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R.W. Gale

Publications and source records attributed to R.W. Gale.

10 recordsLinked to original sources

Semivolatile organic compounds in residential air along the Arizona - Mexico border

Concerns about indoor air quality and the potential effects on people living in these environments are increasing as more reports about the toxicities and the potential indoor air exposure levels of household-use chemicals and chemicals fromhousingandfurnishingmanufactureinairarebeingassessed. Gas chromatography/mass spectrometry was used to confirm numerous airborne contaminants obtained from the analysis of semipermeable membrane devices deployed inside of 52 homes situated along the border between Arizona and Mexico. We also describe nontarget analytes in the organochlorine pesticide fractions of 12 of these homes; this fraction is also the most likelytocontainthebroadestscopeofbioconcentratablechemicals accumulated from the indoor air. Approximately 400 individual components were identified, ranging from pesticides to a wide array of hydrocarbons, fragrances such as the musk xylenes, flavors relating to spices, aldehydes, alcohols, esters and phthalate esters, and other miscellaneous types of chemicals. The results presented in this study demonstrate unequivocally that the mixture of airborne chemicals present indoors is far more complex than previously demonstrated. ?? 2009 American Chemical Society.

Environmental Science & Technology↗

Chemical contaminants, health indicators, and reproductive biomarker responses in fish from rivers in the Southeastern United States

Largemouth bass ( Micropterus salmoides ) and common carp ( Cyprinus carpio ) were collected from 13 sites located in the Mobile (MRB), Apalachicola–Flint–Chattahoochee (ARB), Savannah (SRB), and Pee Dee (PRB) River Basins to document spatial trends in accumulative chemical contaminants, health indicators, and reproductive biomarkers. Organochlorine residues, 2,3,7,8-tetrachlorodibenzo- p -dioxin-like activity (TCDD-EQ), and elemental contaminants were measured in composite samples of whole fish, grouped by species and gender, from each site. Mercury (Hg) and polychlorinated biphenyls (PCBs) were the primary contaminants of concern. Concentrations of Hg in bass samples from all basins exceeded toxicity thresholds for piscivorous mammals (> 0.1 μg/g ww), juvenile and adult fish (> 0.2 μg/g ww), and piscivorous birds (> 0.3 μg/g ww). Total PCB concentrations in samples from the MRB, ARB, and PRB were > 480 ng/g ww and may be a risk to piscivorous wildlife. Selenium concentrations also exceeded toxicity thresholds (> 0.75 μg/g ww) in MRB and ARB fish. Concentrations of other formerly used (total chlordanes, dieldrin, endrin, aldrin, mirex, and hexachlorobenzene) and currently used (pentachlorobenzene, pentachloroanisole, dacthal, endosulfan, γ-hexachlorocyclohexane, and methoxychlor) organochlorine residues were generally low or did not exceed toxicity thresholds for fish and piscivorous wildlife. TCDD-EQs exceeded wildlife dietary guidelines (> 5 pg/g ww) in MRB and PRB fish. Hepatic ethoxyresorufin O -deethylase (EROD) activity was generally greatest in MRB bass and carp. Altered fish health indicators and reproductive biomarker were noted in individual fish, but mean responses were similar among basins. The field necropsy and histopathological examination determined that MRB fish were generally in poorer health than those from the other basins, primarily due to parasitic infestations. Tumors were found in few fish ( n = 5; 0.01%); ovarian tumors of smooth muscle origin were found in two ARB carp from the same site. Intersex gonads were identified in 47 male bass (42%) representing 12 sites and may indicate exposure to potential endocrine disrupting compounds. Comparatively high vitellogenin concentrations (> 0.35 mg/mL) in male fish from the MRB, SRB, and PRB indicate exposure to estrogenic or anti-androgenic chemicals.

Science of the Total Environment↗

A holistic passive integrative sampling approach for assessing the presence and potential impacts of waterborne environmental contaminants

As an integral part of our continuing research in environmental quality assessment approaches, we have developed a variety of passive integrative sampling devices widely applicable for use in defining the presence and potential impacts of a broad array of contaminants. The semipermeable membrane device has gained widespread use for sampling hydrophobic chemicals from water and air, the polar organic chemical integrative sampler is applicable for sequestering waterborne hydrophilic organic chemicals, the stabilized liquid membrane device is used to integratively sample waterborne ionic metals, and the passive integrative mercury sampler is applicable for sampling vapor phase or dissolved neutral mercury species. This suite of integrative samplers forms the basis for a new passive sampling approach for assessing the presence and potential toxicological significance of a broad spectrum of environmental contaminants. In a proof-of-concept study, three of our four passive integrative samplers were used to assess the presence of a wide variety of contaminants in the waters of a constructed wetland, and to determine the effectiveness of the constructed wetland in removing contaminants. The wetland is used for final polishing of secondary-treatment municipal wastewater and the effluent is used as a source of water for a state wildlife area. Numerous contaminants, including organochlorine pesticides, polycyclic aromatic hydrocarbons, organophosphate pesticides, and pharmaceutical chemicals (e.g., ibuprofen, oxindole, etc.) were detected in the wastewater. Herein we summarize the results of the analysis of the field-deployed samplers and demonstrate the utility of this holistic approach.

Chemosphere↗

Evaluation of persistent hydrophobic organic compounds in the Columbia River Basin using semipermeable-membrane devices

Persistent hydrophobic organic compounds are of concern in the Columbia River because they have been correlated with adverse effects on wildlife. We analysed samples from nine main-stem and six tributary sites throughout the Columbia River Basin (Washington and Oregon) for polychlorinated dibenzo-p-dioxins, dibenzofurans, polychlorinated biphenyls, organochlorine pesticides, and priority-pollutant polycyclic aromatic hydrocarbons. Because these compounds may have important biological consequences at aqueous concentrations well below the detection limits associated with conventional sampling methods, we used semipermeable-membrane devices to sample water and achieved parts-per-quintillion detection limits. All of these compound classes were prevalent within the basin, but concentrations of many analytes were highest in the vicinity of Portland-Vancouver, indicating that the Willamette subbasin-and perhaps the urban area in particular-is an important source of these compounds. Data collected during basin low-flow conditions in 1997 and again during basin high-flow conditions in 1998 indicate that in-stream processes such as dilution by relatively clean inflow, and flow through island hyporheic zones may be important mechanisms for attenuating dissolved concentrations of hydrophobic compounds.

Hydrological Processes↗

Comparing polychlorinated biphenyl concentrations and patterns in the Saginaw River using sediment, caged fish, and semipermeable membrane devices

Three techniques of assessing bioavailable polychlorinated biphenyls (PCBs) in the Saginaw River, MI, were compared: sediments, caged fish, and semipermeable membrane devices (SPMDs). SPMDs and caged fish were placed in the river for 28 days at five sites where sediments were also sampled. The samples were analyzed for PCB congeners to determine concentrations and patterns. Total PCB concentrations ranged from 33 to 280 ng/g (dry weight) in sediments, 46 to 290 ng/g (wet weight) in caged fish, and 77 to 790 ng/g in SPMDs. Previously reported rates of PCB accumulation by SPMDs were used to estimate aqueous concentrations from the PCB concentrations detected in the SPMDs. Sediment-water partition coefficients were used to estimate aqueous PCB concentrations from sediment. Steady-state bioconcentration factors and depuration rate constants were used to estimate dissolved PCB concentrations from caged channel catfish. Relative PCB patterns from the SPMDs, caged fish, and sediment were compared using principal components analysis. SPMD and sediment samples provide complementary information. Sediments reflect long-term accumulation and weathering, while SPMDs integrate water concentrations only during the sampling period. Because of higher water solubilities of lower-chlorinated PCBs these predominate in the SPMDs as compared to in the fish and sediments. Contaminant profile differences between caged fish and SPMDs are likely due to metabolism and depuration of certain PCB congeners by fish.Three techniques of assessing bioavailable polychlorinated biphenyls (PCBs) in the Saginaw River, Ml, were compared: sediments, caged fish, and semipermeable membrane devices (SPMDs). SPMDs and caged fish were placed in the river for 28 days at five sites where sediments were also sampled. The samples were analyzed for PCB congeners to determine concentrations and patterns. Total PCB concentrations ranged from 33 to 280 ng/g (dry weight) in sediments, 46 to 290 ng/g (wet weight) in caged fish, and 77 to 790 ng/g in SPMDs. Previously reported rates of PCB accumulation by SPMDs were used to estimate aqueous concentrations from the PCB concentrations detected in the SPMDs. Sediment-water partition coefficients were used to estimate aqueous PCB concentrations from sediment. Steady-state bioconcentration factors and depuration rate constants were used to estimate dissolved PCB concentrations from caged channel catfish. Relative PCB patterns from the SPMDs, caged fish, and sediment were compared using principal components analysis. SPMD and sediment samples provide complementary information. Sediments reflect long-term accumulation and weathering, while SPMDs integrate water concentrations only during the sampling period. Because of higher water solubilities of lower-chlorinated PCBs these predominate in the SPMDs as compared to in the fish and sediments. Contaminant profile differences between caged fish and SPMDs are likely due to metabolism and depuration of certain PCB congeners by fish.At five sites in the Saginaw River, MI, PCB concentrations were determined in the summer of 1993 using three methods: sediment analysis, concentrations in caged fish, and concentrations in semipermeable membrane devices (SPMDs). On average, total PCB concentrations in the SPMDs were twice those found in caged fish, and the SPMD-to-fish concentration ratios of di-, tri-, tetra-, and pentaCB homologues were 10.0, 3.0, 2.5, and 1.4, respectively. Average concentrations in the sediments were approximately half those in the SPMDs, and the caged fish showed a greater preponderance of higher log octanol-water partition coefficient PCBs similar to the sediment pattern. On average, the water PCB concentrations estimated from sediment concentrations were five times higher than those calculated from SPMDs and three times higher than those estimated from caged fish. The total PCB concentrations in sediment, caged fish, and SPMDs ranged 33-280, 46-290, and 77-790 ng/g, respectiv

Environmental Science & Technology↗

Evaluation of planar halogenated and polycyclic aromatic hydrocarbons in estuarine sediments using ethoxyresorufin-O-deethylase induction of H4IIE cells

Polycyclic aromatic hydrocarbons (PAHs) and planar halogenated hydrocarbons (PHHs), including polychlorinated dibenzo- p -dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) were determined in fractionated sediment extracts from the Hudson-Raritan estuary and Newark Bay, New Jersey, USA, as part of a comprehensive risk assessment. Contributions of PCDDs/PCDFs, PCBs, and PAHs to the total toxic equivalents (TEQs) were measured using an H4IIE bioassay and calculated from instrumentally determined concentrations using international toxic equivalency factors. The H4IIE TEQs of whole and fractionated extracts were compared to calculated TEQs to investigate the applicability of the bioassay approach for evaluating 7-ethoxyresorufin- O -deethylease induction by PHHs and PAHs present together in complex mixtures. Although 2,3,7,8-tetrachloro-dibenzo- p -dioxin contributed from 41 to 79% of the calculated TEQs from PCDDs/PCDFs and planar PCBs in all sediments sampled, the PAH-containing fractions accounted for >80% of the total TEQs determined either instrumentally or by bioassay. Calculated TEQs from PAHs, based on reported toxic equivalency factors for only seven PAHs, were severalfold greater than the bioassay-derived TEQs of PAH-only fractions of the sediment extracts. Significant correlations were observed between bioassay and instrumentally determined toxic equivalents in the more purified fractions but not in fractions only purified by size-exclusion or argentate chromatographies alone.

Environmental Toxicology and Chemistry↗

Considerations involved with the use of semipermeable membrane devices for monitoring environmental contaminants

Semipermeable membrane devices (SPMDs) are used with increasing frequency, and throughout the world as samplers of organic contaminants. The devices can be used to detect a variety of lipophilic chemicals in water, sediment/soil, and air. SPMDs are designed to sample nonpolar, hydrophobic chemicals. The maximum concentration factor achievable for a particular chemical is proportional to its octanol–water partition coefficient. Techniques used for cleanup of SPMD extracts for targeted analytes and for general screening by full-scan mass spectrometry do not differ greatly from techniques used for extracts of other matrices. However, SPMD extracts contain potential interferences that are specific to the membrane–lipid matrix. Procedures have been developed or modified to alleviate these potential interferences. The SPMD approach has been demonstrated to be applicable to sequestering and analyzing a wide array of environmental contaminants including organochlorine pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polychlorinated dioxins and dibenzofurans, selected organophosphate pesticides and pyrethroid insecticides, and other nonpolar organic chemicals. We present herein an overview of effective procedural steps for analyzing exposed SPMDs for trace to ultra-trace levels of contaminants sequestered from environmental matrices.

Journal of Chromatography A↗

Loading capacity and chromatographic behavior of a porous graphitic carbon column for polychlorinated biphenyls

A porous graphitic carbon column (Hypercarb) was used for the fractionation of polychlorinated biphenyls (PCBs) into classes of 2-4 ortho chlorines, 1 ortho chlorine and 0 ortho chlorine congeners. A method was developed that combined the fractionation of PCBs, polychlorinated dibenzo- p -dioxins and dibenzofurans in a variety of biotic environmental samples. Many of these samples have high concentrations of PCBs which cause fractionation problems as adsorption sites on the graphitic surface are occupied. The loading capacity of the column for PCBs was determined by injecting up to 1 mg of total PCBs and monitoring changes in chromatographic behavior of tetra-/di- ortho , mono- ortho and non- ortho substituted PCBs. Effective loading capacities were 1 mg for tetra-/di- ortho PCBs, but only 3–5 μg for non- ortho PCBs and about 2 μg for mono- ortho PCBs. Loading capacity of the PGC column for environmental fish and avian egg samples was determined to depend on the mono- ortho and non- ortho PCB levels found in these samples.

Journal of Chromatography A↗

Organochlorine contaminants in double-crested cormorants from Green Bay, WI: I. Large-scale extraction and isolation from eggs using semi-permeable membrane dialysis

A 41.3-kg sample of double-crested cormorant ( Phalacrocorax auritus ) egg contents was extracted, yielding over 2 L of egg lipid. The double-crested cormorant (DCC) egg extract, after clean-up and concentration, was intended for use in egg injection studies to determine the embryotoxicity of the organic contaminants found within the eggs. Large-scale dialysis was used as a preliminary treatment to separate the extracted contaminants from the co-extracted sample lipids. The lipid was dialyzed in 80×5 cm semi-permeable membrane devices (SPMDs) in 50-ml aliquants. After the removal of 87 g of cholesterol by freeze-fractionation, the remaining lipid carryover (56 g) was removed by 100 routine gel permeation chromatography (GPC) operations. A 41,293-g sample was thus extracted and purified to the extent that it could easily be placed at a volume of 5 ml, the volume calculated to be necessary for the egg injection study. Analyses were performed comparing contaminant concentrations in the final purified extract to those present in the original egg material, in the extract after dialysis and cholesterol removal, and in the excluded materials. Recoveries of organochlorine pesticides through dialysis and cholesterol ranged from 96% to 135%. Total polychlorinated biphenyls in the final extract were 96% of those measured in the original egg material. Analysis of excluded lipid and cholesterol indicated that 92% of the polychlorinated dibenzo-dioxins and-furans were separated into the final extract.

Archives of Environmental Contamination and Toxico↗