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Carl E. Orazio

Publications and source records attributed to Carl E. Orazio.

At least 19 recordsLinked to original sources

Mapping elemental contamination on Palmyra Atoll National Wildlife Refuge

Palmyra Atoll, once a WWII U.S. Navy air station, is now a U.S. National Wildlife Refuge with nearly 50 km 2 of coral reef and 275 ha of emergent lands with forests of Pisonia grandis trees and colonies of several bird species. Due to the known elemental and organic contamination from chemicals associated with aviation, power generation and transmission, waste management, and other air station activities, a screening survey to map elemental concentrations was conducted. A map of 1944 Navy facilities was georeferenced and identifiable features were digitized. These data informed a targeted survey of 25 elements in soils and sediment at locations known or suspected to be contaminated, using a hand-held X-ray fluorescence spectrometer. At dozens of locations, concentrations of elements exceeded established soil and marine sediment thresholds for adverse ecological effects. Results were compiled into a publicly available geospatial dataset to inform potential remediation and habitat restoration activities.

Marine Pollution Bulletin

The Penobscot River and environmental contaminants: Assessment of tribal exposure through sustenance lifeways

EPA in collaboration with the Penobscot Indian Nation, U.S. Geological Survey (USGS), Agency for Toxic Substances and Disease Registry (ATSDR), and the U.S. Fish and Wildlife Service (USF&WS) collectively embarked on a four year research study to evaluate the environmental health of the riverine system by targeting specific cultural practices and using traditional science to conduct a preliminary contaminant screening of the flora and fauna of the Penobscot River ecosystem. This study was designed as a preliminary screening to determine if contaminant concentrations in fish, eel, snapping turtle, wood ducks, and plants in Regions of the Penobscot River relevant to where PIN tribal members hunt, fish and gather plants were high enough to be a health concern. This study was not designed to be a statistically validated assessment of contaminant differences among study sites or among species. The traditional methodology for health risk assessment used by the U. S. Environmental Protection Agency (EPA) is based on the use of exposure assumptions (e.g. exposure duration, food ingestion rate, body weight, etc.) that represent the entire American population, either as a central tendency exposure (e.g. average, median) or as a reasonable maximum exposure (e.g. 95% upper confidence limit). Unfortunately, EPA lacked exposure information for assessing health risks for New England regional tribes sustaining a tribal subsistence way of life. As a riverine tribe, the Penobscot culture and traditions are inextricably tied to the Penobscot River watershed. It is through hunting, fishing, trapping, gathering and making baskets, pottery, moccasins, birch-bark canoes and other traditional practices that the Penobscot culture and people are sustained. The Penobscot River receives a variety of pollutant discharges leaving the Penobscot Indian Nation (PIN) questioning the ecological health and water quality of the river and how this may affect the practices that sustain their way of life. The objectives of this Regional Applied Research Effort (RARE) study were to: Develop culturally sensitive methodologies for assessing the potential level of exposure tocontaminants that Penobscot Indian Nation tribal members may have from maintainingtribal sustenance practices. Conduct field surveys and laboratory analysis on targeted flora and fauna for chemicalexposure to dioxins/furans, polychlorinated biphenyls (PCBs), total mercury and methyl-mercury. Assist the Agency for Toxic Substances and Disease Registry (ATSDR) by providing thenecessary data to conduct a Public Health Assessment for the Penobscot Indian Nation. Establish protocols for assessing the level of exposure to PCBs, dioxins/furans and mercuryto PIN tribal members as a consequence of gathering tribal plants for medicinal andnutritional purposes; as well as consuming fish, wood duck, and snapping turtle as a primarysource of nutrition. Survey surface water, drinking water, and sediment from the Penobscot River and IndianIsland to assess the exposure of PIN tribal members to environmental genotoxicants thatcontinue cultural sustenance practices. This research initiative collected and analyzed sediment and biota to determine the level of contaminant exposure to Penobscot tribal members. Natural resource utilization patterns and exposure pathways were identified based on discussions with the Tribal elders. Identification of Tribal exposure factors (exposure pathways and contaminant concentrations) was essential for accurately assessing potential long-term Penobscot Indian Nation tribal members’ exposure. Based on this study, ATSDR’s Public Health Assessment (PHA) concluded that the Penobscot Indian Nation (PIN) tribal members who eat fish and snapping turtle at the ingestion levels suggested in the Wabanaki Traditional Cultural Lifeways Exposure Scenario Report (Wabanaki Exposure Scenario) may be exposed to harmful levels of mercury, dioxins/furans, dioxin-like PCBs, and ot

Maine

Effects of dietary exposure to brominated flame retardant BDE-47 on thyroid condition, gonadal development and growth of zebrafish

Little is known about the effects of brominated flame retardants in teleosts and some of the information currently available is inconsistent. This study examined effects of dietary exposure to 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) on thyroid condition, body mass and size, and gonadal development of zebrafish. Pubertal, 49-day-old (posthatch) fish were fed diets without BDE-47 (control) or with 1, 5 or 25 μg/g BDE-47/diet. Treatments were conducted in triplicate 30-L tanks each containing 50 zebrafish, and 15 fish per treatment (5 per tank) were sampled at days 40, 80 and 120 of exposure. Measurements were taken of body mass, standard length, head depth and head length. Sex (at 40–120 days of exposure), germ cell stage (at 40 days) and thyroid condition (at 120 days; follicular cell height, colloid depletion, angiogenesis) were histologically determined. Whole-body BDE-47 levels at study completion were within the high end of levels reported in environmentally exposed (wild) fishes. Analysis of variance was used to determine differences among treatments at each sampling time. No effects were observed on thyroid condition or germ cell stage in either sex. Reduced head length was observed in females exposed to BDE-47 at 80 days but not at 40 or 120 days. In males, no apparent effects of BDE-47 were observed at 40 and 80 days, but fish exposed to 25 μg/g had lower body mass at 120 days compared to control fish. These observations suggest that BDE-47 at environmentally relevant whole-body concentrations does not affect thyroid condition or pubertal development of zebrafish but does affect growth during the juvenile-to-adult transition, especially in males.

Fish Physiology and Biochemistry

Polybrominated diphenyl ether metabolism in field collected fish from the Gila River, Arizona, USA-Levels, possible sources, and patterns

Polybrominated diphenyl ethers (PBDEs) were determined in fish collected from the Gila River, Arizona, a tributary of the Colorado River in the lower part of the Colorado River Basin. Fish samples were collected at sites on the Gila River downstream from Hayden, Phoenix, and Arlington, Arizona in late summer 2003. The Gila River is ephemeral upstream of the Phoenix urban area due to dams and irrigation projects and has limited perennial flow downstream of Phoenix due to wastewater and irrigation return flows. Fifty PBDE congeners were analyzed by high resolution gas chromatography/high resolution mass spectrometry using labeled surrogate standards in composite samples of male and female common carp ( Cyrpinus carpio ), largemouth bass ( Micropterus salmoides ) and channel catfish ( Ictalurus punctatus ). The predominant PBDE congeners detected and quantified were 47, 100, 153, 49, 28, and 17. Concentrations of total PBDEs in these fish ranged from 1.4 to 12700 ng g -1 wet weight, which are some of the highest concentrations reported in fish from the United States. Differences in metabolism of several PBDE congeners by carp is clear at the Phoenix site; congeners with at least one ring of 2,4,5-substitution are preferentially metabolized as are congeners with 2,3,4-substitution.

Arizona

Immunological and reproductive health assessment in herring gulls and black-crowned night herons in the Hudson–Raritan Estuary

Previous studies have shown inexplicable declines in breeding waterbirds within western New York/New Jersey Harbor between 1996 and 2002 and elevated polychlorinated dibenzo- p -dioxins and polychlorinated biphenyls (PCBs) in double-crested cormorant ( Phalacrocorax auritus ) eggs. The present study assessed associations between immune function, prefledgling survival, and selected organochlorine compounds and metals in herring gulls ( Larus argentatus ) and black-crowned night herons ( Nycticorax nycticorax ) in lower New York Harbor during 2003. In pipping gull embryos, lymphoid cells were counted in the thymus and bursa of Fabricius (sites of T and B lymphocyte maturation, respectively). The phytohemagglutinin (PHA) skin response assessed T cell function in gull and heron chicks. Lymphocyte proliferation was measured in vitro in adult and prefledgling gulls. Reference data came from the Great Lakes and Bay of Fundy. Survival of prefledgling gulls was poor, with only 0.68 and 0.5 chicks per nest surviving to three and four weeks after hatch, respectively. Developing lymphoid cells were reduced 51% in the thymus and 42% in the bursa of gull embryos from New York Harbor. In vitro lymphocyte assays demonstrated reduced spontaneous proliferation, reduced T cell mitogen-induced proliferation, and increased B cell mitogen-induced proliferation in gull chicks from New York Harbor. The PHA skin response was suppressed 70 to 80% in gull and heron chicks. Strong negative correlations ( r = –0.95 to –0.98) between the PHA response and dioxins and PCBs in gull livers was strong evidence suggesting that these chemicals contribute significantly to immunosuppression in New York Harbor waterbirds.

New Jersey, New York

Determination of polychlorinated biphenyls, selected persistent organochlorine pesticides, and polybrominated flame retardants in fillets of fishes from the 2007 Missouri Department of Conservation Monitoring Program

This report presents the results of a study to determine polychlorinated biphenyl, organochlorine pesticide, and polybrominated diphenylether flame retardant concentrations in selected fishes from lakes and streams across Missouri. Fillets were collected from each fish sample and after homogenization, compositing, and preparation, analyte concentrations were determined with dual column capillary gas chromatography-electron-capture detection. Total concentrations of polychlorinated biphenyls in samples ranged from background levels of about 50 to 300 nanograms per gram. In samples with elevated contaminant concentrations, chlordanes, DDT-related chemicals, and dieldrin constituted the primary classes of pesticides present, and ranged from 5 to 75 nanograms per gram. Total concentrations of polybrominated diphenyl ethers in samples ranged from background levels of 5 to 86 nanograms per gram. Channel catfish from the upper and lower Blue River and lake sturgeon from the Mississippi River at Saverton exhibited different polybrominated diphenyl ethers ratios. Concentrations of polychlorinated biphenyls, chlordanes, DDT-related compounds, and polybrominated diphenyl ethers all were greatest in samples of channel catfish from the upper and lower Blue River, and in samples of lake sturgeon from the Mississippi River at Saverton.

Open-File Report

Results of laboratory testing for diphacinone in seawater, fish, invertebrates, and soil following aerial application of rodenticide on Lehua Island, Kauai County, Hawaii, January 2009

In January 2009, rodenticide bait (Ramik Green pellets) containing the active ingredient diphacinone was aerially applied to Lehua Island. Reported herein are the results of laboratory analyses to determine diphacinone concentrations in samples of seawater, fillet of fish, soft tissue of limpets (opihi), whole-body crabs, and soil collected from Lehua Island, Kauai County, Hawaii, after aerial application of the rodenticide bait. Diphacinone was specifically chosen because of its low toxicity to nontarget organisms. Its use on Lehua Island is the second time it has ever been used for an aerial application to eradicate rodents. Testing of the Lehua Island samples for diphacinone utilized high-performance liquid chromatography with photodiode array detection. No detectable concentrations of diphacinone were found in any of the samples from Lehua Island. The limits of detection for diphacinone were 0.4 nanograms per milliliter (parts per billion) seawater, 15 nanograms per gram (dry weight) soil, 20 nanograms per gram (parts per billion) fish fillet, 13 nanograms per gram whole crab, and 34 nanograms per gram soft tissue limpet.

Hawaii

Determination of polychlorinated biphenyls, selected persistent organochlorine pesticides, and polybrominated flame retardants in fillets of fishes from the 2006 Missouri Department of Conservation Monitoring Programs

This report presents the results of a study to determine polychlorinated biphenyl, organochlorine pesticide, and polybrominated diphenyl ether flame retardant concentrations in selected fishes from lakes and streams across Missouri. Fillets were collected from each fish sample, and after homogenization, compositing, and preparation, analyte concentrations were determined with dual column capillary gas chromatography-electron-capture detection. Total concentrations of polychlorinated biphenyls in samples ranged from background levels of about 20 to 1,200 nanograms per gram. Chlordanes and DDT-related chemicals constituted the primary classes of pesticides present at elevated concentrations in most samples, and ranged from 5 to 340 nanograms per gram. Total concentrations of polybrominated diphenyl ethers in samples ranged from background levels of about 5 to about 410 nanograms per gram. Concentrations of total technical chlordane ranged from less than 5 to 260 nanograms per gram. Concentrations of polychlorinated biphenyls, chlordanes, DDT-related compounds, and polybrominated diphenyl ethers were all greatest in samples of blue catfish from Cape Girardeau and Weldon Spring.

Open-File Report

Determination of diphacinone in sea water, vertebrates, invertebrates, and bait pellet formulations following aerial broadcast on Mokapu Island, Molokai, Hawai'i

This report presents the results of a study to determine diphacinone concentrations in samples of sea water and in fillet samples of fish and in limpets from the ocean adjacent to Mokapu Island and from reference samples from Molokai, Hawai'i; concentrations of the active ingredient (diphacinone) were also determined in samples of the Ramik Green bait pellets used for the broadcast study. After preparation, diphacinone concentrations were determined with high-performance liquid chromatography with photodiode array detection. No detectable concentrations of diphacinone were found in the fish, limpets, or sea-water samples from Mokapu Island or from the reference sites. The limit of detection for diphacinone in sea water was 18 nanograms per milliliter (parts per billion); the limit of detection in fish fillets was 10 nanograms per gram (parts per billion); and the limit of detection in limpets was 17 nanograms per gram. The average concentration of diphacinone in the Ramik Green bait pellets was 45 micrograms per gram (parts per million), which represents 90 percent of the nominal concentration stated for the product by the manufacturer.

Open-File Report

Survey of chemical contaminants in the Hanalei River, Kaua'i, Hawai'i, 2001

The Hanalei River on the island of Kaua'i in Hawai'i was designated an American Heritage River in 1998, providing special attention to natural resource protection, economic revitalization, and historic and cultural preservation. Agricultural, urban, and tourism-related activities are potential sources of contamination within the Hanalei River watershed. The objective of this study was to measure certain persistent organic chemicals and elements in the Hanalei River. During a relatively low-flow period in December of 2001, samples of native Akupa sleeper fish ( Eleotris sandwicensis ), freshwater Asian clam ( Corbicula fluminea ), giant mud crab ( Scylla serrata ), surface water, and stream bed sediment were collected from a lower estuarine reach of the river near its mouth at Hanalei Bay and from an upper reach at the Hanalei National Wildlife Refuge. Samples were analyzed for residues of urban and agricultural chemicals including organochlorine pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, and elements (including mercury, lead, cadmium, arsenic, and selenium). Organic contaminants were extracted from the samples with solvent, enriched, and then analyzed by gas chromatographic analysis with electron capture or mass spectrometric detection. Samples were acid-digested for semi-quantitative analysis for elements by inductively-coupled plasma-mass spectrometry and for quantitative analysis by atomic absorption spectrophotometry. Concentrations of organochlorine pesticides, polycyclic aromatic hydrocarbons, and polychlorinated biphenyls in biota, surface water, and bed sediment sampled from the Hanalei River ranged from nondetectable to very low levels. Polychlorinated biphenyls were below detection in all samples. Dieldrin, the only compound detected in the water samples, was present at very low concentrations of 1-2 nanograms per liter. Akupa sleeper fish and giant mud crabs from the lower reach ranged from 1 to 5 nanograms per gram (wet weight) dieldrin and from less than 0.3 to 2.1 nanograms per gram total chlordane. Concentrations of individual polycyclic aromatic hydrocarbons in the lower reach bed sediments ranged from less than 1 to 190 nanograms per gram (dry weight). Relative concentrations (patterns) of the polycyclic aromatic hydrocarbons in one portion of a sediment sample indicated combustion sources. Concentrations of elements in the surface water, biota, and sediment samples were below toxicity thresholds of ecological concern. In summary, concentrations of the organic contaminants and elements targeted by this study of the Hanalei River in 2001 were below U.S. Environmental Protection Agency probable adverse effects levels for aquatic organisms.

Scientific Investigations Report

Towards quantitative monitoring of semivolatile organic compounds using passive air samplers: Chapter 6

Passive air samplers can be used to measure the air concentration of various semivolatile organic compounds (SOCs) with reasonable reliability. To use passive air samplers to measure atmospheric concentrations of pollutants, calibration data are required. Calibration data include parameters such as sampling rates, sampler/air partition coefficients and loss rate constants. These parameters are usually determined in the laboratory, at a reference site or in situ . When using passive sampler data to estimate the air concentration of SOCs, investigators commonly assume that sampling follows first-order exchange kinetics. Thus, during the first stage of sampler uptake, chemicals are accumulated linearly relative to time. The accumulation of many pollutants in passive air samplers is influenced by factors such as changes in wind speed and temperature. The use of performance reference compounds (PRCs) holds considerable promise for assessing the effects of wind speed and temperature on passive sampler performance. The use of PRCs in semipermeable membrane devices (SPMDs) has also shown that photolysis of accumulated polyaromatic hydrocarbons (PAHs) occurs without adequate shading.

Book chapter

Dietary exposure of mink (Mustela vison) to fish from the Housatonic River, Berkshire County, Massachusetts, USA: Effects on organ weights and histology and hepatic concentrations of polychlorinated biphenyls and 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalence

The effects of feeding ranch mink ( Mustela vison ) diets containing polychlorinated biphenyl (PCB)-contaminated fish (88 gold fish [ Carassius auratus ] weighing a total of 70.3 kg and 16 carp [ Cyprinus carpio ] weighing a total of 77.3 kg) collected from the Housatonic River (HR; Berkshire County, MA, USA) in October 1999 on organ weights and histology and hepatic concentrations of total PCBs (ΣPCBs) and 2,3,7,8-tetrachlorodibenzo- p -dioxin toxic equivalence (TEQ) were evaluated. Diets contained 0.22 to 3.54% HR fish, which provided 0.34 to 3.7 μg ΣPCBs/g feed (3.5-69 pg TEQ/g feed). Female mink were fed the diets eight weeks before breeding through weaning of kits at six weeks of age. Offspring were maintained on their respective diets for an additional 180 d. The dietary concentration of PCBs that caused a decrease in kit survival (3.7 μg ΣPCBs/g feed [69 pg TEQ/g]) resulted in a maternal hepatic concentration of 3.1 μg ΣPCBs/g wet weight (218 pg TEQ/g). Organ weights were not consistently affected. Mandibular and maxillary squamous cell proliferation was apparent in 31-week-old juveniles exposed to as low as 0.96 (xg ΣPCBs/g feed (9.2 pg TEQ/g). Juveniles in this treatment group had a liver concentration of 1.7 μg ΣPCBs/g wet weight (40 pg TEQ/g). Because inclusion of PCB-contaminated fish, which comprised approximately 1% of the diet, resulted in mandibular and maxillary squamous cell proliferation, it is possible that consumption of up to 30-fold that quantity of HR fish, as could be expected for wild mink, would result in more severe lesions characterized by loss of teeth, thus impacting survivability.

Environmental Toxicology and Chemistry

An evaluation of a reagentless method for the determination of total mercury in aquatic life

Multiple treatment (i.e., drying, chemical digestion, and oxidation) steps are often required during preparation of biological matrices for quantitative analysis of mercury; these multiple steps could potentially lead to systematic errors and poor recovery of the analyte. In this study, the Direct Mercury Analyzer (Milestone Inc., Monroe, CT) was utilized to measure total mercury in fish tissue by integrating steps of drying, sample combustion and gold sequestration with successive identification using atomic absorption spectrometry. We also evaluated the differences between the mercury concentrations found in samples that were homogenized and samples with no preparation. These results were confirmed with cold vapor atomic absorbance and fluorescence spectrometric methods of analysis. Finally, total mercury in wild captured largemouth bass (n = 20) were assessed using the Direct Mercury Analyzer to examine internal variability between mercury concentrations in muscle, liver and brain organs. Direct analysis of total mercury measured in muscle tissue was strongly correlated with muscle tissue that was homogenized before analysis (r = 0.81, p < 0.0001). Additionally, results using this integrated method compared favorably (p < 0.05) with conventional cold vapor spectrometry with atomic absorbance and fluorescence detection methods. Mercury concentrations in brain were significantly lower than concentrations in muscle (p < 0.001) and liver (p < 0.05) tissues. This integrated method can measure a wide range of mercury concentrations (0-500 ??g) using small sample sizes. Total mercury measurements in this study are comparative to the methods (cold vapor) commonly used for total mercury analysis and are devoid of laborious sample preparation and expensive hazardous waste. ?? Springer 2006.

Water, Air, & Soil Pollution

Biomonitoring of Environmental Status and Trends (BEST) Program: Environmental contaminants, health indicators, and reproductive biomarkers in fish from the Colorado River basin

Seven fish species were collected from 14 sites on rivers in the Colorado River Basin (CDRB) from August to October 2003. Spatial trends in the concentrations of accumulative contaminants were documented and contaminant effects on the fish were assessed. Sites were located on the mainstem of the Colorado River and on the Yampa, Green, Gunnison, San Juan, and Gila Rivers. Common carp (Cyprinus carpio), black bass (Micropterus sp.), and channel catfish (Ictalurus punctatus) were the targeted species. Fish were field-examined for external and internal anomalies, selected organs were weighed to compute somatic indices, and tissue and fluid samples were preserved for fish health and reproductive biomarker analyses. Composite samples of whole fish, grouped by species and gender, from each site were analyzed for organochlorine and elemental contaminants using performance-based and instrumental methods. 2,3,7,8-tetrachlorodibenzo-p-dioxin-like activity (TCDD-EQ) was measured using the H4IIE rat hepatoma cell bioassay. Selenium (Se) and mercury (Hg) concentrations were elevated throughout the CDRB, and pesticides concentrations were greatest in fish from agricultural areas in the Lower Colorado River and Gila River. Selenium concentrations exceeded toxicity thresholds for fish (>1.0 ?g/g ww) at all sites except from the Gila River at Hayden, Arizona. Mercury concentrations were elevated (>0.1 ?g/g ww) in fish from the Yampa River at Lay, Colorado; the Green River at Ouray National Wildlife Refuge (NWR), Utah and San Rafael, Utah; the San Juan River at Hogback Diversion, New Mexico; and the Colorado River at Gold Bar Canyon, Utah, Needles, California, and Imperial Dam, Arizona. Concentrations of p,p'-DDE were relatively high in fish from Arlington, Arizona (>1.0 ?g/g ww) and Phoenix, Arizona (>0.5 ?g/g ww). Concentrations of other banned pesticides including toxaphene, total chlordanes, and dieldrin were also greatest at these two sites but did not exceed toxicity thresholds. Current-use or unlisted pesticides such as dacthal, endosulfan, '-HCH, and methoxychlor were also greatest in fish from Gila River. Total polychlorinated biphenyls (PCBs; >0.11 ?g/g ww) and TCDD-EQs (>5 pg/g ww) exceeded wildlife guidelines in fish from the Gila River at Phoenix, Arizona. Hepatic ethoxyresorufin O-deethylase (EROD) activity was also relatively high in carp from the Gila River at Phoenix, Arizona and in bass from the Green River at Ouray NWR, Utah. Altered biomarkers were noted in fish throughout the CDRB. Fish from some stations responded to chronic contaminant exposure as indicated by fish health and reproductive biomarker results. Multiple fish health indicators including altered body and organ weights and high health assessment index scores may be associated with elevated Se concentrations in fish from the Colorado River at Loma, Colorado and Needles, California. Although grossly visible external or internal lesions were found on most fish from some sites, histopathological analysis determined many of these to be inflammatory responses associated with parasites. Edema, exophthalmos, and cataracts were noted in fish from sites with elevated Se concentrations. Reproductive biomarkers including gonad development and maturation, vitellogenin concentrations, and steroid hormone concentrations were anomalous in fish from the Gila River at Hayden and Phoenix, Arizona. In addition, intersex fish were found at seven of 14 sites. The intersex condition was identified in smallmouth bass (M. dolomieu), largemouth bass (M. salmoides), channel catfish, and carp and may indicate exposure to endocrine disrupting compounds. Seven of ten male smallmouth bass from the Yampa River at Lay, Colorado were intersex. Male carp, bass, and channel catfish with low concentrations of vitellogenin were common in the CDRB. Comparatively high vitellogenin concentrations (>0.2 mg/mL) were measured in male fish from the Green River at Ouray NWR, Utah and the Colorado River at Im

Scientific Investigations Report

Basic alumina flash chromatographic separation of bulk ortho-PCBs from on-ortho-PCBs, PBDEs, PCDFs, PCDDs, PCDTs, OCPs, and PCTs

Comprising nearly 100 congeners in environmental samples, PCBs are often still prevalent in concentrations exceeding 1 μg/g. To effectively measure PCBs, they are isolated as a group from other persistent organic pollutants using silica gel, Florisil, or alumina column chromatography for analysis by GC/MS or dual capillary column GC/ECD. When organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) are also targeted, PCBs are often split into two chromatographic eluates. In contrast to the major ortho-substituted PCB congeners, much lower concentrations occur for congeners of polychlorinated- dibenzo- p -dioxins (PCDDs), dibenzofurans (PCDFs), dibenzothiophenes (PCDTs), naphthalenes (PCNs), and dioxin-like non- ortho -PCBs 1 . Such co-planar compounds are usually separated from the bulk PCBs using a carbon LC 2 or reusable porous graphitic carbon HPLC column 3 eluted forward ( o -PCBs, mono- o -PCBs, then non- o -PCBs) before reversal with toluene (PCDFs and PCDDs) and additional separation with basic alumina to remove PCNs, polychlorinated diphenyl ethers (PCDEs), and residual lipid for PCDF/PCDD GC/HRMS analysis. Recently, smaller particle-size normal phase adsorbents including active basic alumina have become available along with custom-made glass columns for use in low pressure flash chromatography. With low gas pressure (< 1-2 bar) and particles 32-63 μm, flash chromatography is a rapid, inexpensive technique with enhanced resolution compared to gravity column chromatography 4 . However, few environmental researchers use the technique, but basic alumina is in the automated PowerPrep LC system for PCDFs, PCDDs, PCBs and PBDEs 5 . A flash LC column is quickly dry-packed, gives improved flow performance, and has sufficient resistance to gravity flow without a shutoff valve. Contamination from lab air, dust, and sample carryover is minimized by using high purity nitrogen, much smaller eluate volumes and blown down in tubes with high purity nitrogen. The disposable adsorbent is used only once with an inert, nonleachable, reusable and cleanable glass column with glass joints and disposable glass fiber. We evaluated basic alumina flash chromatography initially for PCBs, because Loos et al. 6 had separated 13 selected o -PCB congeners from three non- o -PCBs (77, 126, and 169) and then from PCDFs and PCDDs with eluants of 150- 200 mL each from a large 25-g basic alumina (Super 1 active) column. Because the elution properties of other PCB congeners were unknown in addition to some PBDEs, PCDTs, and other compounds, we chose to evaluate basic alumina flash chromatography comprehensively. We optimized the separation of all bulk o-PCBs from all non- o- PCBs, tested other pollutants (PBDEs, PCDTs, PCDFs and PCDDs) under similar elution conditions, and finally applied the chromatographic technique to samples known or suspected to contain complex mixtures of these.

Organohalogen Compounds

Biomonitoring of Environmental Status and Trends (BEST) Program: Environmental contaminants and their effects on fish in the Yukon River Basin

This project collected, examined, and analyzed 217 fish representing three species at 10 stations in the U.S. portion of the Yukon River Basin (YRB) from May to October 2002. Four sampling sites were located on the Yukon River; two were located on the Porcupine River, and one site was on each of the Ray, Tanana, Tolavana, and Innoko Rivers. Norther pike ( Esox lucius ), longnose sucker ( Catostomus catostomus ), and burbot ( Lota lota ) were weighed and measured, and examined in the field for external and internal lesions, and liver, spleen, and gonads were weighed to compute somatic indices. Selected tissues and fluids were collected and preserved for analysis of fish health and reproductive biomarkers. Composite samples of whole fish from each station were grouped by species and gender and analyzed for organochlorines and elemental contaminants and for dioxin-like activity using H4IIE rat hepatoma cell bioassay.

Alaska