Data report for residues of organic chem

Data Report for Residues of Organic Chemicals and Four Metals in Edible Tissues and Whole Fish for Fish Taken from the Buffalo River, New York Lawrence C Skinner New York State Department of Environmental Conservation 625 Broadway Albany, New York 12233-4756 Betsy Trometer U S Fish and Wildlife Service 405 N French Road, Suite 120A Amherst, NY 14228 Anthony J Gudlewski Brian Buanno New York State Department of Environmental Conservation 182 Steele Avenue Extension Gloversville, NY 12078 John Bourbon U S Environmental Protection Agency 2890 Woodbridge Avenue Edison, NJ 08837-3679 October 2009 Table of Contents Page Abstract ii List of Tables iii List of Figures vi Introduction Methods Field and laboratory methods Data analysis Uncertainty 3 Results and Discussion Overview Data comparability for PCBs and organochlorine pesticides Lipids Polychlorinated biphenyls Organochlorine pesticides Metals Chlorinated dibenzo-p-dioxins and dibenzofurans Polynuclear aromatic hydrocarbons Brominated diphenyl ethers 9 10 10 11 12 13 13 15 Acknowledgments 16 References cited 17 Tables 19 Figures 155 Appendix A 159 Appendix B 164 i ABSTRACT The Buffalo River has a history of chemical inputs from a variety of industrial and municipal sources Chemical residues remain in sediments and contribute to use impairments for a variety of purposes A sediment dredging project is proposed to remove contaminants and to restore some of the beneficial uses As a prerequisite for the dredging project, assessments of chemical residue concentrations in fish are necessary for Human Health Risk Assessment and for an Ecological Risk Assessment This report provides the chemical residue data necessary for these risk assessments Further, this information provides a portion of the baseline from which to assess the efficacy of the dredging project Due to the variety of potential sources of chemical residues to the Buffalo River and Harbor, the area was divided into four zones in an effort to provide, where possible, associations of chemical residues in fish with residues from point or sediment sources The data is provided by zone for each analyte Chemical residues were examined in edible portions of fish and in the whole body of those same fish Species analyzed that may be consumed by humans included brown bullhead, carp, largemouth bass, pumpkinseed and yellow perch A limited number of samples of forage fish were also analyzed and include bluntnose minnows and round goby Chemical analytes examined include polychlorinated biphenyls (PCBs) expressed as Aroclors, organochlorine pesticides, four metals (arsenic, cadmium, lead and mercury), chlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), polynuclear aromatic hydrocarbons (PAHs) and brominated diphenyl ethers (BDEs) It is not the intent of this report to provide any interpretation of the data for the risk assessments Those assessments are the purview of other authorities This report does contain some highlights of the data ii List of Tables Page Table 1: History of health advisories for fish in the Buffalo River and Buffalo Harbor 19 Fish sample descriptions for fish collected from the Buffalo River, October 2007 20 Laboratories conducting chemical analysis of fish tissues from the Buffalo River, and the species and analyte groups analyzed 24 Table 4: 2,3,7,8-TCDD toxicity equivalency factors (TEFs) 25 Table 5: Polycyclic aromatic hydrocarbon (PAH) Potency Equivalency Factors (PEFs) 26 Comparison of lipid, polychlorinated biphenyl and organochlorine pesticide concentrations in edible tissues of carp taken from the Buffalo River in April 2004 and October 2007 27 Comparison of two laboratories analytical results (ng/g wet weight) for lipids, PCBs and organochlorine pesticides in carp and yellow perch samples taken from the Buffalo River in October 2007 29 PCB, organochlorine pesticide and metal concentrations in whole bluntnose minnows and round gobies taken from the Buffalo River; October 2007 30 Polychlorinated biphenyl (Aroclor), organochlorine pesticide and metal concentrations in tissues of brown bullhead taken from the Buffalo River; October 2007 32 Polychlorinated biphenyl (Aroclor), organochlorine pesticide and metal concentrations in tissues of carp taken from the Buffalo River, October 2007 37 Polychlorinated biphenyl (Aroclor), organochlorine pesticide and metal concentrations in tissues of largemouth bass taken from the Buffalo River; October 2007 44 Polychlorinated biphenyl (Aroclor), organochlorine pesticide and metal concentrations in tissues of pumpkinseed taken from the Buffalo River; October 2007 52 Table 2: Table 3: Table 6: Table 7: Table 8: Table 9A-B: Table 10A-B: Table 11A-B: Table 12A-B: iii Table 13: Table 14: Table 15: Table 16A-B: Table 17A-C: Table 18A-B: Table 19: Table 20: Table 21: Table 22: Table 23A-C: Polychlorinated biphenyl (Aroclor) and organochlorine pesticide concentrations in yellow perch taken from the Buffalo River; October 2007 58 Metal concentrations in tissues of yellow perch taken from the Buffalo River, October 2007 61 Chlorinated dibenzo-p-dioxin and dibenzofuran concentrations in whole body composite samples of bluntnose minnows taken from the Buffalo River, October 2007 62 Chlorinated dibenzo-p-dioxin and dibenzofuran concentrations in tissues of brown bullhead taken from the Buffalo River, October 2007 64 Chlorinated dibenzo-p-dioxin and dibenzofuran concentrations in tissues of carp taken from the Buffalo River, October 2007 72 Chlorinated dibenzo-p-dioxins and dibenzofuran concentrations in tissues of pumpkinseed taken from the Buffalo River, October 2007 83 Human and mammalian 2,3,7,8-TCDD toxicity equivalent concentrations1 (TEQs) based on chlorinated dibenzo-p-dioxins and dibenzofurans in fish taken from the Buffalo River, October 2007 89 2,3,7,8-TCDD toxicity equivalent concentrations1 (TEQs) for birds and fish based on chlorinated dibenzo-p-dioxins and dibenzofurans in fish taken from the Buffalo River, October 2007 90 Polynuclear aromatic hydrocarbon concentrations in whole body composites of bluntnose minnows taken from the Buffalo River, October 2007 91 Polynuclear aromatic hydrocarbons in tissues of brown bullhead taken from the Buffalo River, October 2007 93 Concentrations of polynuclear aromatic hydrocarbons in carp taken from the Buffalo River, October 2007 98 Table 24A-D: Polynuclear aromatic hydrocarbon concentrations in tissues of largemouth bass taken from the Buffalo River, October 2007 Table 25A-B: Table 26: 107 Polynuclear aromatic hydrocarbons in tissues of pumpkinseed taken from the Buffalo River, October 2007 118 Potency equivalent concentrations1 (PECs) for select PAHs in fish taken from the Buffalo River, October 2007 126 iv Table 27: Table 28A-B: Table 29: Table 30A-B: Table 31A-B: Table 32: Polybrominated diphenyl ether (BDE) concentrations in whole body composite samples of bluntnose minnows taken from the Buffalo River, October 2007 127 Polybrominated diphenyl ether (BDE) concentrations in tissues of brown bullhead taken from the Buffalo River, October 2007 129 Polybrominated diphenyl ether (BDE) concentrations in tissues of carp taken from the Buffalo River, October 2007 135 Polybrominated diphenyl ether (BDE) concentrations in tissues of largemouth bass taken from the Buffalo River, October 2007 140 Polybrominated diphenyl ether (BDE) concentrations in tissues of pumpkinseed taken from the Buffalo River, October 2007 144 Primary brominated diphenyl ethers (BDEs) detected in fish from the Buffalo River, October 2007 154 v List of Figures Page Figure Zones for sampling fish in the Buffalo River, Erie County, New York 155 Comparison of total PCBs, p,p’-DDE and trans-nonachlor concentrations (ng/g wet weight) in fish from the Buffalo River, 2007 156 Figure Mean PAHs in whole carp from the Buffalo River 157 Figure BDE congener distribution in fish from the Buffalo River 158 Figure vi INTRODUCTION The International Joint Commission, on behalf of the governments of Canada and the United States, defined water quality objectives for waters shared by the two countries within the Great Lakes Water Quality Agreement, as amended in 1987 Within the Agreement, 14 beneficial uses have been defined If an area is found to have at least one beneficial use that is impaired, it may result in the area being declared an Area of Concern The Buffalo River is among the 42 Areas of Concern within the Great Lakes basin and was designated in 1987 The Buffalo River declaration was due to a number of beneficial use impairments (BUI) caused by historic and on-going discharges of a wide variety of chemicals or by physical alterations of the ecosystem Some of the BUIs are: • restrictions on fish consumption; • fish tumors and deformities; • degradation of fish populations; • degradation of benthos; • possible tainting of fish flavor; • possible bird or animal deformities or reproductive problems; • loss of fish and wildlife habitat; and • restrictions on dredging activities Many of the industries discharging those chemicals are no longer operating However, the BUIs due to chemical residuals may still be present but require reassessment (BNRiverkeeper, 2005) The cessation of discharges has caused improvements in water quality sufficient to permit habitation of the waters by a greater array of fish species or by previously present species but in greater abundance These fish are sought by anglers for recreation and/or consumption However, health advisories recommending restrictions on consumption of fish continue to be in place (Table 1; NYSDOH, 2009) The basis for the health advisories is the presence of excessive concentrations of polychlorinated biphenyls (PCBs), although organochlorine pesticides, mercury, cadmium and lead have also been examined in historical assessments A Buffalo River Remedial Action Plan (RAP) was developed by a consortium of agencies, academia and the public The goal of the RAP is “to restore and maintain the chemical, physical, and biological integrity of the Buffalo River ecosystem in accordance with the Great Lakes Water Quality Agreement” Among the recommendations for reducing chemical exposures to fish, wildlife and humans, the RAP recommended the remediation of contaminated sediments and inactive hazardous waste sites, and control of point and non-point sources of pollutants Among the pollutants within the ecosystem are PCBs, PAHs, heavy metals and a variety of industrial organic compounds (NYSDEC, 1989) In a 2005 status report on progress in meeting the goal and objectives of the RAP, it was noted that planning for removal of contaminated sediments was on-going, remediation of 45 inactive hazardous waste sites within the drainage basin was approaching completion, non-point source abatement in the upper drainage basin was being implemented, and track down of illegal connections or illicit discharges to the 33 combined sewer overflows was being planned (BNRiverkeeper, 2005) As noted previously, planning for removal of contaminated sediments from the Buffalo River and Harbor is actively being conducted As part of the planning process, an Ecological Risk Assessment (ERA) and a Human Health Risk Assessment (HHRA) must be conducted to assess actual or potential impacts of chemical residues present in the river and harbor These risk assessments support three sediment assessment projects, i.e., • a project supported by the Great Lakes Legacy Act administered through the U S Environmental Protection Agency’s Great Lakes National Program Office (EPAGLNPO); • a “312 Feasibility Study” pursuant to an agreement with the U S Army Corps of Engineers - Buffalo District; and • the “Upper Buffalo River Remedial Investigation/Feasibility Study (RI/FS)” for the dredging project as required by EPA-GLNPO The data generated pursuant to this project provides the pre-dredging baseline data to be used for assessing one measure of efficacy of dredging at post-remediation In addition to the data needs for remedial purposes, the chemical residue information included in this report will: a) aid the re-evaluation of several BUIs which were the basis for designation of the Buffalo River Area of Concern; b) provide for an expanded evaluation of chemical residues to now include chlorinated dioxins and furans [PCDD/Fs], polynuclear aromatic hydrocarbons [PAHs], brominated diphenyl ethers [BDEs], and arsenic in fish; c) provide for an assessment of an expanded array of fish species which have been exposed to chemical residues; d) provide a basis for a limited assessment of temporal changes in chemical residues; and e) provide a basis for considering the pursuit of a natural resource damage claim for injuries to natural resources in or along the Buffalo River METHODS Field and laboratory methods This project required the cooperative efforts of several agencies and laboratories which are enumerated below In this study, the river was divided into the inner harbor and four sections in an attempt to represent zones potentially impacted by various industries located along the river (Figure 1) The four zones are described below Zone The Buffalo (City) Ship Canal south of the Michigan Street bridge; approximately 1.6 km Zone Buffalo River from the Michigan Street bridge upstream to approximately 1.3 km upstream of the bridge on Ohio Street; approximately 2.4 km Zone Buffalo River from approximately 1.3 km upstream of the Ohio Street bridge to the bridge at South Park Avenue; approximately 3.8 km Zone Bridge at South Park Avenue to the Route 62 bridge upstream of the junction of Buffalo Creek and Cazenovia Creek; approximately 1.6 km Fish were collected by the U S Fish and Wildlife Service (coordinated by the Amherst, NY office) by use of electrofishing All fish were measured, weighed, an individual tag was applied (Table 2), and placed individually in food grade plastic bags Fish were kept on ice until frozen the same day The samples were transported under chain of custody to the NYS Department of Environmental Conservation’s (the Department) analytical laboratory at the Hale Creek Field Station in Gloversville, NY Staff at the Department’s laboratory prepared all samples for chemical analyses Initial sample preparations were dependent on the species of fish Bluntnose minnows (Pimephales notatus) and round goby (Neogobius melanostomus), both representing forage fish species, were composited and ground whole Carp (Cyprinus carpio), pumpkinseed (Lepomis gibbosus), largemouth bass (Micropterus salmoides) and yellow perch (Perca flavescens) were prepared by excising standard filets (scales removed) and reserving the remaining carcass The weight of the standard filets and the carcass were individually weighed and the individual weights recorded Brown bullhead (Ameiurus nebulosus) were prepared by removing the skin, excising filets and reserving the remaining carcass As with other edible fish, the edible portion (filets) were weighed and recorded The bullhead skin plus remaining carcass were combined and weighed, and the weight was recorded as the carcass weight Table presents the length, whole weight of Concentration (pg/g wet weight) in: Parameter/ BDE No Zone Zone Edible tissue Carcass Calculated whole fish Edible tissue Carcass Calculated whole fish 71 21.9