niagara Falls Air Reserve Station, Niagara Falls, New York September 007 Project Number MIPR F5J3AA513G00 i

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3 Tracking Sources of Contaminants in Cayuga Creek on the Niagara Falls Air Reserve Station, Niagara Falls, New York Prepared for: U.S. Air Force th Niagara Falls Air Reserve Station 914 Support Group/CEV 405 Franklin Drive Niagara Falls, NY Prepared by: Timothy L. Preddice New York State Department of Environmental Conservation Division of Fish, Wildlife and Marine Resources Bureau of Habitat Hale Creek Field Station 18 Steele Avenue Extension Gloversville, NY 1078 and Elizabeth Trometer U.S. Department of Interior, Fish and Wildlife Service Lower Great Lakes Fishery Resources Office 405 North French Road, Suite 10A Amherst, New York 148 Project Number MIPR F5J3AA513G00 September 007 iii

4 TABLE OF CONTENTS PAGE LIST OF TABLES... vi List of FIGURES... vii INTRODUCTION...1 Description of Area...1 METHODS.... Study Area... Sampling....3 Chemical Analysis...4 Quality Control....4 Data Handling....4 Protective Wildlife Criteria...4 RESULTS....5 Rainfall and Water Quality Parameters...5 PISCES....5 Young-of Year Fish Composites...6 Length and Weight Data For Y-O-Y Fish Composites QA/AC Results....7 DISCUSSION...8 Cayuga Creek Fish Data...8 Bergholtz Creek Fish Data...9 PISCES Data...9 Source Track-down versus 005 Fish Contaminants and Protective Criteria SUMMARY...11 ACKNOWLEDGMENTS...1 LITERATURE CITED APPENDIX...6 Appendix A - Summary of Analytical Methods for PISCES Appendix B - Summary of Analytical Methods for Y-o-Y Fish Appendix C - Summary of Laboratory Quality Control Results for PISCES Appendix D - Summary of Laboratory Quality Control Results for Fish Tissue Associated with PISCES iv

5 LIST of TABLES PAGE Table 1. Description of 005 Cayuga Creek PISCES sampling locations, Niagara Falls, NY Table. Physical parameters at each PISCES sampling location during sampler deployment and retrieval, Cayuga Creek, Niagara Co., Sept Table 3. PISCES contaminant data (nanograms) for Hassett-style samplers deployed in Cayuga Creek, Niagara Falls, NY, Sept Table 4. PCB Aroclor and organochlorine pesticide residue data (ppb wet weight) for young-of-year fish composites (15 fish/ composite) collected from Cayuga Creek and Bergholtz Creek in the vicinity of the Niagara Falls Air Reserve Station and the Niagara Falls International Airport, Niagara Co., NY, Sept Table 5. PCB Aroclor and organochlorine pesticide residue data (ppb lipid-adjusted) for young-of-year fish composites (15 fish/ composite) collected from Cayuga Creek and Bergholtz Creek in the vicinity of the Niagara Falls Air Reserve Station and the Niagara Falls International Airport, Niagara Co., NY, Sept Table 6. Length and weight measurements for young-of-year fish composites (15 fish per composite) collected in conjunction with PISCES contaminant track-down studies for Cayuga Creek, vicinity of Niagara Falls Air Force Reserve Station and Niagara Falls International Airport, Sept Table 7. Total PCB and mirex concentrations (ppb wet weight) in 005 young of-year fish composites from Cayuga Creek that exceed fish flesh criteria to protect sensitive piscivorus wildlife and waterfowl Table 8. Comparison of 1997 and 005 PCB Aroclors, DDE, DDD and mirex concentrations (ppb lipid) in young-of -year fish collected from Cayuga Creek at Porter Road, Niagara Falls, NY... Table 9. Comparison of 1997 and 005 PCB Aroclors and organochlorine pesticide residue data (ppb lipid adjusted) for young-of-year bluntnose minnow composites (15 fish/composite) collected from Bergholtz Creek, Niagara Co v

6 LIST OF FIGURES PAGE Figure 1. Cayuga Creek PISCES sampling locations and outfalls on the Niagara Falls Air Reserve Station, Niagara Falls, New York, Figure. Daily precipitation recorded at the Niagara Falls International Airport, Sept. 005 (National Weather Service)... 5 Figure 3. AR14 PISCES uptake rates vi

7 Tacking Sources of Contaminants to Cayuga Creek on the Niagara Falls Air Reserve Station, Niagara Falls, New York INTRODUCTION This document reports results for a 005 contaminant track-down study conducted in upper Cayuga Creek, Niagara County, New York. The study, which used passive in-situ concentration extraction samplers (PISCES), was prompted primarily by the discovery of elevated total PCB and mirex in composites of young fish collected in 1997 downstream from the Niagara Falls Air Reserve Station (NFARS) and the Niagara Falls International Airport (Preddice et al., 00). Two other pertinent studies investigated storm water discharges to Cayuga Creek on the air base but neither specifically monitored PCB or organochlorine (OC) pesticides. NFARS (003) found potential water quality impacts from air base outfall #1, # and #3, and demonstrated outfall #6 to have potential for contamination even with best management practices in place. The other study did not find outfall #6 to have affected the benthic macroinvertebrate community structure (Trometer, 005). In addition to PISCES, this document also reports analytical results for 005 young-ofyear (y-o-y) fish composites collected upstream and downstream from air base property following retrieval of the PISCES samplers. These collections allow comparison of contaminant levels in young fish from the two locations and help to denote changes in concentrations at the downstream site last sampled in Young fish were not sampled at other PISCES sites primarily because of limited analytical resources, although sampling difficulties at some sites and the inability to collect enough fish, particularly of the same species, at these sites also played a part in this decision. In drought years fish could not be found at the upstream Lockport Road site and upstream, and at that time, were likely limited on the air base as well. Pollutants in young fish reflect localized contaminant issues and together with PISCES data, result in a more thorough track-down study. Description of Area - Cayuga Creek and its tributaries are the primary waterways on the air base property and, as with most airports, there are large areas of pavement and, consequently, several storm water discharges. NFARS (003) reports potential contamination from historic and current landfill leachates located in outfall #1 drainage, spilled aircraft fuel in outfall # drainage, runoff from a fire training area located adjacent to outfall #4 and the creek, runoff from runways, and non-point agricultural and municipal runoff from upstream. Outfall #5 receives runoff from Lockport Road and a quarry located north of the air base (Trometer, 005). Outfall #6, despite recent best management treatment, is a particular concern because it is near aircraft deicing operations that use a glycol formulation. Outfall #7 is discharged to an open ditch that drains the southwestern section of NFARS and the surrounding area (Trometer, 005). Cayuga Creek also has potential to receive surface and ground water contamination from offsite -1-

8 industrial property (Carborundum Co.) via a small tributary that flows through Niagara Falls International Airport and merges with Cayuga Creek (outfall #8). In 003, the water quality monitoring in Cayuga Creek at NFARB included in-situ and outfall #6 water sampling for: glycol, Chemical Oxygen Demand (COD), Biological Oxygen Demand (BOD), oil and grease, total suspended solids, total Kjeldahl nitrogen, total phosphorus, nitrates, volatile organic compounds (acetone, benzene, -butanone, carbon disulfide, carbon tetrachloride, chloroform, chloromethane; 1,1-dichloroethene; cis-1,-dichloroethene; trans-1,- dichloroethene; 1,-dichloropropane; ethylbenzene, 4-methyl,-pentane, methylene chloride, toluene, trichloroethene, vinyl chloride, total xylene, and metals (antimony, arsenic, beryllium, cadmium, chromium, copper, lead, mercury, nickel, selenium, silver, thallium and zinc). High glycol, BOD and COD have been periodically measured at outfall #6 (NFARS, 003). PCB and OC pesticide residues in air base surface water samples have been less than New York State Department Environmental Conservation (NYSDEC) surface water quality standards and are, therefore, not currently monitored by NFARS (NYSDEC, 006). In 003, the water quality of Cayuga Creek was assessed through analysis of the benthic macroinvertebrate community located upstream and downstream of NFARS outfalls (Trometer, 005). Macroinvertebrate community analysis is a widely used technique to assess the effects of discharges, determine the need for further testing, and to document success story water quality improvements (Bode et al., 00). The results of this analysis found water quality moderately to severely impacted at all locations. Organic pollution impacted the upstream macroinvertebrate community whereas downstream the community was affected by organic pollution and toxic conditions from municipal/industrial discharges. This biological assessment was unable to identify specific contaminants or their exact source. METHODS Study Area - PISCES sites #1 - #7 were located in Cayuga Creek downstream of storm water outfalls on the air base property. PISCES site #8 in Cayuga Creek receives outfall #8 and drainage from the Carborundum plant and the Niagara Falls International airport properties. Insufficient water depth prevented deployment of samplers closer to outfall #7 and outfall #8. Two additional PISCES sites (#9 and #10) were sampled at previously established y-o-y fish sampling sites at Lockport and Porter Roads located upstream and downstream from air base property, respectively (Table 1 and Figure 1). In 005, young fish were once again sampled at both locations. As an aside, because we were one composite short of meeting our Cayuga Creek fish quota, one composite of y-o-y fish was collected from nearby Bergholtz Creek. This creek was also sampled in 1997 but at a slightly different location. In 005, we were unable to collect sufficient numbers of y-o-y fish at the traditional Williams Road crossing so we moved upstream just above the Walmore Road crossing and the Bell Aerospace Textron effluent until sufficient numbers were found for a composite. --

9 Sampling - Hassett-style PISCES samplers were prepared for field sampling following NYSDEC protocol (Preddice, 007). PISCES, which concentrate contaminants such as PCB and OC pesticides from the water column, were chosen for track-down purposes because they are stationary, easy to deploy and retrieve, and because low levels of these contaminants are concentrated in the sampler s solvent which later requires only minor cleanup and evaporation prior to chemical analysis. Another advantage to PISCES is that the membrane stays relatively clean during deployment and does not bio-foul as does the membrane with some other types of semi-permeable membrane devices (SPMDs). Two PISCES were deployed at each of the ten sites for about two weeks beginning on September 14 and 15, 005. At deployment, each sampler was filled with 00 ml of pesticide-- grade hexane and, for quality control purposes, was spiked with 50 ul of solution containing a nominal 10 ng of trans-chlordane. [Note: Where more than one round of track-down sampling is anticipated, it is routine to deploy only two PISCES per site during the initial exposure to conserve analytical resources. Pesticide-grade or Ultra Pure analytical-grade solvent is used in PISCES because it is free of contaminants. The trans-chlordane was added as an analytical surrogate to determine percent recoveries for quality control purposes.] PISCES were tied directly to a concrete half-block anchor and placed in moderately flowing, wadeable water at least 30 cm deep. Samplers were inspected during the exposure period to ensure that PISCES remained submerged. At retrieval, PISCES samples were poured into 50 ml, clean, amber glass jars and placed on ice in a cooler. These were transferred to a secure walk-in cooler (~ 4 C) at the NYSDEC s Hale Creek Field Station (HCFS) pending processing and chemical analysis for PCB Aroclors and OC pesticides. During PISCES deployment and retrieval, United States Fish and Wildlife Service (USFWS) staff recorded parameters such as depth, current, canopy, substrate type, water temperature, conductivity, dissolved oxygen, and ph. At the end of the PISCES exposure on September 8 and 9, 005, y-o-y fish were collected with a 3/16-inch (~5 mm) mesh minnow seine following methodology described in previous NYSDEC Great Lakes Basin y-o-y fish contaminant reports (Preddice et al., 006; Preddice et al., 00; Preddice et al., 1998; Skinner et al., 1994; Skinner, 1993; and Skinner and Jackling, 1989). Up to five composites of y-o-y fish of one species were collected from upstream PISCES site #9 at Lockport Road and from downstream PISCES site #10 at Porter Road (Table 1 and Figure 1). Fish were identified to species and total length (TL) was measured to the nearest millimeter. Each 15-fish composite was weighed to the nearest 0.1 gram, wrapped in hexanerinsed aluminum foil, placed in a one-quart plastic bag and frozen in a cooler with dry ice. Fish samples were transferred to a walk-in freezer (~ -0 C) at NYSDEC s HCFS pending PCB Aroclors and OC pesticides analysis. Fish composites from the Porter Road site were last sampled in 1997 for PCB and OC pesticides (Preddice et al, 00). Young fish from Lockport Road were last sampled in 199 when only dioxins and furans were the focus of chemical monitoring (Skinner, 1993). -3-

10 Chemical Analyses - Filtered and concentrated PISCES samples and lipid extracts from homogenized whole fish composites were analyzed by gas chromatography for analytes: Aroclor (AR)14; AR154/60; 4,4'-DDE; 4,4'-DDD; 4,4'-DDT;,4'-DDE;,4'-DDD;,4'DDT; HCB; heptachlor; heptachlor epoxide; trans-chlordane; cis-chlordane; trans-nonachlor; cis-nonachlor; oxychlordane; aldrin; mirex; photomirex; alpha-hch; beta-hch and gamma- HCH. [Note: For biological tissue such as fish to be analyzed for PCB and OC pesticides it is standard protocol to analyze lipid extracts because it is the lipid fraction of the fat where these substances concentrate. The lipid in fish essentially serves as the solvent used to fill PISCES.] Method detection limits for PISCES samples were 10 ppb for AR14; 30 ppb for AR154/160; ppb for DDE, DDD, DDT, mirex, and HCB; and 5 ppb for the remaining OC pesticide analytes. With the exception of 0 ppb for AR14, method detection limits were the same for y-o-y fish samples. PISCES and y-o-y fish samples were processed and analyzed using standard methods adopted by NYSDEC s Analytical Services Unit (ASU) at HCFS (Appendices A and B). Quality Control - At deployment, each PISCES was spiked with 50 ul of solution containing a nominal 10 ng of trans-chlordane. Percent recovery of the surrogate spike solution was determined for each sample as a measure of potential sample lost during the -week exposure or during analytical procedures. For the same reason, at the laboratory, the volume (± ml) of the hexane sample retrieved and any water in the samples was measured. Generally, samples that loose greater than 5-35 % of the solvent or greater than 50 % of the spiking material are discarded. Matrix spikes, internal spikes and blanks for this project were analyzed by the ASU in conjunction with similar samples from other studies. Acceptable control limits for accuracy, determined from mean percent recoveries of matrix or internal spikes, were between 50 and 150 percent. Acceptable precision was established at greater than 50 % relative standard deviation (RSD) of replicate analysis of matrix or internal spikes (USEPA, 1995). Data Handling - PISCES data (amounts and site means with standard deviations) are presented for each sample. Since exposure periods varied slightly among sites, PISCES uptake rates were calculated to facilitate comparison based on the formula: nanograms/45.6 cm / # days exposure. Membrane surface area for the PISCES used is 45.6 cm. Protective Wildlife Criteria - It is common knowledge that persistent contaminants can bioaccumulate in fish, even in the very young stages collected for this study. Although young-ofyear fish are not generally consumed by humans, they are sometimes eaten by several species of opportunistic wildlife and waterfowl including mink, gulls, terns, mergansers and loons. As a result, contaminant criteria for fish flesh were developed to protect piscivorus wildlife species (Newell et al., 1987; IJC, 1988). Table 7 presents the total PCB and mirex criteria at the top of the respective column. Analyte concentrations in y-o-y fish from Cayuga and Bergholtz Creeks were compared to these protective criteria to show locations with contaminant levels that exceed these criteria. Statistical tests to determine significant difference between residue concentrations in upstream and downstream fish composites, and between years were not performed due to the limited number of samples. -4-

11 RESULTS Rainfall and Water Quality Parameters - During this PISCES exposure from September 14 to 9, 005, four significant (greater than 0.4 inches) rainfall events occurred (September 16, 5, 6 and 9) in the Cayuga Creek watershed which provided good conditions for this kind of study (Figure ). Rainfall resulted in a 0.11 m increase in mean depth, an increase in current velocity from 0.06 m/s to 0.1 m/s and a significant decrease in mean specific conductivity from 1636 ìmhos to 993 ìmhos. Rainfall slightly increased mean creek width, o reduced water temperature by 4 C, and slightly reduced dissolved oxygen and ph (Table ). Of note, during sampler deployment specific conductivity at PISCES # 5 doubled that for upstream sites and was also notably greater than upstream at sample retrieval (Table ). This increase likely indicates the influence of a discharge or another source of water with different chemistry. PISCES - For this study, 0 PISCES samples (two samples per site) were collected and analyzed. PISCES sampler 60 (sample 05) from site #7 was covered with much floating vegetation and debris that caught on the anchor rope. This extraneous material hampered uptake of contaminants and results were excluded from the data set. For this contaminant track-down study, four analytes were detected in PISCES samples: AR14; 4,4'-DDD; 4,4'-DDE and HCB. Contaminant amounts, site means and mean uptake rates for PISCES sites are presented in Table 3. AR14 - AR14 was detected in all PISCES samples and mean amounts for the ten PISCES sites ranged from 1.1 (± 1.8 ng) at site #4 located in the middle of the air base to 71.7 (± 19.1 ng) at the most downstream site (#10) at Porter Road below NFARS (Table 3). Mean AR14 amounts were similar ( ng) for upstream air base sites #1, #, and #3, and for the most upstream site (#9) at Lockport Road above NFARS. Mean amount of AR14 in PISCES from the upper middle of the air base (sites #4 and #5) were about one-half those upstream, and then tripled at site #6 located mid-base. Further downstream at site #8 (below outfall#8 and tributary from the Carborundum site) the mean amount of AR14 basically remained unchanged from that at site #6 (Table 3 and Figure 1). The mean amount of AR14 in PISCES at Cayuga Creek site #7 (only one sampler) located at the southwest boarder of NFARS and at site #10 below air base property at Porter Road was 4 to 4.5 times greater than that at site #5. The lowest (0.0 ng/cm /day) mean uptake rate was at sites #4 and #5, and the highest (0.11 ng/cm /day) was at the most downstream site (#10) at Porter Road. The mean AR14 uptake rates for downstream sites #10 and #7 were practically the same, 0.11 and 0.10 ng/cm /day, which indicated that PCB contamination was similar at these two sites located only 900-1,000 feet apart. 4,4'-DDD - This DDT metabolite was detected in both PISCES samples from sites # 5, #6 and #10, and in one sample from sites #4, #7 and #8 (Table 3). It was not detected in samples from upstream sites #1, #, #3 and #9. The lowest mean of.3 (± 3.3 ng) was at site #4 and the highest mean of 16.5 (± 5.8 ng) was at the most downstream site #10 at Porter Road. Mean uptake rates ranged from ng/cm /day at site #4 to 0.03 ng/cm /day at site #10 (Table 3). -5-

12 4,4'-DDE - This primary metabolite of the insecticide DDT was detected (4.0 and 5.8, mean = 4.9 ng) in only two PISCES samples from downstream site #10 at Porter Road. These low amounts equate to a mean uptake rate of only ng/cm /day (Table 3). HCB - Only 8.8 ng was detected in one PISCES sample from downstream site #10 resulting in a low mean uptake rate of ng/cm /day (Table 3). Young-of-Year Fish - Five y-o-y creek chub composites from upstream PISCES site #9 at Lockport Road and four y-o-y fish (1- creek chub, 3- common shiner) composites from downstream PISCES site #10 at Porter Road were collected. One additional bluntnose minnow composite was collected from nearby Bergholtz Creek at Walmore Road. This site was used because high flow and fast current prevented finding sufficient numbers of y-o-y fish at the traditional Williams Road site. Analytical results show that y-o-y fish from the upstream and downstream Cayuga Creek sites contained AR14; AR154/160; 4,4'-DDD and 4,4'-DDE (Table 4). In addition, all fish composites from the downstream site at Porter Road contained mirex. The list of analytes for Cayuga Creek fish differed from that for PISCES samples with the detection of AR154/160 and mirex, and the absence of trace amounts of HCB (Tables 3 and 4). The analyte list for Bergholtz Creek fish was similar to that for Porter Road fish except for the presence of 4,4'-DDT and the absence of mirex (Table 4). AR14 - This relatively light PCB Aroclor was found in each Cayuga Creek y-o-y fish composite at levels that ranged from 13-0 ppb, mean = 15.8 (± 3. ppb) upstream at Lockport Road and from 3-50 ppb, mean = 36 (± 11.1 ppb) downstream at Porter Road (Table 4). Respective, lipid adjusted ranges were ppb, mean = 543 (± 155 ppb) and 1,1 -,36 ppb, mean = 1,837 (± 514 ppb) (Table 5). The lipid adjusted mean AR14 level for downstream Porter Road fish was 3.4 times greater than the mean level for composites from upstream site # 9 at Lockport Road. The AR14 level in the Bergholtz Creek fish composite was 57 ppb which is about 16 times greater than for fish from Cayuga Creek at Porter Road. On a lipid basis the mean for Bergholtz Creek fish is nearly four times greater, 1,837 ppb vs 7,099 ppb (Table 5). AR154/160 - This relatively heavy PCB Aroclor was detected in two of five upstream fish composites from Lockport Road and in all four downstream Porter Road composites (Table 4). It was also present in the fish composite from Bergholtz Creek (Table 4). Wet weight data show 30 and 39 ppb (99 and 1,3 ppb lipid) in the two composites from upstream at Lockport Road and greater levels ranging from ppb, mean = 17 (± 13. ppb) downstream at Porter Road. On a lipid basis, downstream values at Porter Road ranged from 5,91-7,68 ppb, mean = 6,475 (± 579 ppb). The lipid adjusted mean AR154/ 160 value downstream of 6,475 ppb was about 15 times greater than the mean of 430 ppb for upstream fish. The lipid adjusted AR154/160 level in Bergholtz Creek fish was 19,86 ppb, a level about three times greater than the mean for fish from Cayuga Creek at Porter Road (Table 5). Again, this heavy PCB Aroclor was not detected in any PISCES sample. -6-

13 4,4'- DDD - Low levels of this DDT metabolite, which were detected in all Cayuga Creek y-o-y fish composites, ranged from ppb, mean =.7 (± 0.3 ppb) upstream at Lockport Road and from ppb, mean = 6.9 (± 0.9 ppb) downstream at Porter Road (Table 4). Lipid adjusted means were 90.3 ppb (± 6.1 ppb) upstream and 348 ppb (± ppb) downstream (Table 5). The mean lipid adjusted DDD level in Bergholtz Creek fish was comparable to that for upstream Cayuga Creek fish from Lockport Road and was about onequarter that of downstream Cayuga Creek fish from Porter Road (Table 5). 4,4'-DDE - This primary metabolite of the insecticide DDT was found in all upstream and downstream Cayuga Creek y-o-y fish composites (Table 4). The mean levels for upstream and downstream sites were practically the same, 0.0 (±1.4 ppb) and 19.5 (±5.3 ppb), respectively. On a lipid basis, means were 676 (± 41.1 ppb) and 989 (± 00 ppb) with the greater level downstream at Porter Road (Table 5). The lipid adjusted DDE level in Bergholtz Creek fish was 403 ppb, a value less than one-half that of downstream Cayuga Creek fish from Porter Road (Table 5). 4,4'-DDT - DDT was detected at 11.4 ppb (315 ppb lipid) only in the single Bergholtz Creek fish composite (Tables 4 and 5). Mirex - Mirex was detected in each of the four y-o-y fish composites only from Porter Road (Table 4). Wet weight levels ranged from ppb, mean = 46.9 (± 10.9 ppb). On a lipid basis these values are,066 -,849 ppb, mean =,375 (± 380 ppb) (Table 5). These levels are higher than anticipated and are a concern. Length and Weight Data for Y-O-Y Fish Composites - Creek chub composites from the upstream Cayuga Creek site at Lockport Road weighed g, mean = 6.7 g and total lengths (TL) ranged from 7-47 mm, mean = 37 mm (Table 6). Downstream at Porter Road, three common shiner and one creek chub composite were collected. The creek chub composite was comprised of fish that were considerably larger (15. 9 g, mean TL = 5 mm) than upstream creek chub. These fish may have been 1+ age class minnows rather than young-of-year. Contaminant levels for this creek chub composite were comparable to levels for the three y-o-y common shiner composites from this site which may indicate no age-contaminant level relationships exists for small fish. Composite weights for the common shiner composites from Porter Road were 9.7, 15.4 and 15.5 g and mean total lengths were 44, 49 and 5 mm, respectively. The bluntnose minnows from Bergholtz Creek were comparable in size (9-45 mm, mean = 37 mm TL) to the upstream creek chubs from Lockport Road. QA/QC Results - With the exception of photomirex, mean percent recoveries, measures of accuracy, for each PCB Aroclor and OC analyte in the matrix and internal spikes were within the allowed 50 to 150 % control limits. Photomirex mean recovery was 49 %, only 1 % below the minimum 50 % acceptable recovery criteria. RSDs among replicate matrix spikes and internal spikes, measures of precision, were all acceptable and less than the allowed 50 % maximum. The highest RSD of 34.3 % was for gamma hexachlorocyclohexane (gamma HCH). The five method blanks analyzed for each Aroclor and OC analyte showed no contamination -7-

14 since all levels were less than respective detection limits. Table 3 shows that the amounts of trans-chlordane spike recovered from PISCES samples ranged from 6.3 to 1. g, mean = 8. ng. This range is acceptable because amounts were within 5 ng (50 %) of the original 10 ng spike. Appendix C provides a summary of PISCES quality control results and Appendix D provides a summary of y-o-y fish quality control results. DISCUSSION Weather conditions during this 005 study were good for tracking contaminants with PISCES. Most importantly, rainfall during the two-week exposure period was sufficient to keep the samplers submerged and to flush contaminants into surface waters. Cayuga Creek Fish Data - A comparison of 005 Cayuga Creek data for y-o-y fish, which were collected only downstream at Porter Road and upstream at Lockport Road shows that AR14, AR154/160, 4,4'-DDE and 4,4'-DDD were detected upstream and downstream from NFARS (Tables 4 and 5). The mean wet weight concentration of these analytes was 1.5 to 15 times greater at Porter Road. Additionally, mirex was detected in all four composites from Porter Road but not in any of the five composite from upstream at Lockport Road (Table 4). Table 7 shows that total PCB ( ppb) and mirex ( ppb) levels in the 005 Porter Road fish composites exceed the 110 ppb total PCB criterion and the less than detection criterion for mirex, both established to protective sensitive piscivorus wildlife (Newell, et al., 1987; IJC, 1988). Mirex levels were higher than anticipated and are a concern. DDT metabolite totals for upstream and downstream sites were less than the 00 ppb dietary cancer risk criterion for mink (Newell et al., 1987), and were much lower than the 1,000 ppb level in whole fish designed to protect piscivorus birds (IJC, 1988). Bergholtz Creek Fish Data - The 005 Bergholtz Creek fish contained AR14, AR154/160, DDE, DDD and DDT but no mirex which was found in all Cayuga Creek fish composites from Porter Road (Table 4). Lipid adjusted concentrations of the PCB Aroclors were 3-4 times greater than levels for Porter Road fish (Table 5). The total PCB value for the Bergholtz Creek y-o-y fish composite was found to exceed the protective wildlife criterion nearly nine times (Table 7). The DDT metabolite totals (DDD + DDE + DDT) for all y-o-y fish composites from both creeks were less than the 00 ppb dietary cancer risk criterion for mink (Newell et al., 1987), and were much lower than the 1,000 ppb level in whole fish designed to protect piscivorus birds (IJC, 1988). The greater total PCB level, the presence of DDT, and the lack of mirex suggests that the Bergholtz Creek fish are affected by a different contaminant source. PISCES Data - Analyses of Cayuga Creek PISCES samples detected AR14 at all sites and in amounts greater than for other analytes which made it the most useful analyte for contaminant track-down purposes. AR14 amounts in PISCES were greatest (58. and 85. ng) in the samplers from downstream at Porter Road and diminished upstream, especially upstream from site #6 located across the runway and opposite the western most hanger building (Table 3 and Figure 1). The amount of AR14 in PISCES at site #7, located about 1,000 feet upstream -8-

15 from site #10, was similar; to that at the downstream Porter Road site #10. Identical mean AR14 uptake rates (0.0 ng/cm /day) for the next two upstream sites above site #6 (sites #4 and #5) were the lowest encountered, even lower than mean rates (3-5 ng/cm /day) for sites further upstream. This may be due to dilution by increased flow, although the flow data at sampler deployment and retrieval does not show this clearly (Table ). However, a two fold increase in specific conductivity at site #5 over that for site #4 indicates the presence of other drainage with different chemistry (Table ). The mean AR14 uptake rate (0.07 ng/cm /day) for site #6 more than tripled that for sites #4 and #5 which suggests outfall #6 is a PCB source. The mean AR14 uptake rate at the next downstream site #8, located below the tributary which receives outfall #8, was identical to that at site #6 even with additional dilution by the tributary. Site #8 may be affected by the same PCB source which affects site #6 and may also be affected by another but smaller PCB source which drains to the tributary from the Carborundum site located to the east. Further downstream at PISCES sites #7 and #10, the mean AR14 uptake rates increased to 0.10 and 0.11 ng/cm /day (Table 3). This increase may indicate yet another PCB source in outfall #7 or its drainage ditch to the west and north. Are PISCES sites # 7 and #10 affected by PCB present in PISCES sites #6 and #8 drainage, and also by additional PCB from outfall #7or its drainage to the west and north? DDD was detected upstream as far as site #4 located upper mid-air base but similar to AR14 was detected in greatest amount (1.4 and 0.6 ng) in samplers at the most downstream site #10 at Porter Road. PISCES samples at this downstream site also had low amounts of DDE and HCB not detected at other sites (Table 3). Mirex, which was prevalent in fish only from downstream site #10, was not detected in PISCES samples. Source Track-down - This PISCES study may have identified multiple contaminant sources/ pathways. This contaminant pattern is atypical when compared to results from other NYSDEC PISCES studies, which have bracketed a single contaminant source. For these single source studies, PISCES contaminant amounts increased near the source and then abruptly decreased further upstream. This Cayuga Creek PISCES study found that the mean AR14 PISCES uptake rate tripled at site #6 (located mid-air base), compared with means for the next two upstream sites #5 and #4, which indicates that outfall #6 is a PCB source. Further downstream at site #8, east of the Carborundum site, the mean AR14 uptake rate was identical to that for site #6. This implies that outfall #8 may be affected by the same PCB source in outfall #6 or that this drainage carries an additional but smaller PCB source from the east (Figure 1 and Table 3). The greater mean AR14 uptake rate at downstream site #10 and the nearly identical mean AR14 uptake rate at sites #7 suggests there may be a third PCB source in outfall #7 or its drainage. For future investigations, the first and most plausible contaminant pathway to pursue is outfall #6, followed by outfalls #7 and #8 and their receiving tributaries. Particular attention should be given to the site #7 drainage (blue colored on Figure 1) around the western end of the -9-

16 longest runway at the air base. This rock rip rap lined drainage ditch which joins Cayuga Creek within 5 feet upstream of PISCES site #7 was not sampled directly during this study because the flow was only a trickle. This drainage circumvents are large area of the air base and damaged riparian vegetation indicates that it receives significant runoff. Figure 1 and aerial views (not included) show that this drainage receives input from a small tributary with potential for seasonal or event-related drainage from a large hazardous waste landfill northwest of Lockport Road. Future PISCES sampling should also include 3-5 additional Cayuga Creek sites which extend downstream to Lindberg Avenue (located below the confluence with Bergholtz Creek) and 4 or 5 sites in Bergholtz Creek up to and beyond Walmore Road. Another less plausible contaminant pathway to investigate in the future, which may be affecting Cayuga Creek, particularly PISCES sites #10, #8 and #7, and Bergholtz Creek, is the contribution of contaminants attached to suspended sediment that may be pushed upstream during Niagara River backwash extremes. URS Corporation et al., 005 reports that extremely high river backwash can influence the water level of Cayuga and Bergholtz Creeks for 10,100 (± 100 feet) and 10,900 (± 100 feet), respectively. The model estimated the upper reach affected in Cayuga Creek is about,000 feet downstream from Porter Road but for Bergholtz Creek is near Walmore Road where the young fish were collected for this study. It is common knowledge that downstream sections of Cayuga and Bergholtz Creeks were once very polluted with industrial chemical wastes. Some of these sections, e.g. mouth of Bergholtz Creek were dredged while sediment in others sections, e.g. lower Cayuga Creek, with lower contaminant levels were left for natural attenuation. Future PISCES contaminant track-down studies are recommended to be coordinated with limited sediment sampling at sites in the #6, #7 and #8 outfall drainage, and at the Porter Road site. For these samples it may be prudent to also analyze for selected industrial nd compounds specific to Love Canal and the 10 Street Landfill. In 005, prompted by elevated PCB levels in 1997 y-o-y fish, the Division of Water sampled surface sediment from five (BR01- BR05) Bergholtz Creek locations. Sediment samples were analyzed for seven PCB Aroclors. Sediment from BR03 located just downstream from where the 005 fish composite was collected had 340 ppb AR154 and the sample collected nearer the confluence with Cayuga Creek (BR05) had 300 ppb AR154. A third sample from Williams Road, located about half-way between BR05 and BR03, had a J value (estimated value less than detection) of 100 ppb AR154. Williams Road is where y-o-y fish were collected in Values for the other six Aroclors and all Aroclor values for sediment data from upstream stations BR01 and BR0 were less than detection (less than ppb) personal communication with James Swart, Division of Water, NYSDEC. Is 340 ppb AR154 in sediment sufficient to cause elevated PCB levels in y-o-y fish and is this level reason enough to consider further remediation? 1997 versus 005 Fish Contaminants and Protective Criteria - Footnote 1 on Table 8 indicates that residues of chlordane metabolites, dieldrin, HCB and beta HCH were detected in 1997 y-o-y fish from Cayuga Creek at Porter Road but not in 005 fish from this same site. Despite 1997 levels near analytical detection, these small declines continue to demonstrate -10-

17 decreasing pesticide residues in the Great Lakes Basin. Despite these declines, detectable levels of AR14, AR154/160, DDE, DDD and mirex were common to 1997 and 005 y-o-y fish composites from Cayuga Creek at Porter Road (Table 8). Mean analyte values for 005 Cayuga Creek fish were within one standard deviation of respective1997 means and, as a result, were not likely different. In 005, total PCB and mirex levels in 005 Porter Road fish continued to exceed criteria designed to protect sensitive fish-eating wildlife. Prior to 005, fish composites from the upstream Lockport Road site were analyzed only for dioxins and furans which were not part of the 005 analyte list, so comparisons of earlier PCB and OC pesticides levels for this site were not possible. The mean lipid adjusted AR154/160 value for Bergholtz Creek fish was 3 times greater in 1997 primarily due to a.6 % lower mean percent lipid. Despite the 1970 ban on the usage of the insecticide DDT in New York State, Bergholtz Creek fish again showed the presence of low DDT contamination. SUMMARY This 005 Cayuga Creek (Niagara County) contaminant track-down study, funded by NFARS and the NYSDEC, utilized PISCES and y-o-y fish composites, to address causes for a moderate to severe water quality rating reported in a 003 study (Trometer) and to locate the source of contaminants identified in y-o-y fish collected downstream from NFARS property in 1997 (Preddice et al, 00). PISCES were collected at eight locations which bracketed outfalls on NFARS property. Sampling also included an upstream site at Lockport Road and a downstream site at Porter Road where the 1997 fish were collected. The two PISCES samplers deployed for about two weeks at each site concentrated AR14 from the water column at all sites, and 4,4'-DDE and 4,4'-DDD at downstream sites #4 - #8 and #10. One sampler at the most downstream site #10 also had a low level of HCB. Y-o-y fish composites collected at the most upstream and downstream PISCES sites (#9 and #10) showed AR14; AR154/ 160; 4,4'-DDE; 4,4'-DDD in fish from both sites and mirex only in fish from the downstream site. AR14 was determined to be most useful analyte for contaminant track-down because it was detected in PISCES at each site. Mean AR14 uptake rate (0.07 ng/cm /day) tripled at site #6 compared with that at upstream PISCES sites #5 and #4. This indicated outfall #6 to be a PCB source to Cayuga Creek. The mean AR14 uptake rate at PISCES site #8 located further downstream below outfall #8 was the same as that for site #6 despite additional dilution. As a result, outfall #8 or a source in its drainage such as the Carborundum site to the east may be another but smaller PCB source. The greatest mean AR14 uptake rate of 0.11 ng/cm /day was at the most downstream site #10 at Porter Road. However, less than 1,000 feet upstream at site #7, the mean AR14 uptake rate was nearly the same (0.10 versus 0.11 ng/cm /day). These higher rates may be in part due to a third PCB source in outfall #7 or its drainage to the west and northwest. The PCB source affecting PISCES site #6 may also have an effect at PISCES sites #7, #8 and #10. The presence of 4,4'-DDE and HCB in PISCES only at downstream site #10, and mirex only in site #10 fish could implicate site #7 drainage which was not directly sampled in this study due to low flows. -11-

18 A comparison of lipid adjusted AR14 and AR154/ 160 levels in y-o-y fish from the upstream Lockport Road and downstream Porter Road sites shows means were 3 and 15 times greater at Porter Road, respectively. Mean DDE and DDD levels in fish from the two locations were about the same but, again, all composites of fish from downstream site #10 contained mirex. These downstream increases support the 1997 conclusion that a contaminant source exists upstream from Porter Road. Mean PCB, DDE, DDD and mirex levels in fish from Porter Road were not different from1997 mean values. Total PCB ( ppb) and mirex levels in y-o-y fish continued to exceed the respective criteria to protect sensitive wildlife. However, the levels of chlordane metabolites, dieldrin, HCB and beta HCH which were near method detection limits in 1997 fish, were no longer present in 005. As an aside, one composite of y-o-y fish from Bergholtz Creek, a nearby Cayuga Creek tributary, was also collected in 005. Except for the absence of mirex, Bergholtz Creek fish contained the same main four contaminants found in Cayuga Creek fish, plus DDT. Lipid adjusted PCB values were about 3-4 times greater than for Cayuga Creek fish from Porter Road. The total PCB level in Bergholtz Creek fish (also sampled in 1997) continued to exceed the criterion designed to protect sensitive wildlife species. The greater PCB level plus the presence of DDT and the absence of mirex in the 005 composite suggests that Bergholtz Creek at Walmore Road and Cayuga Creek at Porter Road are affected by different contaminant sources. Both of these sites have potential to be affected by the transport of contaminants from downstream during extreme Niagara River backwash episodes. An expanded PISCES study is recommended with limited sediment sampling. This second PISCES study should include additional Cayuga Creek sites located further downstream and more in Bergholtz Creek, as well as additional sites in outfall #6, #7 and #8 drainage. ACKNOWLEDGMENT This project was completed with the assistance of several individuals. Rachel Vickers, SUNY Cobleskill Intern, cleaned and assembled the PISCES samplers, and both she and Michael Kane, Biologist I (Ecologist) helped author, Timothy Preddice, with the deployment and retrieval of samplers. Coauthor Elizabeth Trometer, USFWS Fishery Biologist and Cara Ewell Hodkin, USFWS Fish and Wildlife Biologist, measured physico-chemical stream parameters at PISCES sites and assisted with fish collection. Chris Castiglione, USFWS, produced the site map for this report. Lawrence Skinner, Biologist III (Ecology) provided valuable constructive comments to the draft report. Anthony Gudlewski and other staff of the NYSDEC Analytical Services Unit deserve to be commended for their timely and excellent analytical work. The authors would also like to thank Jim Mathews of the 914 MSG/CEV for providing project support and access to the th air base, and for editing suggestions. Funding for this study was provided by the 914 Airlift Wing, NFARS and by NYSDEC. -1-

19 LITERATURE CITED Bode, R., M. Novak, L. Abele, D. Heitzman and A. Smith, 00. Quality assurance work plans for biological stream monitoring in New York State. Stream Biomonitoring Unit, Div. Water, N.Y.S. Dept. Environmental Conservation, Albany, NY. International Joint Commission, Revised Great Lakes water quality agreement of 1978, signed November 18, Water Quality Div., IJC, Windsor, Ontario, Canada. Newell, A., D. Johnson and L. Allen, Niagara River biota contaminant project: fish flesh criteria for piscivorus wildlife. Tech. Rep. 87-3, Div. Fish & Wild., N.Y.S. Dept. Environmental Conservation, Albany, NY. Niagara Falls Air Reserve Station, 003. Scope of work - Evaluate the Impact of storm water th discharges from the Niagara Falls Air Reserve Station to Cayuga Creek. 914 Airlift Wing, NFARS, Niagara Falls, NY. New York State Dept. Environmental Conservation, 006. Water quality regulations, surface water and groundwater classification and standards, N.Y.S. Codes, Rules and Regulations, Title 6, Chapter X, Subchapter B, Parts , Albany, NY. Preddice, T., 007. Contaminant track-down with PISCES - standard operating procedures. Hale Creek Field Station, Bur. Habitat, Div. Fish, Wild. & Marine Res., N.Y.S. Dept. Environmental Conservation, Gloversville, N.Y. Preddice, T., L. Skinner and A. Gudlewski, 006. PCBs and organochlorine pesticide residue in young-of-year fish from traditional near-shore sampling areas, N.Y.S s Great Lakes Basin, 003. Bur. Habitat, Div. Fish, Wild. and Marine Res., N.Y.S. Dept. Environmental Conservation, Gloversville, NY...., S. Jackling and L. Skinner, 00. Contaminants in young-of-year fish from nearshore areas of New York s Great Lakes Basin, Bur. Habitat, Div. Fish, Wild. and Marine Res., N.Y.S. Dept. Environmental Conservation, Gloversville, NY...., S. Jackling and L. Skinner, Contaminants in young-of-year fish from selected Lake Ontario tributaries, Bur. Habitat, Div. Fish, Wild. and Marine Res., N.Y.S. Dept. Environmental Conservation, Albany, NY. Skinner, L, Dioxins and furans in fish below Love Canal, New York. - concentration reduction following remediation, Div. Fish & Wild., N.Y.S. Dept. Environmental Conservation, Albany, NY. -13-

20 Skinner, L. and S. Jackling, Chemical contaminants in young-of-year fish from New York s Great Lakes Basin, 1984 through Bur. Environ. Protection, Div. Fish and Wild., N.Y.S. Dept. Environmental Conservation, Albany, NY. Skinner, L., S. Jackling and R. Karcher, Identification of and changes in chemical contaminant levels in young-of-year fish from New York s Great Lakes Basin. Tech. Rep Bur. Environ. Protection, Div. Fish and Wild., N.Y.S. Dept. Environmental Conservation, Albany, NY. Trometer, E, 005. Impacts of storm water discharges from the Niagara Falls Air Reserve Station on Cayuga Creek. Proj. No. MIPRO U.S. Dept. Interior, Fish & Wild. Ser. Amherst, NY. United States Environmental Protection Agency, Guidance for assessing chemical nd contaminant data for use in fish advisories. Office of Water. Vol. 1, Ed., U.S.E.P.A., Washington, D.C. URS Corporation, Gomez and Sullivan Engineers, PC, and E/PRO Engineering & Environmental Consulting, LLC, 005. Upper Niagara River tributary backwater study. Niagara Power Project FERC No

21 Table 1. Description of 005 Cayuga Creek PISCES sampling locations, Cayuga Creek, Niagara Falls, NY. PISCES Site No. 9 upstream Northing Easting Description N E within ~100 feet downstream from Lockport Road crossing N E downstream from outfall #1 near large rock located ~100 feet from culvert under Walmore Road on the eastern side of NFARS N E downstream from outfall # and the bend near a big rock located ~ 400 feet upstream from PISCES site #3 on the eastern side of NFARS N E downstream of outfall #3 on the eastern side of NFARS N E downstream from outfall #4 and the triple culvert under A3 taxiway N E downstream from outfall #5 located mid-nfars N E mid-nfars, downstream from outfall #6, ~ 1,00 feet downstream from PISCES site # N E downstream from outfall #8 at the junction with the drainage from the Carborundum site N 66671E suspended mid-creek from NFARS southwest fence, slightly downstream from jct. with rock rip rap ditch with outfall #7 10 downstream N E within feet downstream from the Porter Road crossing -15-

22 Table. Physical parameters at each PISCES sampling location during sampler deployment and retrieval, Cayuga Creek, Niagara Co., Sept Parameter PISCES Sampling Sites Mean upstream Lockport Road (9) downstream Porter Road (10) Date Set 9/15 9/15 9/15 9/14 9/14 9/14 9/15 9/14 9/14 9/14 - Retrieve 9/8 9/9 9/9 9/9 9/9 9/9 9/9 9/8 9/8 9/8 - Depth (m) Set Retrieve Width (m) Set Current (m/s) Flow (cms) Retrieve Set Retrieve Set Retrieve o Temp. C Set Spec. Cond. (ìmhos) Retrieve Set Retrieve DO (mg/l) Set Retrieve ph Set Retrieve % Canopy Set Retrieve

23 Table 3. PISCES contaminant data (nanograms) for Hassett-style samplers deployed in Cayuga Creek, Niagara Falls, NY, Sept (blanks values were less than detection and were considered zero for calculating means) PISCES Site Hassett No. Sample No. Exposure (days) Amt. AR14 4,4'-DDE 4,4'-DDD HCB Spike Recovered 3 Mean mean UTR (sd) 1 (ng/cm /d) Amt. Mean mean UTR (ng/cm /d) Amt. Mean mean UTR (ng/cm /d) Amt. Mean mean URT (ng/cm /d) (ng) Upstream (6.8) (.0) (3.3) (.4) (1.8) 0.0 (3.3) (.4) 0.0 (.1) (7.) 0.07 (3.3) (1.1) 0.07 (3.8) sample disregarded - membrane covered with vegetation and debris reducing uptake Downstream (19.1) 0.11 (1.3) (5.8) 0.03 (6.) (sd) - standard deviation UTR - uptake rate (ng/cm /day) based on amount in PISCES/membrane surface area/ number of days exposure 3 a nominal 10 ng spike of trans-chlordane was added to each sampler at deployment. -17-

24 Table 4. PCB Aroclor and organochlorine pesticide residue data (ppb wet weight) for young-of-year fish composites (15 fish/ composite) collected from Cayuga and Bergholtz Creeks in the vicinity of the Niagara Falls Air Reserve Station and the Niagara Falls International Airport, Niagara Co., NY, Sept., 005. (blank values were less than detection and were considered zero for calculating means) Site Sample No. Comp. 1 Species AR14 AR154/ 160 4,4'- DDE 4,4'-DDD 4,4'-DDT Mirex upstream Cayuga Lockport Rd. 046 a CC b CC c CC d CC e CC Means 15.8 (3.3) 13.8 (19.1) 0.0 (1.4).7 (0.3) downstream Cayuga Porter Rd. 051 a CS b CC c CS d CS Means 36.0 (11.1) 17 (13.) 19.5 (5.3) 6.9 (0.9) 46.9 (10.9) Bergholtz Walmore Rd. 055 a BN Species : CC - creek chub, CS - common shiner, BN - bluntnose minnow ( ) - standard deviation may be 1+ year class -18-

25 Table 5. PCB Aroclor and organochlorine pesticide residue data (ppb lipid-adjusted) for young-of-year fish composites (15 fish/ composite) collected from Cayuga and Bergholtz Creeks in the vicinity of the Niagara Falls Air Reserve Station and the Niagara Falls International Airport, Niagara Co., NY, Sept., 005. (blank values were less than detection and were considered zero for calculating means) Site Sample No. Com p. Species 1 % Lipid AR14 AR154/ 160 4,4'-DDE 4,4'- DDD 4,4'- DDT Mirex upstream Cayuga Lockport Rd. 046 a CC b CC c CC d CC e CC mean.96 (0.5) 543 (155) 430 (598) 676 (41.1) 90.3 (6.1) downstream Cayuga Porter Rd. 051 a CS b CC c CS d CS mean 1.96 (0.17) 1837 (514) 6475 (579) 989 (00) 348 () 375 (380) Bergholtz Walmore Rd. 055 a BN Species : CC - creek chub, CS - common shiner, BN - bluntnose minnow ( ) standard deviation 3 may be 1+ year class -19-

26 Table 6. Length and weight measurements for young-of-year fish composites (15 fish per composite) collected in conjunction with PISCES contaminant track-down studies for Cayuga Creek, vicinity of Niagara Falls Air Force Reserve Station and Niagara Falls International Airport, Sept Location Composite Species Composite Weight (g) Total Length (mm) Mean Length (mm) Lockport Road a creek chub , 35, 39, 35, 37, 4, 35, 40, 33, 35, 36, 34, 35, 46, (3.7) 1 b creek chub , 39, 43, 33, 45, 43, 34, 47, 44, 33, 39, 4, 4, 46, 3 c creek chub 5.6 3, 36, 31, 3, 35, 34, 3, 34, 34, 41, 35, 35, 36, 3, (6) 34 (5) d creek chub , 39, 9, 7, 39, 39, 34, 8, 37, 34, 39, 3, 35, 37, (4) e creek chub 6.3 3, 36, 39, 33, 3, 38, 35, 36, 40, 34, 38, 3, 40, 38, 4 36 (3) Porter Road a common shiner , 50, 46, 49, 49, 55, 47, 54, 50, 51, 48, 5, 50, 50, (9) b 13 fish creek chub , 54, 48, 51, 54, 44, 55, 51, 49, 58, 51, 57, 49 5 (9) c common shiner , 50, 50, 45, 50, 54, 50, 50, 54, 56, 48, 49, 54, 51, 48 d common shiner , 48, 40, 44, 51, 4, 49, 41, 4, 48, 48, 40, 4, 47, (8) 44 (9) Bergholtz Walmore Rd. a bluntnose minnow , 45, 34, 35, 47, 34, 9, 39, 9, 4, 34, 34, 45, 34, (9) standard deviation 1 may have been 1+ age class rather than y-o-y fish -0-

27 Table 7. Total PCB and Mirex concentrations (ppb wet weight) in 005 young-of-year fish composites from Cayuga Creek that exceed fish flesh criteria to protect sensitive piscivorus wildlife and waterfowl. (includes one site on nearby Bergholtz Creek). Location Composite Species Total PCB , 130 Mirex , 330, < detect. limit Lockport Road a creek chub b c d e Porter Road a common shiner b creek chub c common shiner d Bergholtz Walmore Road a bluntnose minnow NYSDEC 1:100 dietary cancer risk criterion for mink (Newell et al., 1987) NYSDEC non-carcinogenic criterion for the protection of fish-eating wildlife (Newell et al., 1987) 3 level in fish designed to protect piscivorus wildlife (IJC, 1988) -1-

28 Table 8. Comparison of 1997 and 005 PCB Aroclors, DDE, DDD and Mirex concentrations (ppb lipid) in young-of-year fish collected from Cayuga Creek at Porter Road, Niagara Falls, NY. 4 3 Year Species % Lipid AR148 AR154/160 4,4'-DDE 4,4'-DDD Mirex 1997 BN CC CS mean (sd).41 (51) 448 (659) 543 (874) 879 (19) 578 (116) 397 (1433) 005 CS CC CS CS mean (sd) 1.96 (17) 1837 (514) 6475 (579) 989 (00) 349 () 375 (3) 1 Trace levels of beta HCH, trans-chlordane, cis-chlordane, trans-nonachlor, dieldrin and HCB were not included in this table because they were detected only in 1997 fish composites. Species: BN - bluntnose minnow, CC - creek chub, CS - common shiner 3measured as Ar148 in and as AR14 in both are similar light Aroclors with common PCB congeners --

29 Table 9. Comparison of 1997 and 005 PCB Aroclors and organochlorine pesticide residues data (ppb lipid) for young-of-year bluntnose minnow composites (15 fish/composite) collected from Bergholtz Creek, Niagara Co. 4 Location Year Comp % Lipid AR148 AR154/160 4,4'-DDE 4,4'-DDE 4,4'-DDT Williams Road 1997 a b c d e f mean 1.03 (1) (96) (14419) 58 (13) 03 (57) 335 (85) Walmore Road 005 a measured as AR148 in 1997 and as Ar14 in both are similar light Aroclors with common PCB congeners ( ) - standard deviation -3-

30 Figure 1. Cayuga Creek PISCES sampling locations and outfalls on NFARS, Niagara Falls, NY,