@article{rudd_neal_genereux_shea_nichols_2023, title={Vulnerability of wells in unconfined and confined aquifers to modern contamination from flood events}, volume={901}, ISSN={["1879-1026"]}, DOI={10.1016/j.scitotenv.2023.165729}, abstractNote={Groundwater is a primary potable water supply for coastal North Carolina (NC), but the increased intensity of extreme rainfall events and floods may exacerbate surface and subsurface processes that contribute anthropogenic chemicals to wells in the major confined aquifers of this region. We evaluated groundwater for organic chemicals of emerging concern (CEC) and the presence of tritium using flooded and not-flooded wells in the NC Department of Environmental Quality well monitoring network across the NC Coastal Plain. Flooded wells experienced standing water around the well casing at least once during the study period. Tritium concentrations, which indicate modern water presence (water recharged after 1953), were significantly greater in groundwater from flooded wells than not-flooded wells. In confined aquifers, modern water was detected at greater depths in flooded wells (206 m) than not-flooded wells (100 m). Suspect-screening high resolution mass spectrometry (HRMS) analysis of 150 groundwater samples yielded a total of 382 unique organic chemicals. Each groundwater sample contained, on average, 19 tentatively identified chemicals from the NIST 20 mass spectral database (M1) and 9 USEPA ToxCast chemicals. The number of tentatively-identified chemicals per sample was not significantly different among aquifers demonstrating the pervasive presence of the detected CECs in unconfined and confined aquifers. The presence of modern water in groundwater from flooded wells coincided with higher detection frequencies of certain organic contaminant classes, particularly pharmaceuticals, food additives, and regulated aromatic hydrocarbons. These results indicate that wells in both unconfined and confined aquifers are susceptible to modern water contamination during flood events; this finding has critical public health implications for coastal communities.}, journal={SCIENCE OF THE TOTAL ENVIRONMENT}, author={Rudd, Hayden and Neal, Andy and Genereux, David P. and Shea, Damian and Nichols, Elizabeth Guthrie}, year={2023}, month={Nov} } @article{bozinovic_feng_shea_oleksiak_2022, title={Cardiac physiology and metabolic gene expression during late organogenesis among F. heteroclitus embryo families from crosses between pollution-sensitive and -resistant parents}, volume={22}, ISSN={["2730-7182"]}, DOI={10.1186/s12862-022-01959-1}, abstractNote={The teleost fish Fundulus heteroclitus inhabit estuaries heavily polluted with persistent and bioaccumulative chemicals. While embryos of parents from polluted sites are remarkably resistant to toxic sediment and develop normally, embryos of parents from relatively clean estuaries, when treated with polluted sediment extracts, are developmentally delayed, displaying deformities characteristic of pollution-induced embryotoxicity. To gain insight into parental effects on sensitive and resistant phenotypes during late organogenesis, we established sensitive, resistant, and crossed embryo families using five female and five male parents from relatively clean and predominantly PAH-polluted estuaries each, measured heart rates, and quantified individual embryo expression of 179 metabolic genes.Pollution-induced embryotoxicity manifested as morphological deformities, significant developmental delays, and altered cardiac physiology was evident among sensitive embryos resulting from crosses between females and males from relatively clean estuaries. Significantly different heart rates among several geographically unrelated populations of sensitive, resistant, and crossed embryo families during late organogenesis and pre-hatching suggest site-specific adaptive cardiac physiology phenotypes relative to pollution exposure. Metabolic gene expression patterns (32 genes, 17.9%, at p < 0.05; 11 genes, 6.1%, at p < 0.01) among the embryo families indicate maternal pollutant deposition in the eggs and parental effects on gene expression and metabolic alterations.Heart rate differences among sensitive, resistant, and crossed embryos is a reliable phenotype for further explorations of adaptive mechanisms. While metabolic gene expression patterns among embryo families are suggestive of parental effects on several differentially expressed genes, a definitive adaptive signature and metabolic cost of resistant phenotypes is unclear and shows unexpected sensitive-resistant crossed embryo expression profiles. Our study highlights physiological and metabolic gene expression differences during a critical embryonic stage among pollution sensitive, resistant, and crossed embryo families, which may contribute to underlying resistance mechanisms observed in natural F. heteroclitus populations living in heavily contaminated estuaries.}, number={1}, journal={BMC ECOLOGY AND EVOLUTION}, author={Bozinovic, Goran and Feng, Zuying and Shea, Damian and Oleksiak, Marjorie F.}, year={2022}, month={Jan} } @article{brecht_kong_shea_xia_nichols_2022, title={Non-target and suspect-screening analyses of hydroponic soybeans and passive samplers exposed to different watershed irrigation sources}, volume={826}, ISSN={["1879-1026"]}, DOI={10.1016/j.scitotenv.2022.153754}, abstractNote={Water scarcity increases the likelihood of irrigating food crops with municipal wastewater that may pose potential dietary risks of regulated and non-regulated organic chemical uptake to edible plant tissues. Only a few studies have used high resolution mass spectrometry (HRMS) to assess the uptake of chemicals of concern into food crops. This study used non-target and suspect-screening analyses to compare total chemical features, tentatively identified chemicals (TICs), and EPA ToxCast chemicals in soybean plants and passive samplers exposed to five different irrigation sources that were collected from an agricultural watershed during mild drought conditions. Secondary-treated municipal wastewater effluent, two surface waters, two ground waters, and deionized municipal tap water were used for two hydroponic experiments: soybean roots and shoots and Composite Integrative Passive Samplers (CIPS) harvested after fourteen days of exposure and soybeans after fifty-six days. CIPS were sealed in separate glass amber jars to evaluate their efficacy to mimic chemical features, TICs, and ToxCast chemical uptake in plant roots, shoots, and beans. Total soybean biomass and water use were greatest for tap water, municipal wastewater, and surface water downstream of the municipal wastewater facility relative to groundwater samples and surface water collected upstream of the wastewater facility. ToxCast chemicals were ubiquitous across watershed irrigation sources in abundance, chemical use category, and number. Wastewater-exposed soybeans had the fewest extractable TICs in plant tissues of all irrigation sources. More ToxCast chemicals were identified in CIPS than extracted from irrigation sources by solid phase extraction. ToxCast chemicals in beans and CIPS were similar in number, chemical use category, and log Kow range. CIPS appear to serve as a useful surrogate for ToxCast chemical uptake in beans, the edible food product.}, journal={SCIENCE OF THE TOTAL ENVIRONMENT}, author={Brecht, Sarah A. and Kong, Xiang and Shea, Damian and Xia, Xin Rui and Nichols, Elizabeth Guthrie}, year={2022}, month={Jun} } @article{pietari_o'reilly_shea_kamath_2021, title={Incorporating Oil / Water Partitioning in Risk Calculations for PAHs in Petroleum Impacted Soils and Sediments}, volume={4}, ISSN={["1549-7887"]}, DOI={10.1080/15320383.2021.1913573}, abstractNote={ABSTRACT Polycyclic aromatic hydrocarbons (PAHs) may drive remediation at impacted soil or sediment sites. Current equations for calculating the PAH concentrations in soil that are protective of underlying groundwater (i.e., soil screening levels, or SSLs) generally assume a three-phase partitioning model, wherein PAHs partition among the soil matrix, porewater, and pore air. This simplified model does not consider the oil phase, and therefore overestimates the dissolved PAH concentration, and consequently, overpredicts the mobility and toxicity of PAHs to receptors especially when the source of PAHs is oil. This results in unnecessarily stringent cleanup goals and adds to the cost of treatment and management of impacted soils. Complicating factors leading to the overestimation of dissolved PAH are that oil weathering (1) decreases to the effective solubility of the lower molecular weight PAHs, and (2) the presence of the oil itself increases PAH retention in the oil phase, thereby reducing aqueous/dissolved PAH concentrations. This is particularly important when oil is both the source and the factor controlling its solubility. In this paper, we have incorporated additional partitioning factors into existing SSL equations to capture the impact of oil weathering on PAH partitioning: The oil-water partitioning coefficient (KOIL ) for crude oils was measured at different stages of weathering using a passive sampling device (PSD). Results confirm that current methods for deriving SSLs are highly conservative and that the aqueous concentrations and mobility of PAHs are lower in soils and sediments that contain weathered oils. Thus, the mobility of PAHs in historically impacted soils is much lower than what is assumed when calculating SSLs for soil-leaching-to-groundwater scenarios.}, journal={SOIL & SEDIMENT CONTAMINATION}, author={Pietari, Jaana and O'Reilly, Kirk and Shea, Damian and Kamath, Roopa}, year={2021}, month={Apr} } @article{bozinovic_shea_feng_hinton_sit_oleksiak_2021, title={PAH-pollution effects on sensitive and resistant embryos: Integrating structure and function with gene expression}, volume={16}, ISSN={["1932-6203"]}, DOI={10.1371/journal.pone.0249432}, abstractNote={Polycyclic aromatic hydrocarbons (PAHs) are among the most widespread natural and anthropogenic pollutants, and some PAHs are proven developmental toxicants. We chemically characterized clean and heavily polluted sites and exposed fish embryos to PAH polluted sediment extracts during four critical developmental stages. Embryos were collected from Fundulus heteroclitus populations inhabiting the clean and heavily polluted Superfund estuary. Embryos of parents from the clean sites are sensitive to PAH pollutants while those of parents from the heavily polluted site are resistant. Chemical analysis of embryos suggests PAH accumulation and pollution-induced toxicity among sensitive embryos during development that ultimately kills all sensitive embryos before hatching, while remarkably, the resistant embryos develop normally. The adverse effects on sensitive embryos are manifested as developmental delays, reduced heart rates, and severe heart, liver, and kidney morphological abnormalities. Gene expression analysis of early somitogenesis, heartbeat initiation, late organogenesis, and pre-hatching developmental stages reveals genes whose expression significantly differs between sensitive and resistant embryo populations and helps to explain mechanisms of sensitivity and resistance to polluted environments during vertebrate animal development.}, number={4}, journal={PLOS ONE}, author={Bozinovic, Goran and Shea, Damian and Feng, Zuying and Hinton, David and Sit, Tim and Oleksiak, Marjorie F.}, year={2021}, month={Apr} } @article{hedgespeth_mccord_phillips_strynar_shea_nichols_2021, title={Suspect-screening analysis of a coastal watershed before and after Hurricane Florence using high-resolution mass spectrometry}, volume={782}, ISSN={["1879-1026"]}, DOI={10.1016/j.scitotenv.2021.146862}, abstractNote={On September 14, 2018, Hurricane Florence delivered ~686 mm rainfall to a 106 km2 watershed in coastal North Carolina, USA. A forested land treatment site comprises one third of the watershed wherein municipal wastewater effluent is spray-irrigated onto 8.9 km2 of forest. This communication provides insight for land treatment function under excess water duress as well as changes in organic chemical composition in on- and off-site waters before (June 2018) and after (September & December 2018) Hurricane Florence's landfall. We compare the numbers and relative abundances of chemical features detected using suspect screening high resolution mass spectrometry in waste-, ground-, and surface water samples. Values for upstream and receiving waters in September were lower than for sampling events in June and December, indicating an expected dilution effect across the watershed. Chemical diversity was greatest for all surface water samples in December, but only upstream surface water showed a dramatic five-fold increase in relative chemical abundance. Chemical abundance in on-site water and downstream surface water was equal to or lower than the September storm dilution effect. These data suggest that the land treatment system is functionally and hydrologically robust to extreme storm events and contributed to dilution of upstream chemical reservoirs for downstream receiving waters for months after the storm. Similar systems may embody one water reuse strategy robust to the increasing occurrence of extreme precipitation events.}, journal={SCIENCE OF THE TOTAL ENVIRONMENT}, author={Hedgespeth, Melanie L. and McCord, James P. and Phillips, Katherine A. and Strynar, Mark J. and Shea, Damian and Nichols, Elizabeth Guthrie}, year={2021}, month={Aug} } @article{cope_bergeron_archambault_jones_beaty_lazaro_shea_callihan_rogers_2021, title={Understanding the influence of multiple pollutant stressors on the decline of freshwater mussels in a biodiversity hotspot}, volume={773}, DOI={10.1016/j.scitotenv.2020.144757}, abstractNote={The Clinch River watershed of the upper Tennessee River Basin of Virginia and Tennessee, USA supports one of North America's greatest concentrations of freshwater biodiversity, including 46 extant species of native freshwater mussels (Order Unionida), 20 of which are protected as federally endangered. Despite the global biological significance of the Clinch River, mussel populations are declining in some reaches, both in species richness and abundance. The aim of this study was to evaluate the exposure of adult resident mussels to a suite of inorganic and organic contaminant stressors in distinct sections of the Clinch River that encompassed a range of mussel abundance and health. To provide insight into the potential role of pollutants in the decline of mussels, including within a previously documented “zone of mussel decline”, the mainstem Clinch River (8 sites) and its tributaries (4 sites) were examined over two consecutive years. We quantified and related metals and organic contaminant concentrations in mussels to their associated habitat compartments (bed sediment, suspended particulate sediment, pore water, and surface water). We found that concentrations of organic contaminants in resident mussels, particularly the suite of 42 polycyclic aromatic hydrocarbons (PAHs) analyzed, were related to PAH concentrations in all four habitat (media) compartments. Further, PAH concentrations in mussel tissue (range 37.8–978.1 ng/g dry weight in 2012 and 194.3–1073.7 ng/g dry weight in 2013) were negatively related to the spatial pattern in mussel densities (rs = −0.64, p ≤ 0.05 in 2012 and rs = −0.83, p ≤ 0.05 in 2013) within the river, and were highest in the “zone of mussel decline”. In contrast, the suite of 22 metals analyzed in resident mussels were largely unrelated to the spatial pattern of variation of metals in the four habitat compartments except for Manganese (Mn; range 3630.5-23,749.2 μg/g dry weight in 2012 and 1540.4-12,605.8 μg/g dry weight in 2013) in surface water (rs = 0.58, p < 0.1) and pore water (rs = 0.76, p ≤ 0.05). This study revealed that PAHs and Mn are important pollutant stressors to mussels in the Clinch River and that they are largely being delivered through the Guest River tributary watershed. Accordingly, future conservation and management efforts would benefit by identifying, and ideally mitigating, the sources of PAHs, Mn, and other current or legacy mining-associated pollutants to the mainstem river and its tributaries.}, journal={SCIENCE OF THE TOTAL ENVIRONMENT}, author={Cope, W. Gregory and Bergeron, Christine M. and Archambault, Jennifer M. and Jones, Jess W. and Beaty, Braven and Lazaro, Peter R. and Shea, Damian and Callihan, Jody L. and Rogers, Jennifer J.}, year={2021}, month={Jun}, pages={144757} } @article{xiang_wang_zhang_ding_luo_tao_ling_shea_chen_2020, title={Effect of silver nanoparticles on gill membranes of common carp: Modification of fatty acid profile, lipid peroxidation and membrane fluidity}, volume={256}, ISSN={["1873-6424"]}, DOI={10.1016/j.envpol.2019.113504}, abstractNote={Although the toxicity of silver nanoparticles (AgNPs) in aquatic organisms has been extensively investigated, the mechanism by which AgNPs damage membranes remains unclear. This study investigated the toxic effects of a series of sub-lethal concentrations of AgNPs on the membranes of freshwater carp (Cyprinus carpio) gills, based on changes in membrane fatty acid (FA) profile, membrane fluidity, membrane lipid peroxidation, and histopathology. Most of the FAs in fish gill membrane was not significantly affected by exposure to multiple AgNPs concentrations, only few significant changes occurred in some specific FAs species at a high concentration of AgNPs exposure. In particular, high concentrations of AgNPs significantly decreased the proportions of two important long-chain n-3 series polyunsaturated FAs (C20: 5n3, and C22: 6n3), resulting in a decreased ratio of n-3 polyunsaturated FAs to n-6 polyunsaturated FAs (Σn-3UFA/Σn-6UFA). The AgNPs also caused a dose-dependent decrease in fish gill membrane fluidity, increased the level of lipid peroxidation, and inhibited Na+/K+-ATPase enzyme activity. Further histopathological examination revealed that exposure to AgNPs can cause toxic responses in the lamellae, including the thinning of the basement membrane, malformation, and inflammation. Together, the results suggest that the mechanism of AgNPs membrane toxicity involves the oxidization of long-chain omega-3 unsaturated FAs to saturated FAs via lipid peroxidation, resulting in, decreased membrane fluidity and ultimately the destruction of the normal physiological function of the fish gill membrane. The findings contribute significantly to our understanding of nanoparticle-induced membrane toxicity and potential risks in aquatic environments.}, journal={ENVIRONMENTAL POLLUTION}, author={Xiang, Qian-Qian and Wang, Di and Zhang, Ji-Lai and Ding, Cheng-Zhi and Luo, Xia and Tao, Juan and Ling, Jian and Shea, Damian and Chen, Li-Qiang}, year={2020}, month={Jan} } @article{singh_chao_phillips_xia_shea_sobus_schymanski_ulrich_2020, title={Expanded coverage of non-targeted LC-HRMS using atmospheric pressure chemical ionization: a case study with ENTACT mixtures}, volume={412}, ISSN={["1618-2650"]}, DOI={10.1007/s00216-020-02716-3}, abstractNote={Non-targeted analysis (NTA) is a rapidly evolving analytical technique with numerous opportunities to improve and expand instrumental and data analysis methods. In this work, NTA was performed on eight synthetic mixtures containing 1264 unique chemical substances from the U.S. Environmental Protection Agency’s Non-Targeted Analysis Collaborative Trial (ENTACT). These mixtures were analyzed by atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI) using both positive and negative polarities for a total of four modes. Out of the 1264 ENTACT chemical substances, 1116 were detected in at least one ionization mode, 185 chemicals were detected using all four ionization modes, whereas 148 were not detected. Forty-four chemicals were detected only by APCI, and 181 were detected only by ESI. Molecular descriptors and physicochemical properties were used to assess which ionization type was preferred for a given compound. One ToxPrint substructure (naphthalene group) was found to be enriched in compounds only detected using APCI, and eight ToxPrints (e.g., several alcohol moieties) were enriched in compounds only detected using ESI. Examination of physicochemical parameters for ENTACT chemicals suggests that those with higher aqueous solubility preferentially ionized by ESI−. While ESI typically detects a larger number of compounds, APCI offers chromatograms with less background, fewer co-elutions, and additional chemical space coverage, suggesting both should be considered for broader coverage in future NTA research.}, number={20}, journal={ANALYTICAL AND BIOANALYTICAL CHEMISTRY}, author={Singh, Randolph R. and Chao, Alex and Phillips, Katherine A. and Xia, Xin Rui and Shea, Damian and Sobus, Jon R. and Schymanski, Emma L. and Ulrich, Elin M.}, year={2020}, month={Aug}, pages={4931–4939} } @article{hedgespeth_gibson_mccord_strynar_shea_nichols_2019, title={Suspect screening and prioritization of chemicals of concern (COCs) in a forest-water reuse system watershed}, volume={694}, ISSN={0048-9697}, url={http://dx.doi.org/10.1016/j.scitotenv.2019.07.184}, DOI={10.1016/j.scitotenv.2019.07.184}, abstractNote={Much research has assessed organic chemicals of concern (COCs) in municipal wastewater and receiving waters, but few studies have examined COCs in land treatment systems. Many prior studies have implemented targeted methods that quantify a relatively small fraction of COCs present in wastewater and receiving waters. This study used suspect screening to assess chemical features in ground- and surface waters from a watershed where secondary-treated wastewater is irrigated onto 900 ha of temperate forest, offering a more holistic view of chemicals that contribute to the exposome. Chemical features were prioritized by abundance and ToxPi scoring across seasonal sampling events to determine if the forest-water reuse system contributed to the chemical exposome of ground- and surface waters. The number of chemical features detected in wastewater was usually higher than on- and off-site ground- and surface waters; in wastewater, chemical features trended with precipitation in which greater numbers of features were detected in months with low precipitation. The number of chemical features detected in off- and on-site waters was similar. The lower overlap between chemical features found in wastewater and downstream surface waters, along with the similar numbers of features being detected in upstream and downstream surface waters, suggests that though wastewater may be a source of chemicals to ground and surface waters on-site, dissipation of wastewater-derived features (in number and peak area abundance) likely occurs with limited off-site surface water export by the forested land treatment system. Further, the numbers of features detected on site and the overlap between wastewater and surface waters did not increase during periods of low rainfall, counter to our initial expectations. The chemical features tentatively identified in this watershed appear common to features identified in other studies, warranting further examination on the potential for resulting impacts of these on humans and the environment.}, journal={Science of The Total Environment}, publisher={Elsevier BV}, author={Hedgespeth, Melanie L. and Gibson, Nancy and McCord, James and Strynar, Mark and Shea, Damian and Nichols, Elizabeth Guthrie}, year={2019}, month={Dec}, pages={133378} } @article{adebambo_shea_fry_2018, title={Cadmium disrupts signaling of the hypoxia-inducible (HIF) and transforming growth factor (TGF-beta) pathways in placental JEG-3 trophoblast cells via reactive oxygen species}, volume={342}, ISSN={["1096-0333"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-85041525284&partnerID=MN8TOARS}, DOI={10.1016/j.taap.2018.01.010}, abstractNote={Epidemiologic studies indicate an association between exposure to cadmium (Cd) and placental-related pregnancy disorders. While a precise mechanism is unknown, oxidative imbalance and dysregulation of the hypoxia inducible factor (HIF) and transforming growth factor beta (TGF-β) pathways have been implicated in placental disease pathogenesis. Here we investigated key oxidative and placentation pathways in JEG-3 placental trophoblast cells treated with Cd alone, environmental water samples predominated by Cd with low concentrations of other metals (e.g. inorganic arsenic (iAs)) collected from a waste-site, and a matched mixture of Cd and iAs prepared in the laboratory. The induction of cytosolic reactive oxygen species (ROS), expression of metallothionein (MT) isoforms, HIF1α and downstream targets, and expression of TGFβ pathway-associated genes and proteins were assessed. Additionally, the effect of pre-treatment with the antioxidant N-acetyl cysteine (NAC) on ROS generation and effects on HIF, MT and TGF-β signaling pathways was examined. Cd and Cd-mixture treated cells displayed higher levels of ROSs with accompanying disruption of HIF and TGFβ pathway signaling versus controls, with the Cd-mixture eliciting a greater effect. Conversely, pretreatment with NAC reduced Cd-induced ROS production and disruption of HIF, MT and TGFβ pathway signaling. The results indicate that treatment of placental trophoblast cells with Cd results in increased production of ROSs that disrupt placentation pathways involved in disease pathogenesis. Also, co-occurrence of Cd with other toxic metals, particularly arsenic, may induce detrimental health effects that are currently underestimated when analyzed as single metals.}, journal={TOXICOLOGY AND APPLIED PHARMACOLOGY}, author={Adebambo, Oluwadamilare A. and Shea, Damian and Fry, Rebecca C.}, year={2018}, month={Mar}, pages={108–115} } @article{mceachran_hedgespeth_newton_mcmahen_strynar_shea_nichols_2018, title={Comparison of emerging contaminants in receiving waters downstream of a conventional wastewater treatment plant and a forest-water reuse system}, volume={25}, ISSN={0944-1344 1614-7499}, url={http://dx.doi.org/10.1007/s11356-018-1505-5}, DOI={10.1007/s11356-018-1505-5}, abstractNote={Forest-water reuse (FWR) systems treat municipal, industrial, and agricultural wastewaters via land application to forest soils. Previous studies have shown that both large-scale conventional wastewater treatment plants (WWTPs) and FWR systems do not completely remove many contaminants of emerging concern (CECs) before release of treated wastewater. To better characterize CECs and potential for increased implementation of FWR systems, FWR systems need to be directly compared to conventional WWTPs. In this study, both a quantitative, targeted analysis and a nontargeted analysis were utilized to better understand how CECs release to waterways from an FWR system compared to a conventional treatment system. Quantitatively, greater concentrations and total mass load of CECs was exhibited downstream of the conventional WWTP compared to the FWR. Average summed concentrations of 33 targeted CECs downstream of the conventional system were ~ 1000 ng/L and downstream of the FWR were ~ 30 ng/L. From a nontargeted chemical standpoint, more tentatively identified chemicals were present, and at a greater relative abundance, downstream of the conventional system as well. Frequently occurring contaminants included phthalates, pharmaceuticals, and industrial chemicals. These data indicate that FWR systems represent a sustainable wastewater treatment alternative and that emerging contaminant release to waterways was lower at a FWR system than a conventional WWTP.}, number={13}, journal={Environmental Science and Pollution Research}, publisher={Springer Science and Business Media LLC}, author={McEachran, Andrew D. and Hedgespeth, Melanie L. and Newton, Seth R. and McMahen, Rebecca and Strynar, Mark and Shea, Damian and Nichols, Elizabeth Guthrie}, year={2018}, month={Feb}, pages={12451–12463} } @article{buttermore_cope_kwak_cooney_shea_lazaro_2018, title={Contaminants in tropical island streams and their biota}, volume={161}, ISSN={["1096-0953"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-85038027709&partnerID=MN8TOARS}, DOI={10.1016/j.envres.2017.11.053}, abstractNote={Environmental contamination is problematic for tropical islands due to their typically dense human populations and competing land and water uses. The Caribbean island of Puerto Rico (USA) has a long history of anthropogenic chemical use, and its human population density is among the highest globally, providing a model environment to study contaminant impacts on tropical island stream ecosystems. Polycyclic Aromatic Hydrocarbons, historic-use chlorinated pesticides, current-use pesticides, Polychlorinated Biphenyls (PCBs), and metals (mercury, cadmium, copper, lead, nickel, zinc, and selenium) were quantified in the habitat and biota of Puerto Rico streams and assessed in relation to land-use patterns and toxicological thresholds. Water, sediment, and native fish and shrimp species were sampled in 13 rivers spanning broad watershed land-use characteristics during 2009-2010. Contrary to expectations, freshwater stream ecosystems in Puerto Rico were not severely polluted, likely due to frequent flushing flows and reduced deposition associated with recurring flood events. Notable exceptions of contamination were nickel in sediment within three agricultural watersheds (range 123-336ppm dry weight) and organic contaminants (PCBs, organochlorine pesticides) and mercury in urban landscapes. At an urban site, PCBs in several fish species (Mountain Mullet Agonostomus monticola [range 0.019-0.030ppm wet weight] and American Eel Anguilla rostrata [0.019-0.031ppm wet weight]) may pose human health hazards, with concentrations exceeding the U.S. Environmental Protection Agency (EPA) consumption limit for 1 meal/month. American Eel at the urban site also contained dieldrin (range < detection-0.024ppm wet weight) that exceeded the EPA maximum allowable consumption limit. The Bigmouth Sleeper Gobiomorous dormitor, an important piscivorus sport fish, accumulated low levels of organic contaminants in edible muscle tissue (due to its low lipid content) and may be most suitable for human consumption island-wide; only mercury at one site (an urban location) exceeded EPA's consumption limit of 3 meals/month for this species. These results comprise the first comprehensive island-wide contaminant assessment of Puerto Rico streams and biota and provide natural resource and public health agencies here and in similar tropical islands elsewhere with information needed to guide ecosystem and fisheries conservation and management and human health risk assessment.}, journal={ENVIRONMENTAL RESEARCH}, author={Buttermore, Elissa N. and Cope, W. Gregory and Kwak, Thomas J. and Cooney, Patrick B. and Shea, Damian and Lazaro, Peter R.}, year={2018}, month={Feb}, pages={615–623} } @article{hardison_holland_darius_chinain_tester_shea_bogdanoff_morris_quintana_loeffler_et al._2018, title={Investigation of ciguatoxins in invasive lionfish from the greater caribbean region: Implications for fishery development}, volume={13}, ISSN={["1932-6203"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-85048785671&partnerID=MN8TOARS}, DOI={10.1371/journal.pone.0198358}, abstractNote={Lionfish, native to reef ecosystems of the tropical and sub-tropical Indo-Pacific, were introduced to Florida waters in the 1980s, and have spread rapidly throughout the northwestern Atlantic, Caribbean Sea and the Gulf of Mexico. These invasive, carnivorous fish significantly reduce other fish and benthic invertebrate biomass, fish recruitment, and species richness in reef ecosystems. Fisheries resource managers have proposed the establishment of a commercial fishery to reduce lionfish populations and mitigate adverse effects on reef communities. The potential for a commercial fishery for lionfish is the primary reason to identify locations where lionfish accumulate sufficient amounts of ciguatoxin (CTX) to cause ciguatera fish poisoning (CFP), the leading cause of non-bacterial seafood poisoning associated with fish consumption. To address this issue, an initial geographic assessment of CTX toxicity in lionfish from the Caribbean and Gulf of Mexico was conducted. Lionfish samples (n = 293) were collected by spearfishing from 13 locations (74 sampling sites) around the Caribbean and Gulf of Mexico between 2012 and 2015. The highest frequencies of lionfish containing measurable CTX occurred in areas known to be high-risk regions for CFP in the central to eastern Caribbean (e.g., 53% British Virgin Islands and 5% Florida Keys). Though measurable CTX was found in some locations, the majority of the samples (99.3%) contained CTX concentrations below the United States Food and Drug Administration guidance level of 0.1 ppb Caribbean ciguatoxin-1 (C-CTX-1) equivalents (eq.). Only 0.7% of lionfish tested contained more than 0.1 ppb C-CTX-1 eq. As of 2018, there has been one suspected case of CFP from eating lionfish. Given this finding, current risk reduction techniques used to manage CTX accumulating fish are discussed.}, number={6}, journal={PLOS ONE}, author={Hardison, D. Ransom and Holland, William C. and Darius, H. Taiana and Chinain, Mireille and Tester, Patricia A. and Shea, Damian and Bogdanoff, Alex K. and Morris, James A., Jr. and Quintana, Harold A. Flores and Loeffler, Christopher R. and et al.}, year={2018}, month={Jun} } @article{zhang_zhou_pei_xiang_chang_ling_shea_chen_2018, title={Metabolic profiling of silver nanoparticle toxicity in Microcystis aeruginosa}, volume={5}, ISSN={["2051-8161"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-85056476913&partnerID=MN8TOARS}, DOI={10.1039/c8en00738a}, abstractNote={The widespread use of silver nanoparticles (AgNPs) is becoming a growing concern because of the risk they pose to the ecological environment and human health. Unfortunately, little is known about how AgNPs' toxicity affects the mechanisms of metabolite shift in aquatic organisms. The aim of this work is thus to study systematically the cellular metabolism of the cyanobacteria Microcystis aeruginosa upon exposure to AgNPs by using metabolomics based on non-targeted liquid chromatography and mass spectrometry. The results reveal that a total of 97 biochemical metabolites and 16 specific metabolic pathways are significantly altered by exposure to AgNPs, many of which are associated with cellular stress response. Importantly, a metabolic analysis identified some novel metabolic pathways that are specifically regulated by AgNPs, including arginine and proline metabolism, indole alkaloid biosynthesis, and phospholipid metabolism (phosphatidylinositol-4,5-bisphosphate). Further examination revealed that exposure to AgNPs elevates superoxide dismutase activity and malondialdehyde generation, damages the thylakoids, and interrupts the endocytosis process in algae cells. Together, the manifestation of differential metabolic profiles combined with the perturbation of physiological indicators upon AgNP exposure is taken as evidence of damage to photosynthesis and membranes. These results provide holistic information about complex disturbances in metabolite profiles of M. aeruginosa upon exposure to AgNPs and provide new insights into the mechanisms of AgNPs' toxicity in the aquatic environment.}, number={11}, journal={ENVIRONMENTAL SCIENCE-NANO}, author={Zhang, Ji Lai and Zhou, Zhi Peng and Pei, Ying and Xiang, Qian Qian and Chang, Xue Xiu and Ling, Jian and Shea, Damian and Chen, Li Qiang}, year={2018}, month={Nov}, pages={2519–2530} } @book{archambault_prochazka_cope_shea_lazaro_2018, title={Polycyclic aromatic hydrocarbons in surface waters, sediments, and unionid mussels: relation to road crossings and implications for chronic mussel exposure}, volume={810}, ISSN={0018-8158 1573-5117}, url={http://dx.doi.org/10.1007/S10750-017-3101-Y}, DOI={10.1007/s10750-017-3101-y}, number={1}, journal={Hydrobiologia}, publisher={Springer International Publishing}, author={Archambault, J.M. and Prochazka, S.T. and Cope, W.G. and Shea, D. and Lazaro, P.R.}, year={2018}, pages={465–476} } @article{grieshaber_penland_kwak_cope_heise_law_shea_aday_rice_kullman_et al._2018, title={Relation of contaminants to fish intersex in riverine sport fishes}, volume={643}, ISSN={0048-9697}, url={http://dx.doi.org/10.1016/J.SCITOTENV.2018.06.071}, DOI={10.1016/j.scitotenv.2018.06.071}, abstractNote={Endocrine active compounds (EACs) are pollutants that have been recognized as an emerging and widespread threat to aquatic ecosystems globally. Intersex, the presence of female germ cells within a predominantly male gonad, is considered a biomarker of endocrine disruption caused by EACs. We measured a suite of EACs and assessed their associated impacts on fish intersex occurrence and severity in a large, regulated river system in North Carolina and South Carolina, USA. Our specific objective was to determine the relationship of contaminants in water, sediment, and fish tissue with the occurrence and severity of the intersex condition in wild, adult black bass (Micropterus), sunfish (Lepomis), and catfish (Ictaluridae) species at 11 sites located on the Yadkin-Pee Dee River. Polycyclic aromatic hydrocarbons (PAHs), ethinylestradiol (EE2), and heavy metals were the most prevalent contaminants that exceeded effect levels for the protection of aquatic organisms. Fish intersex condition was most frequently observed and most severe in black basses and was less frequently detected and less severe in sunfishes and catfishes. The occurrence of the intersex condition in fish showed site-related effects, rather than increasing longitudinal trends from upstream to downstream. Mean black bass and catfish tissue contaminant concentrations were higher than that of sunfish, likely because of the latter's lower trophic position in the food web. Principal component analysis identified waterborne PAHs as the most correlated environmental contaminant with intersex occurrence and severity in black bass and sunfish. As indicated by the intersex condition, EACs have adverse but often variable effects on the health of wild sport fishes in this river, likely due to fluctuations in EAC inputs and the dynamic nature of the riverine system. These findings enhance the understanding of the relationship between contaminants and fish health and provide information to guide ecologically comprehensive conservation and management decisions.}, journal={Science of The Total Environment}, publisher={Elsevier BV}, author={Grieshaber, C.A. and Penland, T.N. and Kwak, T.J. and Cope, W.G. and Heise, R.J. and Law, J.M. and Shea, Damian and Aday, D.D. and Rice, J.A. and Kullman, S.W. and et al.}, year={2018}, month={Dec}, pages={73–89} } @article{powell_cope_leprevost_augspurger_mccarthy_shea_2017, title={A Retrospective Analysis of Agricultural Herbicides in Surface Water Reveals Risk Plausibility for Declines in Submerged Aquatic Vegetation}, volume={5}, ISSN={["2305-6304"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-85029532128&partnerID=MN8TOARS}, DOI={10.3390/toxics5030021}, abstractNote={The Albemarle-Pamlico Estuarine System (APES) is the second largest estuarine system within the mainland of the United States and is estimated to have lost about half of its submerged aquatic vegetation (SAV) over the past several decades. The issue of herbicide runoff and subsequent toxic effects to SAV is important because of the extensive agricultural production that occurs in the APES region. The aim of this study was to conduct a retrospective analysis of herbicide influx to waters of the APES region during the time period of documented SAV declines and to compare the measured concentrations to SAV toxicity thresholds and changes in agricultural land use. Surface water grab samples were collected at 26 sites in the APES region during May through July 2000. The most consistently measured herbicides were alachlor, atrazine, and metolachlor with geometric mean concentrations ranging from 29 to 2463 ng/L for alachlor, 14 to 7171 ng/L for atrazine, and 17 to 5866 ng/L for metolachlor. Concentrations of alachlor, atrazine, and metolachlor measured in water samples from the APES region in 2000 exceeded several of the established benchmarks, standards, or guidelines for protection of aquatic plants. Although this evaluation was of point-in-time herbicide samples (year 2000) and not analyzed for all possible herbicides used at the time, they were taken during the period of SAV declines, reveal the plausibility of exposure risk to SAV, and suggest that herbicide runoff should be studied along with other variables that influence SAV growth and distribution in future studies.}, number={3}, journal={TOXICS}, publisher={MDPI AG}, author={Powell, Kelly W. and Cope, W. Gregory and LePrevost, Catherine E. and Augspurger, Tom and McCarthy, Annette M. and Shea, Damian}, year={2017}, month={Sep} } @article{mceachran_shea_nichols_2017, title={Pharmaceuticals in a temperate forest-water reuse system}, volume={581-582}, ISSN={0048-9697}, url={http://dx.doi.org/10.1016/j.scitotenv.2016.12.185}, DOI={10.1016/j.scitotenv.2016.12.185}, abstractNote={Forest-water reuse systems infiltrate municipal, industrial, and agricultural wastewaters through forest soils to shallow aquifers that ultimately discharge to surface waters. Their ability to mitigate regulated nutrients, metals, and organic chemicals is well known, but the fate of non-regulated chemicals in these systems is largely unstudied. This study quantified 33 pharmaceuticals and personal care products (PPCPs) in soils, groundwaters, and surface waters in a 2000-hectare forest that receives ~ 1200 mm/year of secondary-treated, municipal wastewater in addition to natural rainfall (~ 1300 mm/year). This forest-water reuse system does contribute PPCPs to soils, groundwater, and surface waters. PPCPs were more abundant in soils versus underlying groundwater by an order of magnitude (5–10 ng/g summed PPCPs in soil and 50–100 ng/L in groundwater) and the more hydrophobic chemicals were predominant in soil over water. PPCP concentrations in surface waters were greater at the onset of significant storm events and during low-rainfall periods when total summed PPCPs were > 80 ng/L, higher than the annual average. With few exceptions, the margins of exposure for PPCPs in groundwater and surface waters were several orders of magnitude above values indicative of human health risk.}, journal={Science of The Total Environment}, publisher={Elsevier BV}, author={McEachran, Andrew D. and Shea, Damian and Nichols, Elizabeth Guthrie}, year={2017}, month={Mar}, pages={705–714} } @article{archambault_bergeron_cope_lazaro_leonard_shea_2016, title={Assessing toxicity of contaminants in riverine suspended sediments to freshwater mussels}, volume={36}, ISSN={0730-7268}, url={http://dx.doi.org/10.1002/etc.3540}, DOI={10.1002/etc.3540}, abstractNote={The Clinch River in Virginia and Tennessee, USA, is well known for its diverse native freshwater mussel assemblages; however, notable declines in mussel populations in recent decades have prompted much concern and subsequent research. The authors examined the toxicity of recently deposited sediments on juveniles of the freshwater mussel Epioblasma brevidens by collecting time‐integrated sediment samples from the water column with sediment traps from 11 sites in the Clinch River basin, including 6 sites within an 88‐km reach deemed a “mussel zone of decline.” Mussels were exposed to the riverine sediments and to 3 control sediments for 28 d; survival, shell length, and biomass were then assessed. Sediment treatment (i.e., river location) had a significant effect on mussel survival (p < 0.01) and biomass (p = 0.02) but did not affect length (p = 0.37), and sediments from 2 of the tributaries were the most toxic. Inorganic and organic analyses of sediments indicated the presence of metals and polycyclic aromatic hydrocarbons at all sites. Manganese was negatively correlated with mussel survival and biomass, as was ammonia with survival and total organic carbon with biomass. Current land uses in the watershed indicate that fossil fuel mining and agriculture may be associated with elevated manganese and ammonia, respectively. The authors found that sediments collected with sediment traps over relatively short deployment durations can help elucidate recent contaminant influx and its potential for inducing toxicity in benthic organisms. Environ Toxicol Chem 2017;36:395–407. © 2016 SETAC}, number={2}, journal={Environmental Toxicology and Chemistry}, publisher={Wiley}, author={Archambault, Jennifer M. and Bergeron, Christine M. and Cope, W. Gregory and Lazaro, Peter R. and Leonard, Jeremy A. and Shea, Damian}, year={2016}, month={Aug}, pages={395–407} } @article{hardison_holland_mccall_bourdelais_baden_darius_chinain_tester_shea_quintana_et al._2016, title={Fluorescent Receptor Binding Assay for Detecting Ciguatoxins in Fish}, volume={11}, ISSN={["1932-6203"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-84963831110&partnerID=MN8TOARS}, DOI={10.1371/journal.pone.0153348}, abstractNote={Ciguatera fish poisoning is an illness suffered by > 50,000 people yearly after consumption of fish containing ciguatoxins (CTXs). One of the current methodologies to detect ciguatoxins in fish is a radiolabeled receptor binding assay (RBA(R)). However, the license requirements and regulations pertaining to radioisotope utilization can limit the applicability of the RBA(R) in certain labs. A fluorescence based receptor binding assay (RBA(F)) was developed to provide an alternative method of screening fish samples for CTXs in facilities not certified to use radioisotopes. The new assay is based on competition binding between CTXs and fluorescently labeled brevetoxin-2 (BODIPY®- PbTx-2) for voltage-gated sodium channel receptors at site 5 instead of a radiolabeled brevetoxin. Responses were linear in fish tissues spiked from 0.1 to 1.0 ppb with Pacific ciguatoxin-3C (P-CTX-3C) with a detection limit of 0.075 ppb. Carribean ciguatoxins were confirmed in Caribbean fish by LC-MS/MS analysis of the regional biomarker (C-CTX-1). Fish (N = 61) of six different species were screened using the RBA(F). Results for corresponding samples analyzed using the neuroblastoma cell-based assay (CBA-N2a) correlated well (R2 = 0.71) with those of the RBA(F), given the low levels of CTX present in positive fish. Data analyses also showed the resulting toxicity levels of P-CTX-3C equivalents determined by CBA-N2a were consistently lower than the RBA(F) affinities expressed as % binding equivalents, indicating that a given amount of toxin bound to the site 5 receptors translates into corresponding lower cytotoxicity. Consequently, the RBA(F), which takes approximately two hours to perform, provides a generous estimate relative to the widely used CBA-N2a which requires 2.5 days to complete. Other RBA(F) advantages include the long-term (> 5 years) stability of the BODIPY®- PbTx-2 and having similar results as the commonly used RBA(R). The RBA(F) is cost-effective, allows high sample throughput, and is well-suited for routine CTX monitoring programs.}, number={4}, journal={PLOS ONE}, author={Hardison, D. Ransom and Holland, William C. and McCall, Jennifer R. and Bourdelais, Andrea J. and Baden, Daniel G. and Darius, H. Taiana and Chinain, Mireille and Tester, Patricia A. and Shea, Damian and Quintana, Harold A. Flores and et al.}, year={2016}, month={Apr} } @article{adrion_singleton_nakamura_shea_aitken_2016, title={Improving Polycyclic Aromatic Hydrocarbon Biodegradation in Contaminated Soil Through Low-Level Surfactant Addition After Conventional Bioremediation}, volume={33}, ISSN={["1557-9018"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-84987652907&partnerID=MN8TOARS}, DOI={10.1089/ees.2016.0128}, abstractNote={Efficacy of bioremediation for soil contaminated with polycyclic aromatic hydrocarbons (PAHs) may be limited by the fractions of soil-bound PAHs that are less accessible to PAH-degrading microorganisms. In previous test-tube-scale work, submicellar doses of nonionic surfactants were screened for their ability to enhance the desorption and biodegradation of residual PAHs in soil after conventional bioremediation in a laboratory-scale, slurry-phase bioreactor. Polyoxyethylene sorbitol hexaoleate (POESH) was the optimum surfactant for enhancing PAH removal, especially the high-molecular weight PAHs. This work extends that concept by treating the effluent from the slurry-phase bioreactor in a second-stage batch reactor, to which POESH was added, for an additional 7 or 12 days. Surfactant amendment removed substantial amounts of the PAHs and oxy-PAHs remaining after conventional slurry-phase bioremediation, including more than 80% of residual 4-ring PAHs. Surfactant-amended treatment decreased soil cytotoxicity, but often increased the genotoxicity of the soil as measured using the DT-40 chicken lymphocyte DNA damage response assay. Potential ecotoxicity, measured using a seed germination assay, was reduced by bioreactor treatment and was reduced further after second-stage treatment with POESH. Of bacteria previously implicated as potential PAH degraders under POESH-amended conditions in a prior study, members of the Terrimonas genus were associated with differences in high-molecular weight PAH removal in the current study. Research using submicellar doses of surfactant as a second-stage treatment step is limited and these findings can inform the design of bioremediation systems at field sites treating soil contaminated with PAHs and other hydrophobic contaminants that have low bioaccessibility.}, number={9}, journal={ENVIRONMENTAL ENGINEERING SCIENCE}, author={Adrion, Alden C. and Singleton, David R. and Nakamura, Jun and Shea, Damian and Aitken, Michael D.}, year={2016}, month={Sep}, pages={659–670} } @article{gardner_bonner_landin_ferzli_shea_2016, title={Nonmajors' Shifts in Attitudes & Perceptions of Biology & Biologists Following an Active-Learning Course}, volume={78}, number={1}, journal={The American Biology Teacher}, author={Gardner, G.E. and Bonner, J. and Landin, J. and Ferzli, M. and Shea, D.}, year={2016}, pages={43–48} } @article{gardner_bonner_landin_ferzli_shea_2016, title={Nonmajors' Shifts in Attitudes & Perceptions of Biology & Biologists Following an Active-Learning Course: An Exploratory Study}, volume={78}, ISSN={["1938-4211"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-84955478007&partnerID=MN8TOARS}, DOI={10.1525/abt.2016.78.1.43}, abstractNote={Abstract This exploratory study examined the impacts of a student-centered, active-learning course on nonmajors' attitudes and perceptions of biology and biologists. Results revealed changes along various measured attitude variables. Most notably, participants saw significant positive shifts in their perceptions of biology as a scientific field that contrasted with their relatively stable perceptions of biologists as scientists. Implications are discussed in the context of the impacts of nonmajors biology courses on future K—12 science instructors and potential influxes of students into the science pipeline.}, number={1}, journal={AMERICAN BIOLOGY TEACHER}, author={Gardner, Grant E. and Bonner, Jeff and Landin, Jennifer and Ferzli, Miriam and Shea, Damian}, year={2016}, month={Jan}, pages={43–48} } @article{adrion_nakamura_shea_aitken_2016, title={Screening Nonionic Surfactants for Enhanced Biodegradation of Polycyclic Aromatic Hydrocarbons Remaining in Soil After Conventional Biological Treatment}, volume={50}, ISSN={["1520-5851"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-84963799085&partnerID=MN8TOARS}, DOI={10.1021/acs.est.5b05243}, abstractNote={A total of five nonionic surfactants (Brij 30, Span 20, Ecosurf EH-3, polyoxyethylene sorbitol hexaoleate, and R-95 rhamnolipid) were evaluated for their ability to enhance PAH desorption and biodegradation in contaminated soil after treatment in an aerobic bioreactor. Surfactant doses corresponded to aqueous-phase concentrations below the critical micelle concentration in the soil-slurry system. The effect of surfactant amendment on soil (geno)toxicity was also evaluated for Brij 30, Span 20, and POESH using the DT40 B-lymphocyte cell line and two of its DNA-repair-deficient mutants. Compared to the results from no-surfactant controls, incubation of the bioreactor-treated soil with all surfactants increased PAH desorption, and all except R-95 substantially increased PAH biodegradation. POESH had the greatest effect, removing 50% of total measured PAHs. Brij 30, Span 20, and POESH were particularly effective at enhancing biodegradation of four- and five-ring PAHs, including five of the seven carcinogenic PAHs, with removals up to 80%. Surfactant amendment also significantly enhanced the removal of alkyl-PAHs. Most treatments significantly increased soil toxicity. Only the no-surfactant control and Brij 30 at the optimum dose significantly decreased soil genotoxicity, as evaluated with either mutant cell line. Overall, these findings have implications for the feasibility of bioremediation to achieve cleanup levels for PAHs in soil.}, number={7}, journal={ENVIRONMENTAL SCIENCE & TECHNOLOGY}, author={Adrion, Alden C. and Nakamura, Jun and Shea, Damian and Aitken, Michael D.}, year={2016}, month={Apr}, pages={3838–3845} } @article{gardner_forrester_jeffrey_ferzli_shea_2015, title={Authentic Science Research Opportunities: How Do Undergraduate Students Begin Integration into a Science Community of Practice?}, volume={44}, number={4}, journal={Journal of College Science Teaching}, author={Gardner, G.E. and Forrester, J.H. and Jeffrey, P.S. and Ferzli, M. and Shea, D.}, year={2015}, pages={61–65} } @article{abdo_wetmore_chappell_shea_wright_rusyn_2015, title={In vitro screening for population variability in toxicity of pesticide-containing mixtures}, volume={85}, ISSN={["1873-6750"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-84941887442&partnerID=MN8TOARS}, DOI={10.1016/j.envint.2015.09.012}, abstractNote={Population-based human in vitro models offer exceptional opportunities for evaluating the potential hazard and mode of action of chemicals, as well as variability in responses to toxic insults among individuals. This study was designed to test the hypothesis that comparative population genomics with efficient in vitro experimental design can be used for evaluation of the potential for hazard, mode of action, and the extent of population variability in responses to chemical mixtures. We selected 146 lymphoblast cell lines from 4 ancestrally and geographically diverse human populations based on the availability of genome sequence and basal RNA-seq data. Cells were exposed to two pesticide mixtures - an environmental surface water sample comprised primarily of organochlorine pesticides and a laboratory-prepared mixture of 36 currently used pesticides - in concentration response and evaluated for cytotoxicity. On average, the two mixtures exhibited a similar range of in vitro cytotoxicity and showed considerable inter-individual variability across screened cell lines. However, when in vitro-to-in vivo extrapolation (IVIVE) coupled with reverse dosimetry was employed to convert the in vitro cytotoxic concentrations to oral equivalent doses and compared to the upper bound of predicted human exposure, we found that a nominally more cytotoxic chlorinated pesticide mixture is expected to have greater margin of safety (more than 5 orders of magnitude) as compared to the current use pesticide mixture (less than 2 orders of magnitude) due primarily to differences in exposure predictions. Multivariate genome-wide association mapping revealed an association between the toxicity of current use pesticide mixture and a polymorphism in rs1947825 in C17orf54. We conclude that a combination of in vitro human population-based cytotoxicity screening followed by dosimetric adjustment and comparative population genomics analyses enables quantitative evaluation of human health hazard from complex environmental mixtures. Additionally, such an approach yields testable hypotheses regarding potential toxicity mechanisms.}, journal={ENVIRONMENT INTERNATIONAL}, author={Abdo, Nour and Wetmore, Barbara A. and Chappell, Grace A. and Shea, Damian and Wright, Fred A. and Rusyn, Ivan}, year={2015}, month={Dec}, pages={147–155} } @article{mceachran_shea_bodnar_nichols_2015, title={Pharmaceutical occurrence in groundwater and surface waters in forests land-applied with municipal wastewater}, volume={35}, ISSN={0730-7268}, url={http://dx.doi.org/10.1002/etc.3216}, DOI={10.1002/etc.3216}, abstractNote={The occurrence and fate of pharmaceutical and personal care products in the environment are of increasing public importance because of their ubiquitous nature and documented effects on wildlife, ecosystems, and potentially humans. One potential, yet undefined, source of entry of pharmaceuticals into the environment is via the land application of municipal wastewater onto permitted lands. The objective of the present study is to determine the extent to which pharmaceuticals are mitigated by or exported from managed tree plantations irrigated with municipal wastewater. A specific focus of the present study is the presence of pharmaceutical compounds in groundwater and surface water discharge. The study site is a municipality that land‐applies secondary treated wastewater onto 930 hectares of a 2000‐hectare managed hardwood and pine plantation. A suite of 33 pharmaceuticals and steroid hormones was targeted in the analysis, which consisted of monthly grab sampling of groundwater, surface water, and wastewater, followed by concentration and cleanup via solid phase extraction and separation, detection, and quantification via liquid chromatography coupled with tandem mass spectrometry. More than one‐half of all compounds detected in irrigated wastewater were not present in groundwater and subsequent surface water. However, antibiotics, nonsteroidal anti‐inflammatory drugs, caffeine, and other prescription and over‐the‐counter drugs remained in groundwater and were transported into surface water at concentrations up to 10 ng/L. These results provide important documentation for pharmaceutical fate and transport in forest systems irrigated with municipal wastewater, a previously undocumented source of environmental entry. Environ Toxicol Chem 2016;35:898–905. © 2015 SETAC}, number={4}, journal={Environmental Toxicology and Chemistry}, publisher={Wiley}, author={McEachran, Andrew D. and Shea, Damian and Bodnar, Wanda and Nichols, Elizabeth Guthrie}, year={2015}, month={Dec}, pages={898–905} } @inbook{gardner_karl_ferzli_shea_haase_day_2015, place={Cham, Switzerland}, series={ASTE Series in Science Education}, title={The Bennett's Millpond Environmental Learning Project: Place-based education with student-teacher research teams}, ISBN={["978-3-319-16410-6"]}, DOI={10.1007/978-3-319-16411-3_14}, abstractNote={This chapter describes a case study of place-based education in action called the Bennett’s Millpond Environmental Learning Project. The work sought to engage high school students and teachers in place-based, collaborative research experiences related to environmental sustainability. Results from a formal evaluation of the project are discussed. Several themes related to science teacher education and professional development that emerged from the data are presented, including teacher development as researchers, teacher development of collaborations with the community, and teacher use of technology to facilitate learning and outreach. An argument is provided for the importance of technology as a mediator that allows both teachers and students to easily move between local place-based environmental sustainability issues and global worldviews.}, booktitle={Educating Science Teachers for Sustainability}, publisher={Springer}, author={Gardner, G.E. and Karl, C. and Ferzli, M. and Shea, D. and Haase, D. and Day, J.B.}, editor={Stratton, S. and Hagevik, R. and Feldman, A. and Bloom, M.Editors}, year={2015}, pages={255–274}, collection={ASTE Series in Science Education} } @article{adebambo_ray_shea_fry_2015, title={Toxicological responses of environmental mixtures: Environmental metal mixtures display synergistic induction of metal-responsive and oxidative stress genes in placental cells}, volume={289}, ISSN={["1096-0333"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-84947768563&partnerID=MN8TOARS}, DOI={10.1016/j.taap.2015.10.005}, abstractNote={Exposure to elevated levels of the toxic metals inorganic arsenic (iAs) and cadmium (Cd) represents a major global health problem. These metals often occur as mixtures in the environment, creating the potential for interactive or synergistic biological effects different from those observed in single exposure conditions. In the present study, environmental mixtures collected from two waste sites in China and comparable mixtures prepared in the laboratory were tested for toxicogenomic response in placental JEG-3 cells. These cells serve as a model for evaluating cellular responses to exposures during pregnancy. One of the mixtures was predominated by iAs and one by Cd. Six gene biomarkers were measured in order to evaluate the effects from the metal mixtures using dose and time-course experiments including: heme oxygenase 1 (HO-1) and metallothionein isoforms (MT1A, MT1F and MT1G) previously shown to be preferentially induced by exposure to either iAs or Cd, and metal transporter genes aquaporin-9 (AQP9) and ATPase, Cu2 + transporting, beta polypeptide (ATP7B). There was a significant increase in the mRNA expression levels of ATP7B, HO-1, MT1A, MT1F, and MT1G in mixture-treated cells compared to the iAs or Cd only-treated cells. Notably, the genomic responses were observed at concentrations significantly lower than levels found at the environmental collection sites. These data demonstrate that metal mixtures increase the expression of gene biomarkers in placental JEG-3 cells in a synergistic manner. Taken together, the data suggest that toxic metals that co-occur may induce detrimental health effects that are currently underestimated when analyzed as single metals.}, number={3}, journal={TOXICOLOGY AND APPLIED PHARMACOLOGY}, author={Adebambo, Oluwadamilare A. and Ray, Paul D. and Shea, Damian and Fry, Rebecca C.}, year={2015}, month={Dec}, pages={534–541} } @inproceedings{gardner_ferzli_jeffrey_shea_2015, title={Undergraduate Research as an Innovative Learning Experience: Student Perspectives on Professional Impacts}, booktitle={Innovations in College Science Teaching}, publisher={Society for College Science Teachers}, author={Gardner, G.E. and Ferzli, M. and Jeffrey, P.S. and Shea, D.}, editor={Latourelle, S.Editor}, year={2015}, pages={35–48} } @article{hu_adrion_nakamura_shea_aitken_2014, title={Bioavailability of (Geno)toxic Contaminants in Polycyclic Aromatic Hydrocarbon-Contaminated Soil Before and After Biological Treatment}, volume={31}, ISSN={["1557-9018"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-84899449644&partnerID=MN8TOARS}, DOI={10.1089/ees.2013.0409}, abstractNote={Contaminated soil from a former manufactured-gas plant site was treated in a laboratory-scale bioreactor. Desorbability and biodegradability of 14 polycyclic aromatic hydrocarbons (PAHs) and 4 oxygenated PAHs (oxy-PAHs) were investigated throughout a treatment cycle. Desorbability was determined using a mixed-function sorbent (Oasis® HLB) or a hydrophobic sorbent (Tenax®) in dialysis tubing suspended in the soil slurry. Toxicity and genotoxicity of the whole soil and the desorbable fractions were determined by DNA damage response analysis with the chicken DT40 B-lymphocyte isogenic cell line and its DNA repair-deficient mutant Rad54-/-. Biological treatment significantly removed both PAHs and oxy-PAHs, and their desorbability decreased throughout the bioreactor treatment cycle. Collectively, oxy-PAHs were more desorbable and biodegradable than the corresponding PAHs; for example, the oxy-PAH present at the highest concentration, 9,10-anthraquinone, was more desorbable and biodegradable than anthracene. For both PAHs and oxy-PAHs, the percentage removed in the bioreactor significantly exceeded the percentage desorbed from untreated soil, indicating that desorption did not control the extent of biodegradation. Consistent with previous results on the same soil, genotoxicity of the whole soil slightly increased after biological treatment. However, both toxicity and genotoxicity of the desorbable constituents in the soil decreased after treatment, suggesting that any genotoxic constituents that may have formed during treatment were primarily associated with less accessible domains in the soil.}, number={4}, journal={ENVIRONMENTAL ENGINEERING SCIENCE}, author={Hu, Jing and Adrion, Alden C. and Nakamura, Jun and Shea, Damian and Aitken, Michael D.}, year={2014}, month={Apr}, pages={176–182} } @article{hardison_sunda_tester_shea_litaker_2014, title={Increased cellular brevetoxins in the red tide dinoflagellate Karenia brevis under CO2 limitation of growth rate: Evolutionary implications and potential effects on bloom toxicity}, volume={59}, ISSN={["1939-5590"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-84895875095&partnerID=MN8TOARS}, DOI={10.4319/lo.2014.59.2.0560}, abstractNote={Karenia brevis blooms impair human health, marine ecosystems, and coastal economies in the Gulf of Mexico via their production of carbon‐based neurotoxins (brevetoxins), which contain no nitrogen (N) or phosphorus (P). N and P limitation of growth rate substantially increases brevetoxins in this dinoflagellate, consistent with predictions of the carbon nutrient balance (CNB) hypothesis. This hypothesis further predicts that an increase in carbon‐based brevetoxins should not occur if growth rate is limited by carbon dioxide (CO2). We tested this prediction by examining the effect of CO2 limitation of K. brevis growth rate on cellular brevetoxins. In contradiction to the prediction of the CNB hypothesis, brevetoxins normalized to cell carbon were on average 81% higher in CO2‐limited cells growing at a rate of 0.1 d−1 than in cells growing at their maximum rates (0.4–0.5 d−1). This increase in brevetoxin : C values in the CO2‐limited cells, however, was 23–42% lower than that previously observed for comparable growth rate limitation by phosphate. The CO2‐limited cells also exhibited 40% higher cellular N : C and 60–100% higher chlorophyll a : C than observed in P‐limited cells at equivalent growth rates. These effects were likely due to the up‐regulation of the cell's CO2‐concentrating mechanism under CO2 limitation, which increased the demand for photosynthetically produced adenosine‐5′‐triphosphate. The results indicate that anthropogenic increases in CO2 concentrations in surface ocean waters are likely to increase the toxicity of K. brevis blooms due to potential increases in bloom biomass yield and to a greater likelihood that dense blooms will become N or P limited rather than CO2 limited.}, number={2}, journal={LIMNOLOGY AND OCEANOGRAPHY}, author={Hardison, D. Ransom and Sunda, William G. and Tester, Patricia A. and Shea, Damian and Litaker, R. Wayne}, year={2014}, month={Mar}, pages={560–577} } @article{hardison_sunda_shea_litaker_2013, title={Increased Toxicity of Karenia brevis during Phosphate Limited Growth: Ecological and Evolutionary Implications}, volume={8}, ISSN={["1932-6203"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-84874839168&partnerID=MN8TOARS}, DOI={10.1371/journal.pone.0058545}, abstractNote={Karenia brevis is the dominant toxic red tide algal species in the Gulf of Mexico. It produces potent neurotoxins (brevetoxins [PbTxs]), which negatively impact human and animal health, local economies, and ecosystem function. Field measurements have shown that cellular brevetoxin contents vary from 1–68 pg/cell but the source of this variability is uncertain. Increases in cellular toxicity caused by nutrient-limitation and inter-strain differences have been observed in many algal species. This study examined the effect of P-limitation of growth rate on cellular toxin concentrations in five Karenia brevis strains from different geographic locations. Phosphorous was selected because of evidence for regional P-limitation of algal growth in the Gulf of Mexico. Depending on the isolate, P-limited cells had 2.3- to 7.3-fold higher PbTx per cell than P-replete cells. The percent of cellular carbon associated with brevetoxins (%C-PbTx) was ∼ 0.7 to 2.1% in P-replete cells, but increased to 1.6–5% under P-limitation. Because PbTxs are potent anti-grazing compounds, this increased investment in PbTxs should enhance cellular survival during periods of nutrient-limited growth. The %C-PbTx was inversely related to the specific growth rate in both the nutrient-replete and P-limited cultures of all strains. This inverse relationship is consistent with an evolutionary tradeoff between carbon investment in PbTxs and other grazing defenses, and C investment in growth and reproduction. In aquatic environments where nutrient supply and grazing pressure often vary on different temporal and spatial scales, this tradeoff would be selectively advantageous as it would result in increased net population growth rates. The variation in PbTx/cell values observed in this study can account for the range of values observed in the field, including the highest values, which are not observed under N-limitation. These results suggest P-limitation is an important factor regulating cellular toxicity and adverse impacts during at least some K. brevis blooms.}, number={3}, journal={PLOS ONE}, author={Hardison, Donnie Ransom and Sunda, William G. and Shea, Damian and Litaker, Richard Wayne}, year={2013}, month={Mar} } @article{hardison_sunda_shea_tester_litaker_2013, title={When hungry, Karenia brevis goes toxic}, volume={52}, number={4}, journal={Phycologia}, author={Hardison, D.R. and Sunda, W.G. and Shea, D. and Tester, P.A. and Litaker, W.R.}, year={2013}, pages={41} } @inproceedings{hawkins_ferzli_overman_shea_2012, title={A Studio Lab for the Undergraduate Biology Curriculum: Using a Comparative Endocrinology Model to Recruit Future Scientists}, volume={52}, number={Suppl 1}, booktitle={Integrative and Comparative Biology}, author={Hawkins, M.B. and Ferzli, M. and Overman, E. and Shea, D.}, year={2012}, pages={260} } @article{mosher_cope_weber_kwak_shea_2012, title={Assessing accumulation and sublethal effects of lead in a unionid mussel}, volume={15}, number={1}, journal={Walkerana}, author={Mosher, S. and Cope, W.G. and Weber, F.X. and Kwak, T.J. and Shea, D.}, year={2012}, month={Mar}, pages={60–68} } @article{gjeltema_stoskopf_shea_de voe_2012, title={Assessment of Polycyclic Aromatic Hydrocarbon Contamination of Breeding Pools Utilized by the Puerto Rican Crested Toad, Peltophryne lemur}, volume={2012}, DOI={10.5402/2012/309853}, abstractNote={Habitat preservation and management may play an important role in the conservation of the Puerto Rican crested toad, Peltophryne lemur, due to this species' small geographic range and declining native wild population. Bioavailable water concentrations of Polycyclic Aromatic Hydrocarbon (PAH) contaminants within breeding pools at 3 sites were established using Passive Sampling Devices (PSDs) and gas chromatography-mass spectrometry (GC/MS). A more diverse population of PAH analytes were found in higher concentrations at the breeding site that allowed direct vehicular access, but calculated risk quotients indicated low risk to toad reproduction associated with the current PAH analyte levels.}, journal={International Scholarly Research Notices}, author={Gjeltema, J. and Stoskopf, M. and Shea, D. and De Voe, R.}, year={2012}, pages={309853} } @article{shea_thorsen_2012, title={Ecological Risk Assessment}, volume={112}, ISBN={["978-0-12-415813-9"]}, ISSN={["1877-1173"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-84866551834&partnerID=MN8TOARS}, DOI={10.1016/b978-0-12-415813-9.00012-x}, abstractNote={Ecological risk assessment (ERA) has matured since the 1970s when it began as ecological assessment. ERA has its foundations in human health risk assessment, and as such, similarities exist between the two processes. However, the inherent complex nature of the ecosystem and its interwoven processes make the practice typically more complex for ERA than for human health risk assessment. In the early 1990s, the Environmental Protection Agency and others issued guidance documents that present a basic framework approach for conducting ERAs. This basic framework persists today and includes the three main components of the risk assessment process: problem formulation, analysis, and risk characterization. Over time, scientists, risk analysts, and risk managers have augmented the component steps with iterative feedbacks and a weight-of-evidence approach that integrates numerous lines of evidence for analyzing stressor effects, exposure likelihood, and ecosystem risks. This chapter aims to present the reader with an overview and examples of the current ERA process.}, journal={TOXICOLOGY AND HUMAN ENVIRONMENTS}, author={Shea, Damian and Thorsen, Waverly}, year={2012}, pages={323–348} } @inbook{shea_thorsen_2012, place={London}, series={Progress in Molecular Biology and Translational Science}, title={Ecological Risk Assessment}, ISBN={9780124158139}, booktitle={Toxicology and Human Environments}, publisher={Academic Press}, author={Shea, D. and Thorsen, W.}, editor={Hodgson, E.Editor}, year={2012}, pages={323–348}, collection={Progress in Molecular Biology and Translational Science} } @article{mosher_cope_weber_shea_kwak_2012, title={Effects of lead on Na+, K+-ATPase and hemolymph ion concentrations in the freshwater mussel Elliptio complanata}, volume={27}, ISSN={1520-4081}, url={http://dx.doi.org/10.1002/tox.20639}, DOI={10.1002/tox.20639}, abstractNote={Freshwater mussels are an imperiled fauna exposed to a variety of environmental toxicants such as lead (Pb) and studies are urgently needed to assess their health and condition to guide conservation efforts. A 28‐day laboratory toxicity test with Pb and adult Eastern elliptio mussels (Elliptio complanata) was conducted to determine uptake kinetics and to assess the toxicological effects of Pb exposure. Test mussels were collected from a relatively uncontaminated reference site and exposed to a water‐only control and five concentrations of Pb (as lead nitrate) ranging from 1 to 245 μg/L in a static renewal test with a water hardness of 42 mg/L. Endpoints included tissue Pb concentrations, hemolymph Pb and ion (Na+, K+, Cl−, Ca2+) concentrations, and Na+, K+‐ATPase enzyme activity in gill tissue. Mussels accumulated Pb rapidly, with tissue concentrations increasing at an exposure‐dependent rate for the first 2 weeks, but with no significant increase from 2 to 4 weeks. Mussel tissue Pb concentrations ranged from 0.34 to 898 μg/g dry weight, were strongly related to Pb in test water at every time interval (7, 14, 21, and 28 days), and did not significantly increase after day 14. Hemolymph Pb concentration was variable, dependent on exposure concentration, and showed no appreciable change with time beyond day 7, except for mussels in the greatest exposure concentration (245 μg/L), which showed a significant reduction in Pb by 28 days, suggesting a threshold for Pb binding or elimination in hemolymph at concentrations near 1000 μg/g. The Na+, K+‐ATPase activity in the gill tissue of mussels was significantly reduced by Pb on day 28 and was highly correlated with tissue Pb concentration (R2 = 0.92; P = 0.013). The Na+, K+‐ATPase activity was correlated with reduced hemolymph Na+ concentration at the greatest Pb exposure when enzyme activity was at 30% of controls. Hemolymph Ca2+ concentration increased significantly in mussels from the greatest Pb exposure and may be due to remobilization from the shell in an attempt to buffer the hemolymph against Pb uptake and toxicity. We conclude that Na+, K+‐ATPase activity in mussels was adversely affected by Pb exposure, however, because the effects on activity were variable at the lower test concentrations, additional research is warranted over this range of exposures. © 2010 Wiley Periodicals, Inc. Environ Toxicol, 2012.}, number={5}, journal={Environmental Toxicology}, publisher={Wiley}, author={Mosher, Shad and Cope, W. Gregory and Weber, Frank X. and Shea, Damian and Kwak, Thomas J.}, year={2012}, month={May}, pages={268–276} } @article{hardison_sunda_litaker_shea_tester_2012, title={NITROGEN LIMITATION INCREASES BREVETOXINS IN KARENIA BREVIS (DINOPHYCEAE): IMPLICATIONS FOR BLOOM TOXICITY}, volume={48}, ISSN={["1529-8817"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-84864505726&partnerID=MN8TOARS}, DOI={10.1111/j.1529-8817.2012.01186.x}, abstractNote={Laboratory and field measurements of the toxin content in Karenia brevis cells vary by >4‐fold. These differences have been largely attributed to genotypic variations in toxin production among strains. We hypothesized that nutrient limitation of growth rate is equally or more important in controlling the toxicity of K. brevis, as has been documented for other toxic algae. To test this hypothesis, we measured cellular growth rate, chlorophyll a, cellular carbon and nitrogen, cell volume, and brevetoxins in four strains of K. brevis grown in nutrient‐replete and nitrogen (N)‐limited semi‐continuous cultures. N‐limitation resulted in reductions of chlorophyll a, growth rate, volume per cell and nirtogen:carbon (N:C) ratios as well as a two‐fold increase (1%–4% to 5%–9%) in the percentage of cellular carbon present as brevetoxins. The increase in cellular brevetoxin concentrations was consistent among genetically distinct strains. Normalizing brevetoxins to cellular volume instead of per cell eliminated much of the commonly reported toxin variability among strains. These results suggest that genetically linked differences in cellular volume may affect the toxin content of K. brevis cells as much or more than innate genotypic differences in cellular toxin content per unit of biomass. Our data suggest at least some of the >4‐fold difference in toxicity per cell reported from field studies can be explained by limitation by nitrogen or other nutrients and by differences in cell size. The observed increase in brevetoxins in nitrogen limited cells is consistent with the carbon:nutrient balance hypothesis for increases in toxins and other plant defenses under nutrient limitation.}, number={4}, journal={JOURNAL OF PHYCOLOGY}, author={Hardison, D. Ransom and Sunda, William G. and Litaker, R. Wayne and Shea, Damian and Tester, Patricia A.}, year={2012}, month={Aug}, pages={844–858} } @article{cope_holliman_kwak_oakley_lazaro_shea_augspurger_law_henne_ware_et al._2011, title={Assessing water quality suitability for shortnose sturgeon in the Roanoke River, North Carolina, USA with an in situ bioassay approach}, volume={27}, ISSN={["0175-8659"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-78751690460&partnerID=MN8TOARS}, DOI={10.1111/j.1439-0426.2010.01570.x}, abstractNote={Summary The aim of this study was to determine the suitability of water quality in the Roanoke River of North Carolina for supporting shortnose sturgeon Acipenser brevirostrum, an endangered species in the United States. Fathead minnows Pimephales promelas were also evaluated alongside the sturgeon as a comparative species to measure potential differences in fish survival, growth, contaminant accumulation, and histopathology in a 28-day in situ toxicity test. Captively propagated juvenile shortnose sturgeon (total length 49 ± 8 mm, mean ± SD) and fathead minnows (total length 39 ± 3 mm, mean ± SD) were used in the test and their outcomes were compared to simultaneous measurements of water quality (temperature, dissolved oxygen, pH, conductivity, total ammonia nitrogen, hardness, alkalinity, turbidity) and contaminant chemistry (metals, polycyclic aromatic hydrocarbons, organochlorine pesticides, current use pesticides, polychlorinated biphenyls) in river water and sediment. In the in situ test, there were three non-riverine control sites and eight riverine test sites with three replicate cages (25 × 15-cm (OD) clear plexiglass with 200-μm tear-resistant Nitex® screen over each end) of 20 shortnose sturgeon per cage at each site. There was a single cage of fathead minnows also deployed at each site alongside the sturgeon cages. Survival of caged shortnose sturgeon among the riverine sites averaged 9% (range 1.7–25%) on day 22 of the 28-day study, whereas sturgeon survival at the non-riverine control sites averaged 64% (range 33–98%). In contrast to sturgeon, only one riverine deployed fathead minnow died (average 99.4% survival) over the 28-day test period and none of the control fathead minnows died. Although chemical analyses revealed the presence of retene (7-isopropyl-1-methylphenanthrene), a pulp and paper mill derived compound with known dioxin-like toxicity to early life stages of fish, in significant quantities in the water (251–603 ng L−1) and sediment (up to 5000 ng g−1 dry weight) at several river sites, no correlation was detected of adverse water quality conditions or measured contaminant concentrations to the poor survival of sturgeon among riverine test sites. Histopathology analysis determined that the mortality of the river deployed shortnose sturgeon was likely due to liver and kidney lesions from an unknown agent(s). Given the poor survival of shortnose sturgeon (9%) and high survival of fathead minnows (99.4%) at the riverine test sites, our study indicates that conditions in the Roanoke River are incongruous with the needs of juvenile shortnose sturgeon and that fathead minnows, commonly used standard toxicity test organisms, do not adequately predict the sensitivity of shortnose sturgeon. Therefore, additional research is needed to help identify specific limiting factors and management actions for the enhancement and recovery of this imperiled fish species.}, number={1}, journal={JOURNAL OF APPLIED ICHTHYOLOGY}, author={Cope, W.G. and Holliman, F.M. and Kwak, T.J. and Oakley, N.C. and Lazaro, P.R. and Shea, Damian and Augspurger, T. and Law, J.M. and Henne, J.P. and Ware, K.M. and et al.}, year={2011}, month={Feb}, pages={1–12} } @article{bringolf_heltsley_newton_eads_fraley_shea_cope_2010, title={ENVIRONMENTAL OCCURRENCE AND REPRODUCTIVE EFFECTS OF THE PHARMACEUTICAL FLUOXETINE IN NATIVE FRESHWATER MUSSELS}, volume={29}, ISSN={["1552-8618"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-77953583998&partnerID=MN8TOARS}, DOI={10.1002/etc.157}, abstractNote={The present study measured the occurrence, distribution, and bioaccumulation of fluoxetine in samples of water, polar organic chemical integrative sampler (POCIS), sediment, and caged freshwater mussels at stream sites near a municipal wastewater treatment facility effluent discharge. We assessed the relation of the environmental concentrations to reproductive endpoints in mussels in acute laboratory tests. Concentrations of fluoxetine in water and POCIS samples were similar (<20% difference) within each site and were greatest in the effluent channel (104–119 ng/L), and decreased at 50 m and 100 m downstream. Likewise, concentrations of fluoxetine in sediment and mussel (Elliptio complanata) tissue were greatest in the effluent channel (17.4 ng/g wet wt for sediment and 79.1 ng/g wet wt for mussels). In 96‐h lab tests, fluoxetine significantly induced parturition of nonviable larvae from female E. complanata exposed to 300 µg/L (p = 0.0118) and 3,000 µg/L (p < 0.0001) compared to controls. Fluoxetine exposure at 300 µg/L (p = 0.0075) and 3,000 µg/L (p = 0.0001) also resulted in stimulation of lure display behavior in female Lampsilis fasciola and Lampsilis cardium, respectively. In male E. complanata, 3,000 µg fluoxetine/L significantly induced release of spermatozeugmata during a 48‐h exposure. These results suggest that fluoxetine accumulates in mussel tissue and has the potential to disrupt several aspects of reproduction in freshwater mussels, a faunal group recognized as one of the most imperiled in the world. Despite the disparity between measured environmental concentrations of fluoxetine and effects concentrations in our short‐term tests with these long‐lived animals, additional tests are warranted to evaluate the effects of long‐term exposure to environmentally relevant concentrations and critical lifestages (e.g., juveniles). Environ. Toxicol. Chem. 2010;29:1311–1318. © 2010 SETAC}, number={6}, journal={ENVIRONMENTAL TOXICOLOGY AND CHEMISTRY}, author={Bringolf, Robert B. and Heltsley, Rebecca M. and Newton, Teresa J. and Eads, Chris B. and Fraley, Stephen J. and Shea, Damian and Cope, W. Gregory}, year={2010}, month={Jun}, pages={1311–1318} } @inbook{shea_2010, place={Hoboken, NJ USA}, edition={4th}, title={Environmental Risk Assessment}, ISBN={9780470462065}, booktitle={A Textbook of Modern Toxicology}, publisher={John Wiley & Sons, Inc}, author={Shea, D.}, editor={Hodgson, E.Editor}, year={2010}, pages={571–590} } @inbook{shea_2010, place={Hoboken, NJ USA}, edition={4th}, title={Transport and Fate of Toxicants in the Environment}, ISBN={9780470462065}, booktitle={A Textbook of Modern Toxicology}, publisher={John Wiley & Sons, Inc}, author={Shea, D.}, editor={Hodgson, E.Editor}, year={2010}, pages={549–570} } @article{henson-ramsey_levine_kennedy-stoskopf_taylor_shea_stoskopf_2009, title={Development of a Dynamic Pharmacokinetic Model to Estimate Bioconcentration of Xenobiotics in Earthworms}, volume={14}, ISSN={["1573-2967"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-67349243406&partnerID=MN8TOARS}, DOI={10.1007/s10666-007-9132-4}, number={3}, journal={ENVIRONMENTAL MODELING & ASSESSMENT}, author={Henson-Ramsey, Heather and Levine, Jay and Kennedy-Stoskopf, Suzanne and Taylor, Sharon K. and Shea, Damian and Stoskopf, Michael K.}, year={2009}, month={Jun}, pages={411–418} } @article{patisaul_burke_hinkle_adewale_shea_2009, title={Systemic administration of diarylpropionitrile (DPN) or phytoestrogens does not affect anxiety-related behaviors in gonadally intact male rats}, volume={55}, ISSN={["1095-6867"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-58849100773&partnerID=MN8TOARS}, DOI={10.1016/j.yhbeh.2008.11.004}, abstractNote={The development of highly selective agonists for the two major subforms of the estrogen receptor (ERalpha and ERbeta) has produced new experimental methodologies for delineating the distinct functional role each plays in neurobehavioral biology. It has also been suggested that these compounds might have the potential to treat estrogen influenced behavioral disorders, such as anxiety and depression. Prior work has established that the ERbeta agonist, diarylpropionitrile (DPN) is anxiolytic in gonadectomized animals of both sexes, but whether or not this effect persists in gonadally intact individuals is unknown. Isoflavone phytoestrogens, also potent but less selective ERbeta agonists, have also been shown to influence anxiety in multiple species and are becoming more readily available to humans as health supplements. Here we determined the effects of 0.5, 1 or 2 mg/kg DPN, 1 mg/kg of the ERalpha agonist propyl-pyrazole-triol (PPT), 3 or 20 mg/kg of the isoflavone equol (EQ) and 3 or 20 mg/kg of the isoflavone polyphenol resveratrol (RES) on anxiety behavior in the gonadally intact male rat using the light/dark box and the elevated plus maze. We first determined that DPN can be successfully administered either orally or by subcutaneous injection, although plasma DPN levels are significantly lower if given orally. Once injected, plasma levels peak rapidly and then decline to baseline levels within 3 h of administration. For the behavioral studies, all compounds were injected and the animals were tested within 3 h of treatment. None of the compounds, at any of the doses, significantly altered anxiety-related behavior. Plasma testosterone levels were also not significantly altered suggesting that these compounds do not interfere with endogenous androgen levels. The results suggest that the efficacy of ERbeta agonists may depend on gonadal status. Therefore the therapeutic potential of ERbeta selective agonists to treat mood disorders may be limited.}, number={2}, journal={HORMONES AND BEHAVIOR}, author={Patisaul, Heather B. and Burke, Katherine T. and Hinkle, Ruth E. and Adewale, Heather B. and Shea, Damian}, year={2009}, month={Feb}, pages={319–328} } @article{henson-ramsey_kennedy-stoskopf_levine_taylor_shea_stoskopf_2008, title={Acute toxicity and tissue distributions of malathion in Ambystoma tigrinum}, volume={55}, ISSN={["1432-0703"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-51849109593&partnerID=MN8TOARS}, DOI={10.1007/s00244-007-9091-4}, abstractNote={The kinetics of the bioaccumulation of malathion (O,O-dimethyl phosphorodithioate of diethyl mercaptosuccinate) and the biological impact of exposure for tiger salamanders, Ambystoma tigrinum, were assessed through exposure to soil surface contaminated with 50 microg/cm(2) or 100 microg/cm(2 )malathion and ingestion of an earthworm exposed to soil contaminated with 200 microg/cm(2) malathion. Malathion and malaoxon burdens in salamanders sampled at different times after exposure(s) were measured by gas chromatography in four tissue/organ subgroups: liver, epaxial muscle, pooled viscera (except the liver and brain), and pooled avisceral carcass (muscle, skin, and bone). The total tiger salamander xenobiotic burdens were calculated from these data. The malathion/malaoxon burden 1 day after exposure was greatest in the avisceral carcass and 2 days after exposure was greatest in the viscera. Bioconcentration and bioaccumulation factors remained less than unity throughout the experiment and did not support the hypothesis of bioaccumulation of malathion in the tiger salamander. Biological impact was assessed with a colorimetric brain cholinesterase microassay. Brain cholinesterase activities in salamanders exposed to malathion-contaminated soil (50 microg/cm(2) or 100 microg/cm(2 )malathion) were suppressed approximately 50-65% and 90%, respectively, compared to unexposed controls. The exposed animals did not exhibit overt clinical signs of malathion toxicosis.}, number={3}, journal={ARCHIVES OF ENVIRONMENTAL CONTAMINATION AND TOXICOLOGY}, author={Henson-Ramsey, H. and Kennedy-Stoskopf, S. and Levine, J. F. and Taylor, S. K. and Shea, D. and Stoskopf, M. K.}, year={2008}, month={Oct}, pages={481–487} } @article{chaves_shea_danehower_2008, title={Analysis of chlorothalonil and degradation products in soil and water by GC/MS and LC/MS}, volume={71}, ISSN={["0045-6535"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-39849092250&partnerID=MN8TOARS}, DOI={10.1016/j.chemosphere.2007.11.015}, abstractNote={We present a method using gas chromatography (GC) and liquid chromatography (LC) coupled to a mass selective detector to measure concentrations of the fungicide chlorothalonil and several of its metabolites in soil and water. The methods employed solid-phase extraction using a hydrophobic polymeric phase for the isolation of analytes. In lake water, average analyte recoveries ranged from 70% to 110%, with exception of pentachloronitrobenzene that gave low recoveries (23%). The method detection limits were determined to be in the range of 1 and 0.1 μg l−1 for the LC and GC methods, respectively. In soil samples, recoveries ranged from 80% to 95% for 4-hydroxy-2,5,6-trichloroisophthalonitrile (metabolite II) and 1,3-dicarbamoyl-2,4,5,6-tetrachlorobenzene (metabolite III). Limits of detection (LOD) were 0.05 and 0.02 μg g−1, respectively. Chlorothalonil and other metabolites were analyzed by GC giving recoveries ranging from 54% to 130% with LOD of 0.001−0.005 μg g−1.}, number={4}, journal={CHEMOSPHERE}, author={Chaves, Alicia and Shea, Damian and Danehower, David}, year={2008}, month={Mar}, pages={629–638} } @article{henson-ramsey_shea_levine_kennedy-stoskopf_taylor_stoskopf_2008, title={Assessment of the Effect of Varying Soil Organic Matter Content on the Bioavailability of Malathion to the Common Nightcrawler, Lumbricus terrestris L.}, volume={80}, ISSN={0007-4861 1432-0800}, url={http://dx.doi.org/10.1007/s00128-007-9349-6}, DOI={10.1007/s00128-007-9349-6}, abstractNote={This study investigated the effect of soil organic matter content on the bioavailability of malathion to the common nightcrawler, Lumbricus terrestris. Earthworms were exposed for 72 h to malathion on two soil types, 8% organic matter and 55% organic matter. Two different measures of bioavailability, malathion body burdens and tissue cholinesterase activities, were then measured in the malathion exposed animals. There were no significant differences in body burden or cholinesterase levels in L. terrestris exposed to malathion on soils with differing organic matter content. This suggests that absorption into organic matter is not a limiting factor of malathion bioavailability to earthworm species.}, number={3}, journal={Bulletin of Environmental Contamination and Toxicology}, publisher={Springer Science and Business Media LLC}, author={Henson-Ramsey, Heather and Shea, Damian and Levine, Jay F. and Kennedy-Stoskopf, Suzanne and Taylor, Sharon K. and Stoskopf, Michael K.}, year={2008}, month={Jan}, pages={220–224} } @article{mendoza_mead_brand_shea_2008, title={Determination of brevetoxin in recent marine sediments}, volume={73}, ISSN={["1879-1298"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-54049118729&partnerID=MN8TOARS}, DOI={10.1016/j.chemosphere.2008.07.089}, abstractNote={Harmful algal blooms (HAB) of Karenia brevis (K. brevis) produce a suite of lipid soluble polyether brevetoxins, known to cause environmental, health and economic ill effects. There is evidence that K. brevis has increased in abundance over the past 50 years, but the dataset is incomplete. The objective of this paper was to analyze sediment from an area where K. brevis blooms have occurred and investigate if these compounds are incorporated into the underlying sediment, thus potentially allowing the use of brevetoxins as an indicator of past K. Brevis blooms. The results from LC-ESI-MS-MS analyses of brevetoxin analogs detected in surficial sediments from three sites (Fort Meyers Beach [FMB], Big Hickory Pass [BHP] and Big Carlos Pass [BCP]) along the Southwest Florida coastline with prior HAB history are promising. The analogs detected from BHP sediments were PbTx-2 and PbTx-3 with values of 0.81 and 3.1 ng g(-1) dry sediment, respectively. The detected PbTx-2 from BCP was 3.6 ng g(-1) dry sediment, while the detected PbTx-3 from BCP was 9.7 ng g(-1) dry sediment. PbTx-3 was only detected at the FMB site (2.7 ng g(-1) dry sediment). The detection of brevetoxins in recent sediments where K. brevis have occurred indicates brevetoxin incorporation into marine sediments.}, number={8}, journal={CHEMOSPHERE}, author={Mendoza, Wilson G. and Mead, Ralph N. and Brand, Larry E. and Shea, Damian}, year={2008}, month={Nov}, pages={1373–1377} } @article{tester_shea_kibler_varnam_black_litaker_2008, title={Relationships among water column toxins, cell abundance and chlorophyll concentrations during Karenia brevis blooms}, volume={28}, ISSN={["0278-4343"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-37349112218&partnerID=MN8TOARS}, DOI={10.1016/j.csr.2007.04.007}, abstractNote={The assumptions that Karenia brevis cell abundance and brevetoxin concentrations are proportional and that cell abundance and chlorophyll are related were tested in a 3-year field study off the west coast of Florida. The relationship between K. brevis cell abundance and brevetoxins (PbTx-2+PbTx-3) in whole water samples was strong (R2=0.92). There was no significant difference between the brevetoxin concentrations in whole water and the >0.7 μm particulate fraction. Only 7% of the total brevetoxin concentration was measured in the <0.7 μm (cell free) filtrate. The relationship of K. brevis cell abundance >5000 cells L−1 with chlorophyll for all cruises and at all depths was robust (R2=0.78). These data substantiate the use of chlorophyll as a proxy for K. brevis cell abundance and K. brevis cell abundance as a proxy for brevetoxins during blooms. The ratios of the brevetoxins, PbTx-2:PbTx-3, was significantly higher in surface water than in bottom water. This information in conjunction with K. brevis growth rates may provide a useful indicator for determining the physiological state of the bloom over time.}, number={1}, journal={CONTINENTAL SHELF RESEARCH}, author={Tester, Patricia A. and Shea, Damian and Kibler, Steven R. and Varnam, Sabrina M. and Black, Megan D. and Litaker, R. Wayne}, year={2008}, month={Jan}, pages={59–72} } @article{henson-ramsey_kennedy-stoskopf_levine_shea_taylor_stoskopf_2007, title={A comparison of two exposure systems to apply malathion to Lumbricus terrestris L}, volume={78}, ISSN={["0007-4861"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-34548014761&partnerID=MN8TOARS}, DOI={10.1007/s00128-007-9194-7}, number={6}, journal={BULLETIN OF ENVIRONMENTAL CONTAMINATION AND TOXICOLOGY}, author={Henson-Ramsey, H. and Kennedy-Stoskopf, S. and Levine, J. and Shea, D. and Taylor, S. K. and Stoskopf, M. K.}, year={2007}, month={Jun}, pages={427–431} } @article{bringolf_cope_mosher_barnhart_shea_2007, title={Acute and chronic toxicity of glyphosate compounds to glochidia and juveniles of Lampsilis Siliquoidea (Unionidae)}, volume={26}, ISSN={["1552-8618"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-35348838337&partnerID=MN8TOARS}, DOI={10.1897/06-519R1.1}, abstractNote={Abstract}, number={10}, journal={ENVIRONMENTAL TOXICOLOGY AND CHEMISTRY}, author={Bringolf, Robert B. and Cope, W. Gregory and Mosher, Shad and Barnhart, M. Chris and Shea, Damian}, year={2007}, month={Oct}, pages={2094–2100} } @article{bringolf_cope_barnhart_mosher_lazaro_shea_2007, title={Acute and chronic toxicity of pesticide formulations (atrazine, chlorpyrifos, and permethrin) to glochidia and juveniles of Lampsilis Siliquoidea}, volume={26}, ISSN={["1552-8618"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-35348815483&partnerID=MN8TOARS}, DOI={10.1897/06-555R.1}, abstractNote={Abstract}, number={10}, journal={ENVIRONMENTAL TOXICOLOGY AND CHEMISTRY}, author={Bringolf, Robert B. and Cope, W. Gregory and Barnhart, M. Chris and Mosher, Shad and Lazaro, Peter R. and Shea, Damian}, year={2007}, month={Oct}, pages={2101–2107} } @article{bringolf_cope_eads_lazaro_barnhart_shea_2007, title={Acute and chronic toxicity of technical-grade pesticides to glochidia and juveniles of freshwater mussels (Unionidae)}, volume={26}, ISSN={["1552-8618"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-35348863633&partnerID=MN8TOARS}, DOI={10.1897/06-522R.1}, abstractNote={Abstract}, number={10}, journal={ENVIRONMENTAL TOXICOLOGY AND CHEMISTRY}, author={Bringolf, Robert B. and Cope, W. Gregory and Eads, Chris B. and Lazaro, Peter R. and Barnhart, M. Christopher and Shea, Damian}, year={2007}, month={Oct}, pages={2086–2093} } @article{chaves_shea_cope_2007, title={Environmental fate of chlorothalonil in a Costa Rican banana plantation}, volume={69}, ISSN={["1879-1298"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-34548803918&partnerID=MN8TOARS}, DOI={10.1016/j.chemosphere.2007.03.048}, abstractNote={The environmental fate of chlorothalonil (CHT) and its metabolites were studied under field-variable conditions in a commercial banana plantation in Costa Rica. Weather conditions were representative of a tropical environment and the fungicide applications were typical of those in banana production. The test plots were treated with Bravo 720® at 1.2 l ha−1 of formulated product. Field persistence of CHT in soil and on banana leaves was measured during five consecutive months and after three aerial applications of the fungicide. Residues were analyzed in soil, sediment, water, banana leaves and drift cards by gas and liquid chromatography coupled to mass spectrometry. In soil and on the surface of banana leaves, CHT dissipated rapidly with half-lives of 2.2 and 3.9 d, respectively. Soil residues persisted and were detected 85 d after application. The main metabolite found in soil, 4-hydroxy-chlorothalonil, accounted for approximately 65% of residues detected and was measured up to 6 d after application.}, number={7}, journal={CHEMOSPHERE}, author={Chaves, Alicia and Shea, Damian and Cope, W. Gregory}, year={2007}, month={Oct}, pages={1166–1174} } @article{mccarthy_bales_cope_shea_2007, title={Modeling pesticide fate in a small tidal estuary}, volume={200}, ISSN={["0304-3800"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-36248954131&partnerID=MN8TOARS}, DOI={10.1016/j.ecolmodel.2006.07.013}, abstractNote={Abstract The exposure analysis modeling system (EXAMS), a pesticide fate model developed by the U.S. Environmental Protection Agency, was modified to model the fate of the herbicides atrazine and metolachlor in a small tidally dominated estuary (Bath Creek) in North Carolina, USA where freshwater inflow accounts for only 3% of the total flow. The modifications simulated the changes that occur during the tidal cycle in the estuary, scenarios that are not possible with the original EXAMS model. Two models were created within EXAMS, a steady-state model and a time-variant tidally driven model. The steady-state model accounted for tidal flushing by simply altering freshwater input to yield an estuary residence time equal to that measured in Bath Creek. The tidal EXAMS model explicitly incorporated tidal flushing by modifying the EXAMS code to allow for temporal changes in estuary physical attributes (e.g., volume). The models were validated with empirical measurements of atrazine and metolachlor concentrations in the estuary shortly after herbicide application in nearby fields and immediately following a rain event. Both models provided excellent agreement with measured concentrations. The steady-state EXAMS model accurately predicted atrazine concentrations in the middle of the estuary over the first 3 days and under-predicted metolachlor by a factor of 2–3. The time-variant, tidally driven EXAMS model accurately predicted the rise and plateau of both herbicides over the 6-day measurement period. We have demonstrated the ability of these modified EXAMS models to be useful in predicting pesticide fate and exposure in small tidal estuaries. This is a significant improvement and expansion of the application of EXAMS, and given the wide use of EXAMS for surface water quality modeling by both researchers and regulators and the ability of EXAMS to interface with terrestrial models (e.g., pesticide root zone model) and bioaccumulation models, we now have an easily-accessible and widely accepted means of modeling chemical fate in estuaries.}, number={1-2}, journal={ECOLOGICAL MODELLING}, author={McCarthy, Annette M. and Bales, Jerad D. and Cope, W. Gregory and Shea, Damian}, year={2007}, month={Jan}, pages={149–159} } @article{kong_shea_baynes_riviere_xia_2007, title={Regression method of the hydrophobicity for determining octanol/water partition ruler approach coefficients of very hydrophobic compounds}, volume={66}, ISSN={["0045-6535"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-33751246493&partnerID=MN8TOARS}, DOI={10.1016/j.chemosphere.2006.06.060}, abstractNote={A regression method was developed for the hydrophobicity ruler approach, which is an indirect method for determining the octanol/water partition coefficients of very hydrophobic compounds. Two constants introduced into the mathematical model were obtained by regression of the absorption data sampled before the partition equilibrium. A water miscible organic solvent was used to increase the solubility of the very hydrophobic compounds in the aqueous solution so that the hydrophobicity scale was reduced and the equilibration was accelerated. Polydimethylsiloxane/methanol aqueous solution and a series of 21 polychlorinated biphenyls (PCBs) were used to demonstrate the regression method. The PCB compounds with known experimental logK(o/w) values served as reference compounds, while the PCB compounds without known logK(o/w) values were determined. The distribution coefficients (logK(p/s)), uptake and elimination rate constants were obtained from the two regression constants for each compound (reference or unknown). The correlation of the logK(p/s) values of the reference PCB compounds with their logK(o/w) values was linear (logK(o/w)=2.69logK(p/s)+0.76, R(2)=0.97). The logK(o/w) values were compared with literature values and suggested that some values from the literature far off the calibration line could be inaccurate. The critical experimental factors, the merits of the regression method were discussed.}, number={6}, journal={CHEMOSPHERE}, author={Kong, Xiang Q. and Shea, Damian and Baynes, Ronald E. and Riviere, Jim E. and Xia, Xin-Rui}, year={2007}, month={Jan}, pages={1086–1093} } @inbook{thorsen_cope_shea_2007, place={Pensacola, FL}, title={Toxicokinetics of Environmental Contaminants in Freshwater Bivalves}, booktitle={Freshwater Bivalve Ecotoxicology}, publisher={Society of Environmental Toxicology and Chemistry Publishers}, author={Thorsen, W.A. and Cope, W.G. and Shea, D.}, editor={Van Hassel, JH and Farris, JLEditors}, year={2007}, pages={169–213} } @article{shea_tester_cohen_kibler_varnam_2006, title={Accumulation of brevetoxins by passive sampling devices}, volume={28}, ISSN={["1814-232X"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-33749641340&partnerID=MN8TOARS}, DOI={10.2989/18142320609504182}, abstractNote={We report on initial investigations into the use of polymer-based passive sampling devices for the chronic time-integrated measure of brevetoxins in natural waters. Polyethylene membranes readily accumulated brevetoxins, but reached steady state within a few days, likely owing to surface saturation on the polyethylene membrane and steric hinderance of movement of the large brevetoxins through the membrane. In contrast, polydimethylsiloxane (PDMS) exhibited no apparent steric hindrance and followed linear uptake kinetics of brevetoxins for at least two weeks. The PDMS membranes show excellent promise as a passive sampling device for the measurement of chronic exposure to brevetoxins in nature.}, number={2}, journal={AFRICAN JOURNAL OF MARINE SCIENCE}, author={Shea, D. and Tester, P. and Cohen, J. and Kibler, S. and Varnam, S.}, year={2006}, month={Sep}, pages={379–381} } @article{hewitt_cope_kwak_augspurger_lazaro_shea_2006, title={Influence of water quality and associated contaminants on survival and growth of the endangered Cape Fear shiner (Notropis mekistocholas)}, volume={25}, ISSN={["0730-7268"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-33750596805&partnerID=MN8TOARS}, DOI={10.1897/05-569r.1}, abstractNote={Abstract}, number={9}, journal={ENVIRONMENTAL TOXICOLOGY AND CHEMISTRY}, author={Hewitt, Amanda H. and Cope, W. Gregory and Kwak, Thomas J. and Augspurger, Tom and Lazaro, Peter R. and Shea, Damian}, year={2006}, month={Sep}, pages={2288–2298} } @article{heltsley_cope_shea_bringolf_kwak_malindzak_2005, title={Assessing organic contaminants in fish: Comparison of a nonlethal tissue sampling technique to mobile and stationary passive sampling devices}, volume={39}, ISSN={["1520-5851"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-26044466979&partnerID=MN8TOARS}, DOI={10.1021/es051037s}, abstractNote={As concerns mount over the human health risks associated with consumption of fish contaminated with persistent organic pollutants, there exists a need to better evaluate fish body burdens without lethally sampling many of the important commercial and sport species of interest. The aim of this study was to investigate two novel methods for estimating organic contaminants in fish that are a concern for both fish and human health. The removal of fish adipose fins, commonly done in mark-recapture studies with salmonid species, was evaluated as a nonlethal sampling technique to estimate concentrations of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in flathead catfish (Pylodictis olivaris), relative to those found in muscle fillets of the same fish. We also assessed the efficacy of using poly(dimethylsiloxane) (PDMS) as a mobile passive sampling device (PSD) attached directly to wild flathead catfish for assessing location-specific exposure of the fish to waterborne contaminants. The results of this study have demonstrated for the first time that organic contaminant concentrations in adipose fin were highly correlated (R2 = 0.87) with muscle fillet concentrations, indicating that the adipose fin of certain fishes may be used to accurately estimate tissue concentrations without the need for lethal sampling. Moreover, mobile PSDs attached directly to fish and used here for the first time accurately estimated ultratrace concentrations of waterborne PCBs and OCPs without any apparent harm to the fish, indicating that there are no practical or physical barriers to the use of mobile passive samplers attached to aquatic organisms. Among the many practical implications of this research, two potential priority items include the analysis of organic contaminants in farm-raised and sport fish intended for human consumption, without the economic and population losses associated with lethally sampling fish to obtain tissues, and identifying specific areas where fish may be accumulating large portions of their contaminant burden.}, number={19}, journal={ENVIRONMENTAL SCIENCE & TECHNOLOGY}, author={Heltsley, RM and Cope, WG and Shea, D and Bringolf, RB and Kwak, TJ and Malindzak, EG}, year={2005}, month={Oct}, pages={7601–7608} } @article{gregory_shea_guthrie-nichols_2005, title={Impact of vegetation on sedimentary organic matter composition and polycyclic aromatic hydrocarbon attenuation}, volume={39}, ISSN={["1520-5851"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-22344433253&partnerID=MN8TOARS}, DOI={10.1021/es048028o}, abstractNote={Results from natural and engineered phytoremediation systems provide strong evidencethatvegetated soils mitigate polycyclic aromatic hydrocarbon (PAH) contamination. However, the mechanisms by which PAH mitigation occurs and the impact of plant organic matter on PAH attenuation remain unclear. This study assessed the impact of plant organic matter on PAH attenuation in labile and refractory sediments fractions from a petroleum distillate waste pit that has naturally revegetated. Samples were collected in distinct zones of barren and vegetated areas to assess changes to organic matter composition and PAH content as vegetation colonized and became established in the waste pit. Sediments were fractionated into bulk sediment and humin fractions and analyzed for organic matter composition by isotope ratio mass spectrometry (delta (13)C), 13C nuclear magnetic resonance (13C NMR), delta 14C AMS (accelerator mass spectrometry), and percent organic carbon (%TOC). Gas chromatography mass spectrometry (GC/ MS) of lipid extracts of SOM fractions provided data for PAH distribution histograms, compound weathering ratios, and alkylated and nonalkylated PAH concentrations. Inputs of biogenic plant carbon, PAH weathering, and declines in PAH concentrations are most evidentfor vegetated SOM fractions, particularly humin fractions. Sequestered PAH metabolites were also observed in vegetated humin. These results show that plant organic matter does impact PAH attenuation in both labile and refractory fractions of petroleum distillate waste.}, number={14}, journal={ENVIRONMENTAL SCIENCE & TECHNOLOGY}, author={Gregory, ST and Shea, D and Guthrie-Nichols, E}, year={2005}, month={Jul}, pages={5285–5292} } @article{kong_shea_gebreyes_xia_2005, title={Novel hydrophobicity ruler approach for determining the octanol/water partition coefficients of very hydrophobic compounds via their polymer/solvent solution distribution coefficients}, volume={77}, ISSN={["1520-6882"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-14744281423&partnerID=MN8TOARS}, DOI={10.1021/ac048847r}, abstractNote={A novel hydrophobicity ruler approach for determining the octanol/water partition coefficients of very hydrophobic compounds is proposed, which is an indirect method that measures the polymer/solvent solution distribution coefficients (log Kp/s) of reference and unknown compounds. The log Kp/s values of the unknown compounds can be calibrated to their log Ko/w values via the correlation of the log Kp/s values of the reference compounds with their log Ko/w values. An organic solvent was used to increase the solubility of the very hydrophobic compounds in the aqueous solution, so that their concentrations and absorption amounts were high enough to be measured precisely. The solvent also reduced the hydrophobicity scale of the very hydrophobic compounds and controlled the amounts absorbed into the polymer phase, so that compounds spanning a very wide range of log Ko/w values could be measured in a single measurement and the coexisting compounds would not interfere each other. Poly(dimethylsiloxane) (PDMS), aqueous methanol solutions, and a series of 21 PCB (polychlorinated biphenyl) compounds were used to demonstrate the principle of the hydrophobicity ruler approach. The PCB compounds with known experimental log Ko/w values served as reference compounds, whereas the PCB compounds without known log Ko/w values were determined. The log Ko/w values determined for PCB126, PCB187, PCB197, PCB180, PCB170, and PCB195 were 6.94, 7.84, 8.33, 8.17, 7.92, and 8.49, respectively. The correlation of the log Kp/s values of the reference PCB compounds with their log Ko/w values was linear (log Ko/w=2.56 log Kp/s+1.08, R2=0.95). The hydrophobicity ruler approach is also a valuable tool for validating the experimental and theoretical log Ko/w values and identifying outliers in log Ko/w databases.}, number={5}, journal={ANALYTICAL CHEMISTRY}, author={Kong, XQ and Shea, D and Gebreyes, WA and Xia, XR}, year={2005}, month={Mar}, pages={1275–1281} } @article{neal_bacheler_noble_shea_cope_2005, title={The mystery of Dos Bocas Reservoir, Puerto Rico: Explaining extreme spatial heterogeneity in largemouth bass distribution}, volume={41}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-31344439731&partnerID=MN8TOARS}, number={4}, journal={Caribbean Journal of Science}, author={Neal, J.W. and Bacheler, N.M. and Noble, R.L. and Shea, D. and Cope, W.G.}, year={2005}, pages={804–814} } @article{thorsen_cope_shea_2004, title={Bioavailability of PAHs: Effects of soot carbon and PAH source}, volume={38}, ISSN={["1520-5851"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-1842728707&partnerID=MN8TOARS}, DOI={10.1021/es0306056}, abstractNote={The bioavailability of 38 individual polycyclic aromatic hydrocarbon (PAH) compounds was determined through calculation of biota-sediment-accumulation factors (BSAF). BSAF values were calculated from individual PAH concentrations in freshwater mussel, marine clam, and sediment obtained from field and laboratory bioaccumulation studies. Sediment that was amended with different types of soot carbon (SC) was used in some of the bioaccumulation experiments. BSAF values for petrogenic PAH were greater than those for pyrogenic PAH (e.g., 1.57 +/- 0.53 vs 0.25 +/- 0.23, respectively), indicating that petrogenic PAH are more bioavailable than pyrogenic PAH (p < 0.05). This trend was consistent among marine and freshwater sites. Increased SC content of sediment resulted in a linear decrease in the bioavailability of pyrogenic PAHs (r2 = 0.85). The effect of increasing SC content on petrogenic PAH was negligible. SC was considered as an additional sorptive phase when calculating BSAF values, and using PAH-SC partition coefficients from the literature, we obtained unreasonably large BSAF values for all petrogenic PAH and some pyrogenic PAH. This led us to conclude that a quantitative model to assess bioavailability through a combination of organic carbon and soot carbon sorption is not applicable among field sites with a wide range of soot carbon fractions and PAH sources, at least given our current knowledge of PAH-SC partitioning. Our data offer evidence that many factors including analysis of a full suite of PAH analytes, PAH hydrophobicity, sediment organic carbon content, sediment soot carbon content, and PAH source are importantto adequately assess PAH bioavailability in the environment.}, number={7}, journal={ENVIRONMENTAL SCIENCE & TECHNOLOGY}, author={Thorsen, WA and Cope, WG and Shea, D}, year={2004}, month={Apr}, pages={2029–2037} } @article{thorsen_forestier_sandifer_lazaro_cope_shea_2004, title={Elimination rate constants of 46 polycyclic aromatic hydrocarbons in the unionid mussel, Elliptio complanata}, volume={47}, ISSN={["0090-4341"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-4644281509&partnerID=MN8TOARS}, DOI={10.1007/s00244-004-3186-y}, abstractNote={Elimination rate constants (k2), biological half-lives (t(1/2)), and the time required to reach 95% of steady-state (t95) are reported for 46 individual polycyclic aromatic hydrocarbons (PAHs) including both parent and alkyl homologues, for the freshwater unionid mussel, Elliptio complanata. Elimination rate constants generally follow first-order kinetics and range from 0.04/day (d) for perylene to 0.26/d for 2,6-dimethylnapthalene, half-lives range from 2.6 to 16.5 d, and t95 values range from 11.3 to 71.3 d. These values compare well with other k2, t(1/2), and t95 values reported in the literature for PAHs and other classes of hydrophobic organic contaminants. A linear regression of k2 versus log Kow demonstrates dependence of PAH elimination on hydrophobicity, as measured by an r2 value of 0.83, and produces the following regression equation: k2 = -0.06 (log Kow) + 0.44. This study provides evidence that mussels experiencing different forms of physiological stress (e.g., handling stress and fungal or bacterial growth) can exhibit large variation in toxicokinetic parameters. These results are particularly relevant to the extrapolation of laboratory results to field situations.}, number={3}, journal={ARCHIVES OF ENVIRONMENTAL CONTAMINATION AND TOXICOLOGY}, author={Thorsen, WA and Forestier, D and Sandifer, T and Lazaro, PR and Cope, WG and Shea, D}, year={2004}, month={Oct}, pages={332–340} } @inbook{shea_2004, place={Hoboken, NJ USA}, edition={3rd}, title={Environmental Risk Assessment}, ISBN={9780471265085 9780471646778}, DOI={https://doi.org/10.1002/0471646776.ch28}, abstractNote={Introduces the procedures necessary to formulate the particular environmental risk problem through assessment of appropriate endpoints and the development of conceptual models, analyzing exposure and effects information, and characterizing exposure and ecological effects. On this basis the risk is characterized and subsequently managed.}, booktitle={A Textbook of Modern Toxicology}, publisher={John Wiley & Sons, Inc}, author={Shea, D.}, editor={Hodgson, E.Editor}, year={2004}, pages={501–517} } @inbook{shea_2004, place={Hoboken, NJ USA}, edition={3rd}, title={Transport and Fate of Toxicants in the Environment}, ISBN={9780471265085 9780471646778}, DOI={10.1002/0471646776.ch27}, abstractNote={More than 100,000 chemicals are released into the global environment every year through their normal production, use, and disposal. To understand and predict the potential risk that this environmental contamination poses to humans and wildlife, we must couple our knowledge on the toxicity of a chemical to our knowledge on how chemicals enter into and behave in the environment. The simple box model shown in Figure 27.1 illustrates the relationship between a toxicant source, its fate in the environment, its effective exposure or dose, and resulting biological effects. A prospective or predictive assessment of a chemical hazard would begin by characterizing the source of contamination, modeling the chemical’s fate to predict exposure, and using exposure/dose-response functions to predict effects (moving from left to right in Figure 27.1). A common application would be to assess the potential effects of a new waste discharge. A retrospective assessment would proceed in the opposite direction starting with some observed effect and reconstructing events to find a probable cause. Assuming that we have reliable dose/exposure-response functions, the key to successful use of this simple relationship is to develop a qualitative description and quantitative model of the sources and fate of toxicants in the environment. Toxicants are released into the environment in many ways, and they can travel along many pathways during their lifetime. A toxicant present in the environment at a given point in time and space can experience three possible outcomes: it can be stationary and add to the toxicant inventory and exposure at that location, it can be transported to another location, or it can be transformed into another chemical species. Environmental contamination and exposure resulting from the use of a chemical is modified by the transport and transformation of the chemical in the environment. Dilution and degradation can attenuate the source emission, while processes that focus and accumulate the chemical can magnify the source emission. The actual fate of a chemical depends on the chemical’s use pattern and physical-chemical properties, combined with the characteristics of the environment to which it is released.}, booktitle={Textbook of Modern Toxicology}, publisher={John Wiley & Sons, Inc}, author={Shea, D.}, editor={Hodgson, E.Editor}, year={2004}, pages={479–499} } @article{xia_baynes_monteiro-riviere_leidy_shea_riviere_2003, title={A novel in-vitro technique for studying percutaneous permeation with a membrane-coated fiber and gas chromatography/mass spectrometry: Part I. Performances of the technique and determination of the permeation rates and partition coefficients of chemical mixtures}, volume={20}, ISSN={["0724-8741"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0037331884&partnerID=MN8TOARS}, DOI={10.1023/A:1022287524024}, abstractNote={[[{:Label=>"PURPOSE", :NlmCategory=>"OBJECTIVE"}, "To develop a novel in-vitro technique for rapid assessment of percutaneous absorption of chemical mixtures."], [{:Label=>"METHODS", :NlmCategory=>"METHODS"}, "A silastic membrane was coated on to a fiber to be used as a permeation membrane. The membrane-coated fiber was immersed in the donor phase to partition the compounds into the membrane. At a given partition time, the membrane-coated fiber was transferred into a GC injector to evaporate the partitioned compounds for quantitative and qualitative analyses."], [{:Label=>"RESULTS", :NlmCategory=>"RESULTS"}, "This technique was developed and demonstrated to study the percutaneous permeation of a complex mixture consisting of 30 compounds. Each compound permeated into the membrane was identified and quantified with GC/MS. The standard deviation was less than 10% in 12 repeated permeation experiments. The partition coefficients and permeation rates in static and stirred donor solution were obtained for each compound. The partition coefficients measured by this technique were well correlated (R2 = 0.93) with the reported octanol/water partition coefficients."], [{:Label=>"CONCLUSIONS", :NlmCategory=>"CONCLUSIONS"}, "This technique can be used to study the percutaneous permeation of chemical mixtures. No expensive radiolabeled chemicals are required. Each compound permeated into the membrane can be identified and quantified. The initial permeation rate and equilibrium time can be obtained for each compound, which could serve as characteristic parameters regarding the skin permeability of the compound."]]}, number={2}, journal={PHARMACEUTICAL RESEARCH}, author={Xia, XR and Baynes, RE and Monteiro-Riviere, NA and Leidy, RB and Shea, D and Riviere, JE}, year={2003}, month={Feb}, pages={275–282} } @article{luellen_shea_2003, title={Semipermeable membrane devices accumulate conserved ratios of sterane and hopane petroleum biomarkers}, volume={53}, ISSN={["0045-6535"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0642311223&partnerID=MN8TOARS}, DOI={10.1016/S0045-6535(03)00576-9}, abstractNote={Semipermeable membrane devices (SPMDs) are commonly used as a time-integrated measure of aqueous concentrations of persistent hydrophobic chemicals, including PAH, pesticides, dioxins, and PCBs. Another class of persistent hydrophobic chemicals is petroleum biomarker compounds (hopanes and steranes) that are used for hydrocarbon source identification and allocation. In this study three different passive sampling device designs were exposed to a complex hydrocarbon mixture (Alaska North Slope crude) in a laboratory experiment to determine uptake rates of biomarkers into SPMDs. In addition to the standard triolein filled SPMDs, iso-octane filled SPMDs (ISPMDs) and unfilled low-density polyethylene strips (PESDs) were tested. Uptake rates and effective sampling rates were determined for 53 compounds. There was little variation in sampling rates among the individual biomarkers; average values (ld(-1)) for hopanes were 0.43+/-0.07 (PESD), 0.33+/-0.06 (SPMD), and 0.44+/-0.03 (ISPMD) and average sterane sampling rates were 0.57+/-0.04 (PESD), 0.42+/-0.03 (SPMD), and 0.53+/-0.03 (ISPMD). The primary reason for biomarker analysis is for source discrimination of petroleum. Nineteen different diagnostic ratios were measured, and were found to be remarkably well conserved between the oil, water, and all three devices. This indicates that SPMDs, PESDs, and ISPMDs should each be effective for source discrimination studies of petroleum contamination.}, number={7}, journal={CHEMOSPHERE}, author={Luellen, DR and Shea, D}, year={2003}, month={Nov}, pages={705–713} } @article{luellen_shea_2002, title={Calibration and field verification of semipermeable membrane devices for measuring polycyclic aromatic hydrocarbons in water}, volume={36}, ISSN={["1520-5851"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0037089031&partnerID=MN8TOARS}, DOI={10.1021/es0113504}, abstractNote={The use of semipermeable membrane devices (SPMDs) has become common in environmental sampling of nonpolar organic contaminants, yet few data exist for the uptake or sampling rates of polycyclic aromatic hydrocarbons (PAH). Two separate laboratory calibration experiments were conducted to determine the sampling rates of 28 individual PAH and 19 homologues. PAH with a log Kow > 4.5 remained in the linear uptake phase for 30 days, but PAH with a log Kow < 4.5 began to approach steady state within 15 days. Sampling rates, corrected for dissolved organic carbon, ranged from 2.11 to 6.06 L d(-1). Shear flow across the membrane had no statistically significant effect on rates over the range of 0.01-0.50 cm s(-1). Field verification of these sampling rates yielded agreement within about a factor of 2 for most PAH and a factor of 4 for all PAH. The worst agreement was for the most hydrophobic PAH, where partitioning into dissolved and particulate organic carbon pools are more important and less certain. These SPMD sampling rate data will allow quantitative estimations of freely dissolved concentrations of 47 compounds that are commonly used for PAH and petroleum product source identification and allocation.}, number={8}, journal={ENVIRONMENTAL SCIENCE & TECHNOLOGY}, author={Luellen, DR and Shea, D}, year={2002}, month={Apr}, pages={1791–1797} } @inproceedings{thorsen_cope_shea_2002, title={Soot carbon and PAH source control PAH bioavailability}, volume={42}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-23844508863&partnerID=MN8TOARS}, number={2}, booktitle={ACS Division of Environmental Chemistry, Preprints}, author={Thorsen, W.A. and Cope, W.G. and Shea, D.}, year={2002}, pages={283–289} } @article{weisbrod_shea_moore_stegeman_2001, title={Species, tissue and gender-related organochlorine bioaccumulation in white-sided dolphins, pilot whales and their common prey in the Northwest Atlantic}, volume={51}, ISSN={["1879-0291"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0035239021&partnerID=MN8TOARS}, DOI={10.1016/S0141-1136(00)00032-5}, abstractNote={Organochlorine concentrations were measured in white-sided dolphins, pilot whales, and their prey from the Gulf of Maine and used to identify species, tissue, and gender differences, and trophic transfer trends, in bioaccumulation. Polychlorinated biphenyl concentrations ([PCB]) in dolphin blubber (13±7.1 μg/g fresh wt.) were twice those in pilot whales, but pesticide concentrations (20±13 μg/g fresh) were similar between species. 4,4′-DDE, trans-nonachlor, Cl6(153) and Cl6(138) concentrations were highest. Skin tissues had more recalcitrant organochlorines than the internal organs. Male dolphins bioaccumulated higher concentrations of nonmetabolizable PCBs and hexachlorocyclohexane (HCH) isomers, whereas pilot whales had no gender-related differences in bioaccumulation. Pilot whales, mackerel, and herring had proportionately higher concentrations of DDTs, whereas [PCB] were higher in dolphins and squid. Although these odontocetes feed at the same trophic level and store a similar suite of contaminants, dolphins bioaccumulated higher and potentially hazardous 4,4′-DDE and PCB concentrations from food in their more geographically restricted range.}, number={1}, journal={MARINE ENVIRONMENTAL RESEARCH}, author={Weisbrod, AV and Shea, D and Moore, MJ and Stegeman, JJ}, year={2001}, month={Feb}, pages={29–50} } @article{weisbrod_shea_moore_john_2000, title={Bioaccumulation patterns of polychlorinated biphenyls and chlorinated pesticides in Northwest Atlantic pilot whales}, volume={19}, ISSN={["1552-8618"]}, DOI={10.1897/1551-5028(2000)019<0667:BPOPBA>2.3.CO;2}, abstractNote={Environmental Toxicology and ChemistryVolume 19, Issue 3 p. 667-677 Environmental Toxicology Bioaccumulation patterns of polychlorinated biphenyls and chlorinated pesticides in Northwest Atlantic pilot whales† Anne V. Weisbrod, Corresponding Author Anne V. Weisbrod [email protected] Procter&Gamble, Sharon Woods Technical Center, 11530 Reed Hartman Highway, Cincinnati, Ohio 45241–2422, USA North Carolina State University, Department of Toxicology, Box 8604, Raleigh, North Carolina 27606, USAProcter&Gamble, Sharon Woods Technical Center, 11530 Reed Hartman Highway, Cincinnati, Ohio 45241–2422, USASearch for more papers by this authorDamian Shea, Damian Shea North Carolina State University, Department of Toxicology, Box 8604, Raleigh, North Carolina 27606, USASearch for more papers by this authorMichael J. Moore, Michael J. Moore Woods Hole Oceanographic Institution, Biology Department, Mailstop 33, Woods Hole, Massachusetts 02543, USASearch for more papers by this authorJohn J. Stegeman, John J. Stegeman Woods Hole Oceanographic Institution, Biology Department, Mailstop 33, Woods Hole, Massachusetts 02543, USASearch for more papers by this author Anne V. Weisbrod, Corresponding Author Anne V. Weisbrod [email protected] Procter&Gamble, Sharon Woods Technical Center, 11530 Reed Hartman Highway, Cincinnati, Ohio 45241–2422, USA North Carolina State University, Department of Toxicology, Box 8604, Raleigh, North Carolina 27606, USAProcter&Gamble, Sharon Woods Technical Center, 11530 Reed Hartman Highway, Cincinnati, Ohio 45241–2422, USASearch for more papers by this authorDamian Shea, Damian Shea North Carolina State University, Department of Toxicology, Box 8604, Raleigh, North Carolina 27606, USASearch for more papers by this authorMichael J. Moore, Michael J. Moore Woods Hole Oceanographic Institution, Biology Department, Mailstop 33, Woods Hole, Massachusetts 02543, USASearch for more papers by this authorJohn J. Stegeman, John J. Stegeman Woods Hole Oceanographic Institution, Biology Department, Mailstop 33, Woods Hole, Massachusetts 02543, USASearch for more papers by this author First published: 02 November 2009 https://doi.org/10.1002/etc.5620190319Citations: 27 † The views expressed herein are those of the authors and do not necessarily reflect the views of the National Oceanic and Atmospheric Administration, its subagencies, or other sponsors. Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Abstract Contaminant exposure is widespread among marine mammals but is of unknown significance. This study characterized organochlorine bioaccumulation in pilot whales, and these bioaccumulation patterns are proposed as representative of Northwest (NW) Atlantic cetacea. Samples were collected from whales stranded in Massachusetts and caught in nets. Polychlorinated biphenyl (PCB) and chlorinated pesticide concentrations were determined via GC/ECD and found to be similar to those reported for other NW Atlantic odontocetes. The organochlorine in highest concentration was 4,4′-DDE, followed by trans-nonachlor, 4,4′-DDD, dieldrin, cis-chlordane, Cl4(52), Cl5(95), Cl5(101), Cl5(118), Cl6(138), Cl6(149), Cl6(153), Cl7(180), and Cl7(187). The concentration of 19 pesticides was higher in blubber (21 ± 26 μg/g lipid "ppm") than liver (5.0 ± 7.1 ppm). The concentration of 26 PCB congeners was also greater in blubber (7.6 ±7.1 ppm) than liver (0.4 ± 7.3 ppm). Principal component analysis and ANOVA indicated that blubber accumulated proportionately more of the most recalcitrant compounds, such as 4,4′-DDE and nonmetabolizable PCBs, compared to liver. Whales that stranded together had more similar bioaccumulation than animals of the same gender or maturity. The high variation among individuals in tissue concentrations and the similarity within a stranding group suggest that pilot whale pods are exposed to a large range of pollutant sources, such as through different prey and feeding locations. References 1 Waring GT, Palka DL, Mullin KD, Hain JHW, Hansen LJ, Bisack KD. 1997. U.S. Atlantic and Gulf of Mexico marine mammal stock assessments-1996. NMFS-NE-114. Technical Memorandum. National Oceanographic and Atmospheric Administration, Woods Hole, MA, USA. 2 Addison RF, Brodie PF. 1977. Organochlorine residues in maternal blubber, milk, and pup blubber from grey seals (Halichoerus grypus) from Sable Island, Nova Scotia. J Fish Res Board Can 34: 937– 941. 3 U.S. Environmental Protection Agency. 1993. Assessment of potential impact of the MWRA outfall on endangered species. Biological assessment prepared pursuant to Section 7 of the Endangered Species Act. Boston, MA. 4 Gauthier JM, Metcalfe CD, Sears R. 1997. Validation of the blubber biopsy technique for monitoring organochlorine contaminants in balaenopterid whales. Mar Environ Res 43: 157– 179. 5 Lake CA, Lake JL, Haebler R, McKinney R, Boothman WS, Sadove SS. 1995. Contaminant levels in harbor seals from the Northeastern United States. Arch Environ Contam Toxicol 29: 128– 134. 6 Westgate AJ, Muir DCG, Gaskin DE, Kingsley MCS. 1997. Concentrations and accumulation patterns of organochlorine contaminants in the blubber of harbour porpoises, Phocoena phocoena, from the coast of Newfoundland, the Gulf of St. Lawrence and the Bay of Fundy/Gulf of Maine. Environ Pollut 95: 105– 119. 7 Kuehl DW, Haebler R, Potter C. 1991. Chemical residues in dolphins from the U.S. Atlantic coast including Atlantic bottlenose obtained during the 1987/88 mass mortality. Chemosphere 22: 1071– 1084. 8 Martineau D, Beland P, Desjardins C, Lagace A. 1987. Levels of organochlorine chemicals in tissues of beluga whales (Delphi-napterus leucus) from the St. Lawrence Estuary, Quebec, Canada. Arch Environ Contam Toxicol 16: 137– 147. 9 Meador JP, Varanasi U, Robisch PA, Chan S-L. 1993. Toxic metals in pilot whales (Globicephala melaena) from strandings in 1986 and 1990 on Cape Cod, MA. Can J Fish Aquat Sci 50: 2698– 2706. 10 Muir DCG, Wagemann R, Grift NP, Norstrom RJ, Simon M, Lien J. 1988. Organochlorine chemical and heavy metal contaminants in white-beaked dolphins (Lagenorhynchus albirostris) and pilot whales (Globicephala melaena) from the coast of Newfoundland. Can Arch Environ Contam Toxicol 17: 613– 629. 11 Muir DCG, Ford CA, Steward REA, Smith TG, Addison RF, Zinck ME, Beland P. 1990. Organochlorine contaminants in belugas, Delphinapterus leucas, from Canadian waters. In TG Smith, DJ St. Aubin, JR Geraci, eds, Advances in Research on the Beluga Whale, Delphinapterus leucas, Vol 224. Canadian Bulletin of Fisheries and Aquatic Sciences, Special Issue. pp 165– 190. 12 O'Shea TJ, Brownell RL Jr., 1994. Organochlorine and metal contaminants in baleen whales: A review and evaluation of conservation implications. Sci Total Environ 154: 179– 200. 13 Taruski AG, Olney CE, Winn HE. 1975. Chlorinated hydrocarbons in cetaceans. J Fish Res Board Can 32: 2205– 2209. 14 Hellou J, Stenson G, Ni I-H, Payne JF. 1990. Polycyclic aromatic hyrdocarbons in muscle tissue of marine mammals from the Northwest Atlantic. Mar Pollut Bull 21: 469– 473. 15 Woodley TH, Brown MW, Kraus SD, Gaskin DE. 1991. Organ-ochlorine levels in North Atlantic right whale. Arch Environ Con-tam Toxicol 21: 141– 145. 16 Weisbrod AV. 1998. Organochlorine bioaccumulation and potential effects in three Northwest Atlantic whales. PhD thesis. North Carolina State University, Raleigh, NC, USA. 17 Sergeant DE. 1962. The biology of the pilot or pothead whale Globicephala melaena (Traill) in Newfoundland waters. Bulletin 132. Fisheries Research Board of Canada. 18 Donovan GP. 1993. Biology of northern hemisphere pilot whales. IWC Report 14. International Whaling Commission, Cambridge, UK. 19 Martin AR, Reynolds P, Richardson MG. 1987. Aspects of the biology of pilot whales (Globicephala melaena) in recent mass strandings on the British coast. J Zool Lond 211: 11– 23. 20 Amos B, Bloch D, Desportes G, Majerus TMO, Bancroft DR, Barrett JA, Dover GA. 1993. A review of molecular evidence relating to social organization and breeding system in the long-finned pilot whale. In GP Donovan, CH Lockyer, AR Martin, eds, Biology of Northern Hemisphere Pilot Whales, Vol 14. International Whaling Commission, Cambridge, UK, pp 209– 217. 21 Payne PM, Heinemann DW. 1993. The distribution of pilot whales (Globicephala spp.) in the shelf/shelf-edge and slope waters of the Northeastern United States, 1978–1988. In GP Donovan, CH Lockyer, AR Martin, eds, Biology of Northern Hemisphere Pilot Whales, Vol 14. International Whaling Commission, Cambridge, UK, pp 51– 68. 22 Selzer LA, Payne PM. 1988. The distribution of white-sided dolphin (Lagenorhynchus acutus) and common dolphins (Delphinus delphis) vs. environmental features of the continental shelf of the Northeastern United States. Mar Mamm Sci 4: 141– 153. 23 Stone GS, Kraus SD, Prescott JH, Hazard KW. 1988. Significant aggregations of the endangered right whale, Eubalaena glacialis, on the continental shelf of Nova Scotia. Can Field-Nat 102: 471– 474. 24 Gannon DP, Read AJ, Mead JG. 1997. Stomach content of long-finned pilot whales (Globicephala melas) stranded on the U.S. mid-Atlantic coast. Mar Mamm Sci 13: 405– 418. 25 Arai MN. 1988. Interactions of fish and pelagic coelenterates. Can J Zool 66: 1913– 1927. 26 Checkley DMJ. 1982. Selective feeding by Atlantic herring (Clu-pea harengus) larvae on zooplankton in natural assemblages. Mar Ecol Prog Ser 9: 245– 253. 27 Mayo CA, Marx MK. 1990. Surface foraging behaviour of the North Atlantic right whale, Eubalaena glacialis, and associated zooplankton characteristics. Can J Zool 68: 2214– 2220. 28 Fairfield CP, Waring GT, Sano MH. 1993. Pilot whales incidentally taken during the distant water fleet Atlantic mackerel fishery in the Mid-Atlantic Bight, 1984–88. In GP Donovan, CH Lockyer, AR Martin, eds, Biology of Northern Hemisphere Pilot Whales, Vol 14. International Whaling Commission, Cambridge, UK, pp 107– 116. 29 Aguilar A. 1987. Using organochlorine pollutants to discriminate marine mammal populations: A review and critique of the methods. Mar Mamm Sci 3: 242– 262. 30 Hickie BE, Mackay D, DeKoning J. 1999. Lifetime pharmaco-kinetic model system for hydrophobic contaminants in marine mammals. Environ Toxicol Chem 18: 11. 31 Nelson D, Lien J. 1994. The status of the long-finned pilot whale, Globicephala melas, in Canada. Can Field-Nat 110: 511– 524. 32 Felleman FL, Heimlich-Boran JR, Osborne RW. 1991. The feeding ecology of killer whales (Orcinus orca) in the Pacific Northwest. In K Pryor, KS Norris, eds, Dolphin Societies, Vol 1. University of California Press, Berkeley, CA, USA, pp 113– 147. 33 Ross P, Ikonomou MG, Ellis GM, Barrett-Lennard LG, Addison RF. 1998. Elevated levels of PCBs, PCDDs, and PCDFs in harbour seals (Phoca vitulina) and killer whales (Orcinus orca) inhabiting the Strait of Georgia, BC, Canada. Proceedings, World Marine Mammal Science Congress, Monaco, January 20–24, p 160. 34 Ballschmiter K, Zell M. 1980. Analysis of polychlorinated-biphenyls (PCB) by glass capillary gas chromatography: Composition of technical Aroclor and Clophen-PCB mixtures. Fres J Anal Chem 302: 20– 31. 35 Afifi AA, Clark V. 1984. Computer-Aided Multivariate Analysis. Wadsworth, London, UK. 36 Pattern Recognition Systems. 1993. Sirius for Windows. Bergen, Norway. 37 Boon JP, Oostingh I, van der Meer J, Hillebrand MTJ. 1994. A model for the bioaccumulation of chlorobiphenyl congeners in marine mammals. Eur J Pharmacol Environ Toxicol Pharmacol 270: 237– 251. 38 Wells DE, Echarri I. 1992. Determination of individual chloro-biphenyls (CBs), including non-ortho, and mono-ortho chloro substituted CBs in marine mammals from Scottish waters. Int J Environ Anal Chem 47: 75– 97. 39 Safe SH. 1994. Polychlorinated biphenyls (PCBs): Environmental impact, biochemical and toxic responses, and implications for risk assessment. Crit Rev Toxicol 24: 87– 149. 40 Underwood AJ. 1981. Techniques of analysis of variance in experimental marine biology and ecology. Oceanogr Mar Biol Annu Rev 19: 513– 605. 41 Misra RK, Uthe JF, Vynke W. 1989. Monitoring of time trends in contaminant levels using a multispecies approach: Contaminant trends in Atlantic cod and European flounder on the Belgian coast, 1978–1985. Mar Pollut Bull 20: 500– 502. 42 Borrell A, Aguilar A. 1990. Loss of organochlorine compounds in the tissues of a decomposing stranded dolphin. Bull Environ Contam Toxicol 45: 46– 53. 43 Jepson PD, et al., 1998. Chronic PCB exposure is associated with infectious disease mortality in harbour porpoises stranded in England and Wales 1990–1996. Proceedings, World Marine Mammal Science Congress, Monaco, January 20–24, p 160. 44 Kuiken T, et al., 1994. PCBs, cause of death and body condition in harbor porpoises (Phocoena phocoena) from British waters. Aquat Toxicol 28: 128– 134. 45 Lockyer CH. 1993. Seasonal changes in body fat condition of Northeast Atlantic pilot whales, and their biological significance. In GP Donovan, CH Lockyer, AR Martin, eds, Biology of Northern Hemisphere Pilot Whales, Vol 14. International Whaling Commission, Cambridge, UK, pp 325– 349. 46 Aguilar A, Borrell A. 1991. Heterogeneous distribution of or-ganochlorine contaminants in the blubber of baleen whales: Implications for sampling procedures. Mar Environ Res 31: 275– 286. 47 Hawker DW, Connell DW. 1988. Octanol-water partition coefficients of polychlorinated biphenyl congeners. Environ Sci Tech-nol 22: 382– 387. 48 Martin AR, Rothery P. 1993. Reproductive parameters of female long-finned pilot whales (Globicephala melas) around the Faroe Islands. In GP Donovan, CH Lockyer, AR Martin, eds, Biology of Northern Hemisphere Pilot Whales, Vol 14. International Whaling Commission, Cambridge, UK, pp 263– 304. 49 Borrell A, Aguilar A. 1993. DDT and PCB pollution in blubber and muscle of the long-finned pilot whales from the Faroe Islands. In GP Donovan, CH Lockyer, AR Martin, eds, Biology of the Northern Hemisphere Pilot Whale, Vol 14. International Whaling Commission, Cambridge, UK, pp 351– 367. 50 Muir DCG, Nordstrom RJ, Simon M. 1988. Organochlorine contaminants in Arctic marine food chains: Accumulation of specific polychlorinated biphenyls and chlordane-related compounds. Environ Sci Technol 22: 1071– 1079. 51 Schantz MM, Koster BJ, Wise SA, Becker PR. 1993. Determination of PCBs and chlorinated hydrocarbons in marine mammal tissues. Sci Total Environ 139/140: 323– 345. 52 Wise SA, et al., 1993. Development of frozen whale blubber and liver reference materials for the measurement of organic and inorganic contaminants. Fres J Anal Chem 345: 270– 277. 53 Nordstrom RJ, Simon M, Muir DCG, Schweinsburg RE. 1988. Organochlorine contaminants in Arctic marine food chains: Identification, geographical distribution, and temporal trends in polar bears. Environ Sci Technol 22: 931– 940. Citing Literature Volume19, Issue3March 2000Pages 667-677 ReferencesRelatedInformation}, number={3}, journal={ENVIRONMENTAL TOXICOLOGY AND CHEMISTRY}, author={Weisbrod, AV and Shea, D and Moore, MJ and John, JJ}, year={2000}, month={Mar}, pages={667–677} } @article{weisbrod_shea_moore_stegeman_2000, title={Bioaccumulation patterns of polychlorinated biphenyls and chlorinated pesticides in northwest atlantic pilot whales}, volume={19}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0034000857&partnerID=MN8TOARS}, DOI={10.1002/etc.5620190319}, abstractNote={Contaminant exposure is widespread among marine mammals but is of unknown significance. This study characterized organochlorine bioaccumulation in pilot whales, and these bioaccumulation patterns are proposed as representative of Northwest (NW) Atlantic cetacea. Samples were collected from whales stranded in Massachusetts and caught in nets. Polychlorinated biphenyl (PCB) and chlorinated pesticide concentrations were determined via GC/ECD and found to be similar to those reported for other NW Atlantic odontocetes. The organochlorine in highest concentration was 4,4′‐DDE, followed by trans‐nonachlor, 4,4′‐DDD, dieldrin, cis‐chlordane, Cl4(52), Cl5(95), Cl5(101), Cl5(118), Cl6(138), Cl6(149), Cl6(153), Cl7(180), and Cl7(187). The concentration of 19 pesticides was higher in blubber (21 ± 26 μg/g lipid “ppm”) than liver (5.0 ± 7.1 ppm). The concentration of 26 PCB congeners was also greater in blubber (7.6 ±7.1 ppm) than liver (0.4 ± 7.3 ppm). Principal component analysis and ANOVA indicated that blubber accumulated proportionately more of the most recalcitrant compounds, such as 4,4′‐DDE and nonmetabolizable PCBs, compared to liver. Whales that stranded together had more similar bioaccumulation than animals of the same gender or maturity. The high variation among individuals in tissue concentrations and the similarity within a stranding group suggest that pilot whale pods are exposed to a large range of pollutant sources, such as through different prey and feeding locations.}, number={3}, journal={Environmental Toxicology and Chemistry}, author={Weisbrod, A.V. and Shea, D. and Moore, M.J. and Stegeman, J.J.}, year={2000}, pages={667–677} } @article{white_shea_schlezinger_hahn_stegeman_2000, title={In vitro metabolism of polychlorinated biphenyl congeners by beluga whale (Delphinapterus leucas) and pilot whale (Globicephala melas) and relationship to cytochrome P450 expression}, volume={126}, ISSN={["1878-1659"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-2042506296&partnerID=MN8TOARS}, DOI={10.1016/s0742-8413(00)00123-7}, abstractNote={We measured rates of oxidative metabolism of two tetrachlorobiphenyl (TCB) congeners by hepatic microsomes of two marine mammal species, beluga whale and pilot whale, as related to content of selected cytochrome P450 (CYP) forms. Beluga liver microsomes oxidized 3,3',4,4'-TCB at rates averaging 21 and 5 pmol/min per mg for males and females, respectively, while pilot whale samples oxidized this congener at 0.3 pmol/min per mg or less. However, rates of 3,3',4,4'-TCB metabolism correlated with immunodetected CYP1A1 protein content in liver microsomes of both species. The CYP1A inhibitor alpha-naphthoflavone inhibited 3,3',4,4'-TCB metabolism by 40% in beluga, supporting a role for a cetacean CYP1A as a catalyst of this activity. Major metabolites of 3,3',4,4'-TCB generated by beluga liver microsomes were 4-OH-3,3',4',5-TCB and 5-OH-3,3',4,4'-TCB (98% of total), similar to metabolites formed by other species CYP1A1, and suggesting a 4,5-epoxide-TCB intermediate. Liver microsomes of both species metabolized 2,2',5,5'-TCB at rates of 0.2-1.5 pmol/min per mg. Both species also expressed microsomal proteins cross-reactive with antibodies raised against some mammalian CYP2Bs (rabbit; dog), but not others (rat; scup). Whether CYP2B homologues occur and function in cetaceans is uncertain. This study demonstrates that PCBs are metabolized to aqueous-soluble products by cetacean liver enzymes, and that in beluga, rates of metabolism of 3,3',4,4'-TCB are substantially greater than those of 2,2',5,5'-TCB. These directly measured rates generally support the view that PCB metabolism plays a role in shaping the distribution patterns of PCB residues found in cetacean tissue.}, number={3}, journal={COMPARATIVE BIOCHEMISTRY AND PHYSIOLOGY C-TOXICOLOGY & PHARMACOLOGY}, author={White, RD and Shea, D and Schlezinger, JJ and Hahn, ME and Stegeman, JJ}, year={2000}, month={Jul}, pages={267–284} } @article{weisbrod_shea_leblanc_moore_stegeman_2000, title={Organochlorine bioaccumulation and risk for whales in a northwest Atlantic food web}, volume={50}, ISSN={0141-1136}, url={http://dx.doi.org/10.1016/s0141-1136(00)00216-6}, DOI={10.1016/s0141-1136(00)00216-6}, abstractNote={The poor recovery of multiple whale populations raises concern for the integrity of the US marine environment. Fifty organochlorines were measured in samples of pilot whales, white-sided dolphins, endangered right whales and their prey. As expected from their high trophic position and proximity to land-based sources, the bioaccumulation of 4,4′-DDE, several chlordanes and polychlorinated biphenyl (PCB) congeners was substantial (ppm) in squid and the stranded odontocetes. Concentrations in fish and right whale biopsies were one to two orders of magnitude less than in odontocetes. Although the prevalent pesticides were different between odontocetes and balaenopterids, the magnitude of pesticide concentrations was similar across species. PCB concentrations were higher in the Gulf of Maine dolphins than pilot and right whales. Gender and tissue type were the important characteristics contributing to the bioaccumulation patterns observed in dolphins. Season of sample collection and exposure to different prey seemed critical for the bioaccumulation observed in right and pilot whales. Dolphin and pilot whale organs contained ample concentrations of specific compounds, notably 4,4′-DDE, that have been shown to alter endocrine function.}, number={1-5}, journal={Marine Environmental Research}, publisher={Elsevier BV}, author={Weisbrod, A. and Shea, D. and Leblanc, G. and Moore, M. and Stegeman, J.J.}, year={2000}, month={Jul}, pages={440–441} } @article{weisbrod_shea_moore_stegeman_2000, title={Organochlorine exposure and bioaccumulation in the endangered Northwest Atlantic right whale (Eubalaena glacialis) population}, volume={19}, ISSN={["1552-8618"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0033995640&partnerID=MN8TOARS}, DOI={10.1897/1551-5028(2000)019<0654:OEABIT>2.3.CO;2}, number={3}, journal={ENVIRONMENTAL TOXICOLOGY AND CHEMISTRY}, author={Weisbrod, AV and Shea, D and Moore, MJ and Stegeman, JJ}, year={2000}, month={Mar}, pages={654–666} } @article{miller_shea_khaledi_2000, title={Separation of acidic solutes by nonaqueous capillary electrophoresis in acetonitrile-based media - Combined effects of deprotonation and heteroconjugation}, volume={888}, ISSN={["0021-9673"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0034604766&partnerID=MN8TOARS}, DOI={10.1016/S0021-9673(00)00467-2}, abstractNote={Nonaqueous capillary electrophoresis (NACE) is a chemical separation technique that has grown in popularity over the past few years. In this report, we focus on the combination of heteroconjugation and deprotonation in the NACE separation of phenols using acetonitrile (ACN) as the buffer solvent. By preparing various dilute buffers consisting of carboxylic acids and tetrabutylammonium hydroxide in ACN, selectivity may be manipulated based on a solute's dissociation constant as well as its ability to form heterogeneous ions with the buffer components. ACN's low viscosity, coupled with its ability to allow for heteroconjugation, often leads to rapid and efficient separations that are not possible in aqueous media. In this report, equations are derived showing the dependence of mobility on various factors, including the pKa of the analyte, the pH and concentration of the buffer, and the analyte-buffer heteroconjugation constant (Kf). The validity of these equations is tested as several nitrophenols are separated at different pH values and concentrations. Using nonlinear regression, the Kf values for the heteroconjugate formation between the nitrophenols and several carboxylate anions are calculated. Also presented in this report are the NACE separations of the 19 chlorophenol congeners and the 11 priority pollutant phenols (used in US Environmental Protection Agency methods 604, 625/1625 and 8270B).}, number={1-2}, journal={JOURNAL OF CHROMATOGRAPHY A}, author={Miller, JL and Shea, D and Khaledi, MG}, year={2000}, month={Aug}, pages={251–266} } @article{tester_turner_shea_2000, title={Vectorial transport of toxins from the dinoflagellate Gymnodinium breve through copepods to fish}, volume={22}, ISSN={1464-3774}, url={http://dx.doi.org/10.1093/plankt/22.1.47}, DOI={10.1093/plankt/22.1.47}, abstractNote={Toxins from the dinoflagellate Gymnodinium breve were traced through experimental food chains from dinoflagellates, through copepod grazers, to juvenile fish. The generality of this food web transfer was demonstrated using three different combinations of copepods and juvenile fish during different seasons. Fish were not exposed directly to the toxic dinoflagellates but were fed toxin-laden copepods in order to examine sublethal vectorial intoxication. Toxins were shown to move from fish viscera to muscle tissue within periods of 2-6 h to 25 h. A new toxin detection method was used in this first stepwise demonstration of multi-trophic-level intoxication of a planktonic food chain by G.breve. Micellar electrokinetic capillary electrophoresis with laser-induced fluorescence allowed measurements of toxins at trace levels and nanoliter-sized volumes critical for planktonic food web transfer studies.}, number={1}, journal={Journal of Plankton Research}, publisher={Oxford University Press (OUP)}, author={Tester, P.A. and Turner, J.T. and Shea, D.}, year={2000}, month={Jan}, pages={47–62} } @article{shea_penmetsa_leidy_1999, title={Enantiomeric and isomeric separation of pesticides by cyclodextrin-modified micellar electrokinetic chromatography}, volume={82}, DOI={10.1093/jaoac/82.6.1550}, abstractNote={Cyclodextrin-modified micellar electrokinetic chromatography was applied successfully to the enantiomeric and isomeric separation of 7 commonly used pesticides (propiconazole, bioallethrin, fenpropathrin, phenothrin, bitertanol, triadimenol, and dimethomorph). Commercially available surfactants used alone or in combination with cyclodextrins were evaluated for separation of the enantiomers/isomers of the 7 pesticides. The enantiomers/isomers of the pesticides used in this study were baseline resolved with resolutions of >1.5. The resolution was found to depend on the type of surfactant and cyclodextrin employed in the running buffer. In the case of propiconazole and dimethomorph, baseline resolution was also achieved by adding sodium cholate (a chiral surfactant) alone to the running buffer. Analysis of fortified water samples yielded recoveries ranging from 45 to 89% and method detection limits ranging from 0.18 to 2.1 ppb. The reported capillary electrophoresis methods are simple, rapid, and reproducible.}, number={6}, journal={Journal of AOAC International}, author={Shea, D. and Penmetsa, K.V. and Leidy, R.B.}, year={1999}, month={Nov}, pages={1550–1561} } @article{shea_penmetsa_leidy_1999, title={Enantiomeric and isomeric separation of pesticides by cyclodextrin-modified micellar electrokinetic chromatography}, volume={82}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0002723580&partnerID=MN8TOARS}, number={6}, journal={Journal of AOAC International}, author={Shea, D. and Penmetsa, K.V. and Leidy, R.B.}, year={1999}, pages={1550–1561} } @article{baldwin_graham_shea_leblanc_1998, title={Altered metabolic elimination of testosterone and associated toxicity following exposure of Daphnia magna to nonylphenol polyethoxylate}, volume={39}, ISSN={["0147-6513"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0032005539&partnerID=MN8TOARS}, DOI={10.1006/eesa.1997.1614}, abstractNote={The ability of nonylphenol polyethoxylate (nonylphenyl polyethylene glycol, NPPG) to alter the metabolic elimination of testosterone and elicit reproductive toxicity to Daphnia magna was assessed. NPPG (5.0 mg/liter) inhibited the elimination of testosterone as glucose and sulfate conjugates, but had minimal effect on the rate of elimination of oxido-reduced and hydroxylated derivatives of the steroid hormone. This exposure concentration of NPPG also approximated the acute threshold-effect concentration and the chronic value for daphnids. Results demonstrated that NPPG qualitatively elicits similar effects on the metabolic elimination of testosterone by daphnids as previously characterized with its degradation product 4-nonylphenol. Unlike 4-nonylphenol, significant chronic toxicity of NPPG, due to effects on steroid elimination processes, was not evident. Results from the present study provide no indication that concentrations of nonylphenol polyethoxylates typically measured in the environment pose a risk of chronic toxicity to invertebrates.}, number={2}, journal={ECOTOXICOLOGY AND ENVIRONMENTAL SAFETY}, author={Baldwin, WS and Graham, SE and Shea, D and LeBlanc, GA}, year={1998}, month={Feb}, pages={104–111} } @article{miller_khaledi_shea_1998, title={Separation of hydrophobic solutes by nonaqueous capillary electrophoresis through dipolar and charge-transfer interactions with pyrylium salts}, volume={10}, ISSN={["1040-7685"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0001258994&partnerID=MN8TOARS}, DOI={10.1002/(SICI)1520-667X(1998)10:8<681::AID-MCS7>3.0.CO;2-6}, abstractNote={In this study, the use of pyrylium salts for the separation of uncharged hydrophobic solutes in nonaqueous capillary electrophoresis (NACE) is examined. In an aprotic solvent such as acetonitrile, large polarizable compounds selectively interact with planar organic cations, thereby facilitating the analysis of solutes that have low solubilities in aqueous or mixed solvents. Presented in this article are the separations of polycyclic aromatic hydrocarbons (PAHs) that were achieved through dipolar and charge-transfer interactions with various substituted pyrylium cations. It was found that the number of rings contained in the PAH molecule, the presence of functional groups on the molecule, the concentration of the pyrylium cation, and the number of phenyl substituents on the pyrylium ring affected the electrophoretic mobility of the solute–cation complex. © 1998 John Wiley & Sons, Inc. J Micro Sep 10: 681–685, 1998}, number={8}, journal={JOURNAL OF MICROCOLUMN SEPARATIONS}, author={Miller, JL and Khaledi, MG and Shea, D}, year={1998}, pages={681–685} } @article{hofelt_shea_1997, title={Accumulation of Organochlorine Pesticides and PCBs by Semipermeable Membrane Devices andMytilus edulisin New Bedford Harbor}, volume={31}, ISSN={0013-936X 1520-5851}, url={http://dx.doi.org/10.1021/es9602509}, DOI={10.1021/es9602509}, abstractNote={We deployed semipermeable membrane devices (SPMDs) and transplanted blue mussels (Mytilus edulis) side-by-side at five sites in New Bedford Harbor, MA. A good correlation was obtained between accumulation in the SPMDs and the caged mussels, with r 2 values ranging from 0.57 to 0.85 for individual pesticides (n = 16) and from 0.81 to 0.96 for individual PCB congeners (n = 20). An excellent correlation also was found between the log K ow and the log BAF (bioaccumulation factor in mussels) and between the log K ow and log AF (accumulation factor in SPMDs). Accumulation in the mussels was approximately 2-fold higher than in the SPMDs when concentrations were expressed on a lipid basis. These correlations are significantly better than any reported previously and probably result from modifications that we made to the original design of the SPMD. A close examination of accumulation into SPMDs demonstrates that the uptake rate and equilibrium status of an SPMD can be easily manipulated by modifying membrane thickness, surface area, and lipid substrate volume. Knowledge of these parameters and their effect on SPMD uptake rates is critical to the interpretation of SPMD data and can be used to optimize the design of SPMDs for specific applications.}, number={1}, journal={Environmental Science & Technology}, publisher={American Chemical Society (ACS)}, author={Hofelt, Chris S. and Shea, Damian}, year={1997}, month={Jan}, pages={154–159} } @misc{shea_hofelt_1997, title={Accumulation of organochlorine pesticides and PCBs by semipermeable membrane devices and Mytilus edulis in New Bedford Harbor - Response}, volume={31}, ISSN={["0013-936X"]}, DOI={10.1021/es972014j}, abstractNote={ADVERTISEMENT RETURN TO ISSUEPREVCorrespondence/Rebut...Correspondence/RebuttalNEXTResponse to Comment on “Accumulation of Organochlorine Pesticides and PCBs by Semipermeable Membrane Devices and Mytilus edulis in New Bedford Harbor”Damian Shea and Chris S. HofeltView Author Information Department of Toxicology North Carolina State University 3709 Hillsborough Street Raleigh, North Carolina 27607Cite this: Environ. Sci. Technol. 1997, 31, 12, 3734–3735Publication Date (Web):November 26, 1997Publication History Published online26 November 1997Published inissue 1 December 1997https://doi.org/10.1021/es972014jCopyright © 1997 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views143Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (49 KB) Get e-AlertsSUBJECTS:Computer simulations,Equilibrium,Modification,Phenyls Get e-Alerts}, number={12}, journal={ENVIRONMENTAL SCIENCE & TECHNOLOGY}, author={Shea, D and Hofelt, CS}, year={1997}, month={Dec}, pages={3734–3735} } @article{shea_1997, title={Analysis of brevetoxins by micellar electrokinetic capillary chromatography and laser-induced fluorescence detection}, volume={18}, ISSN={["0173-0835"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0031053797&partnerID=MN8TOARS}, DOI={10.1002/elps.1150180216}, abstractNote={Abstract}, number={2}, journal={ELECTROPHORESIS}, author={Shea, D}, year={1997}, month={Feb}, pages={277–283} } @article{penmetsa_leidy_shea_1997, title={Analysis of primisulfuron and triasulfuron in water and soil samples by micellar electrokinetic capillary chromatography}, volume={766}, ISSN={["0021-9673"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0030972670&partnerID=MN8TOARS}, DOI={10.1016/S0021-9673(96)01051-5}, abstractNote={A capillary electrophoresis (CE) method was developed to separate and determine residues of two sulfonylurea herbicides (primisulfuron and triasulfuron) in water and soil samples. Fortified water samples were extracted by solvent partitioning with methylene chloride and analysis by CE. Fortified soil samples were extracted by shaking in methanol–phosphate buffer (1:1) followed by partitioning of the residues into methylene chloride and analysis by CE. The method was simple, rapid and yielded excellent recoveries. Average recoveries were greater than 90% for both herbicides fortified at 10 μg/l in lakewater samples and at 50 μg/kg in soil samples. Our results demonstrate that capillary electrophoresis provides a powerful analytical tool for determination of the residues of primisulfuron and triasulfuron in water and soil samples.}, number={1-2}, journal={JOURNAL OF CHROMATOGRAPHY A}, author={Penmetsa, KV and Leidy, RB and Shea, D}, year={1997}, month={Apr}, pages={225–231} } @article{huckins_petty_lebo_orazio_prest_shea_hofelt_1997, title={Comment on 'accumulation of organochlorine pesticides and PCBs by semipermeable membrane devices and Mytilus edulis in New Bedford harbor' [1] (multiple letters)}, volume={31}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0031472849&partnerID=MN8TOARS}, DOI={10.1021/es9704287}, abstractNote={ADVERTISEMENT RETURN TO ISSUEPREVCorrespondence/Rebut...Correspondence/RebuttalNEXTComment on “Accumulation of Organochlorine Pesticides and PCBs by Semipermeable Membrane Devices and Mytilus edulis in New Bedford Harbor”James N. Huckins, Jimmie D. Petty, Jon A. Lebo, Carl E. Orazio, and Harry F. PrestView Author Information Midwest Science Center U.S. Geological Survey Columbia, Missouri 65201 Long Marine Laboratory University of California−Santa Cruz Santa Cruz, California 95060Cite this: Environ. Sci. Technol. 1997, 31, 12, 3732–3733Publication Date (Web):November 26, 1997Publication History Published online26 November 1997Published inissue 1 December 1997https://doi.org/10.1021/es9704287Copyright © 1997 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views207Altmetric-Citations4LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (75 KB) Get e-AlertsSUBJECTS:Computer simulations,Equilibrium,Lipids,Membranes,Water Get e-Alerts}, number={12}, journal={Environmental Science and Technology}, author={Huckins, J.N. and Petty, J.D. and Lebo, J.A. and Orazio, C.E. and Prest, H.F. and Shea, D. and Hofelt, C.S.}, year={1997}, pages={3732–3735} } @article{penmetsa_leidy_shea_1997, title={Enantiomeric and isomeric separation of herbicides using cyclodextrin-modified capillary zone electrophoresis}, volume={790}, ISSN={["0021-9673"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0031475018&partnerID=MN8TOARS}, DOI={10.1016/S0021-9673(97)00765-6}, abstractNote={Cyclodextrin-modified capillary zone electrophoresis (CD-CZE) was applied successfully to the enantiomeric and isomeric separation of three herbicides (imazaquin, diclofop and imazamethabenz). Commercially available cyclodextrins were evaluated for separation of the enantiomers and isomers of the three herbicides having varied molecular structures. The enantiomers of imazaquin and diclofop, and the isomers of imazamethabenz could be resolved with a resolution of ≥1.5. The resolution was found to depend on pH of the run buffer, cyclodextrin type and cyclodextrin concentration. By employing mixed cyclodextrins in the running buffer, the three herbicides were simultaneously separated in a single run. In addition, rapid (less than 3 min) enantiomeric separation is demonstrated using imazaquin as a model herbicide. The reported capillary electrophoresis (CE) methods are simple, rapid, efficient and reproducible and our results demonstrate that CE provides a powerful analytical tool for enantiomeric and isomeric separation of herbicides.}, number={1-2}, journal={JOURNAL OF CHROMATOGRAPHY A}, author={Penmetsa, KV and Leidy, RB and Shea, D}, year={1997}, month={Nov}, pages={225–234} } @article{white_shea_solow_stegeman_1997, title={Induction and post-transcriptional suppression of hepatic cytochrome P450 1A1 by 3,3',4,4'-tetrachlorobiphenyl}, volume={53}, ISSN={["1873-2968"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0030956844&partnerID=MN8TOARS}, DOI={10.1016/S0006-2952(96)00902-1}, abstractNote={3,3′,4,4′-Tetrachlorobiphenyl (TCB) can induce and inhibit cytochrome P450 1A1 (CYP1A1) in vertebrates. TCB may also suppress CYP1A1 protein levels, but the mechanism is unknown. This study examined transcriptional and translational aspects of hepatic CYP1A1 regulation in the fish scup (Stenotomus chrysops) given single intraperitoneal injections of low (0.1 mg/kg) or high (5 mg/kg) doses of TCB, and sampled over 16 days. The low dose strongly induced hepatic CYP1A1 mRNA (25-fold), protein (12-fold), and activity [ethoxyresorufin O-deethylase (EROD)](15-fold). The high dose also strongly induced CYP1A1 mRNA (29-fold), in a pattern like that at the low dose, but microsomal CYP1A1 protein content was induced only 4-fold and EROD rates were near control levels. Both TCB doses caused similar increases in microsomal cytochrome b5 content, and in rates of NADPH-cytochrome c (P450) reductase and UDP-glucuronosyltransferase (with p-nitrophenol). The contents of CYP forms other than CYP1A1 (putative CYP2B or CYP3A) were only weakly affected by TCB at either dose. The strong and largely specific post-transcriptional suppression of CYP1A1 content was associated with high concentrations of TCB measured in the liver. Incubation of scup hepatic microsomes with TCB plus NADPH led to a time-dependent inactivation of CYP1A1 that was distinct from catalytic inhibition, and appeared not to involve reactive metabolites of TCB. This in vitro result suggests that TCB may inactivate CYP1A1 in vivo, which could account for the apparent antagonistic effect of TCB on CYP1A1 induction.}, number={7}, journal={BIOCHEMICAL PHARMACOLOGY}, author={White, RD and Shea, D and Solow, AR and Stegeman, JJ}, year={1997}, month={Apr}, pages={1029–1040} } @article{baldwin_graham_shea_leblanc_1997, title={Metabolic androgenization of female Daphnia magna by the xenoestrogen 4-nonylphenol}, volume={16}, ISSN={["1552-8618"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0030807616&partnerID=MN8TOARS}, DOI={10.1897/1551-5028(1997)016<1905:MAOFDM>2.3.CO;2}, number={9}, journal={ENVIRONMENTAL TOXICOLOGY AND CHEMISTRY}, author={Baldwin, WS and Graham, SE and Shea, D and LeBlanc, GA}, year={1997}, month={Sep}, pages={1905–1911} } @article{white_shea_stegeman_1997, title={Metabolism of the aryl hydrocarbon receptor agonist 3,3',4,4'- tetrachlorobiphenyl by the marine fish scup (Stenotomus chrysops) in vivo and in vitro}, volume={25}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0030996090&partnerID=MN8TOARS}, number={5}, journal={Drug Metabolism and Disposition}, author={White, R.D. and Shea, D. and Stegeman, J.J.}, year={1997}, pages={564–572} } @article{penmetsa_leidy_shea_1997, title={Separation of fungicides by micellar electrokinetic capillary chromatography}, volume={18}, ISSN={["0173-0835"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0031039532&partnerID=MN8TOARS}, DOI={10.1002/elps.1150180210}, abstractNote={Abstract}, number={2}, journal={ELECTROPHORESIS}, author={Penmetsa, KV and Leidy, RB and Shea, D}, year={1997}, month={Feb}, pages={235–240} } @article{miller_khaledi_shea_1997, title={Separation of polycyclic aromatic hydrocarbons by nonaqueous capillary electrophoresis using charge-transfer complexation with planar organic cations}, volume={69}, ISSN={["0003-2700"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0031569134&partnerID=MN8TOARS}, DOI={10.1021/ac960734n}, abstractNote={In this study, we examine the use of charge-transfer interactions between polycyclic aromatic hydrocarbons (PAHs) and planar organic cations in nonaqueous capillary electrophoresis. Since the separations are performed in a purely nonaqueous medium, this method also facilitates the analysis of solutes that have low solubilities in aqueous or mixed media. Presented in this study are the separations of PAHs as well as the quantitative structure-migration relationships that assisted in achieving a better understanding of the forces through which the PAH molecules interact with the acceptor cation. It was found that, in addition to charge-transfer interactions, electrostatic and dispersive forces play an important role in PAH-cation binding.}, number={6}, journal={ANALYTICAL CHEMISTRY}, author={Miller, JL and Khaledi, MG and Shea, D}, year={1997}, month={Mar}, pages={1223–1229} } @article{spies_stegeman_hinton_woodin_smolowitz_okihiro_shea_1996, title={Biomarkers of hydrocarbon exposure and sublethal effects in embiotocid fishes from a natural petroleum seep in the Santa Barbara Channel}, volume={34}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0029668909&partnerID=MN8TOARS}, DOI={10.1016/0166-445X(95)00039-7}, abstractNote={Several markers of hydrocarbon exposure and sublethal effects were measured in rainbow surfperch Hypsurus caryi and rubberlip surfperch Rachochilus toxodes from a shallow natural petroleum seep and from reference areas in the Santa Barbara Channel. Hydrocarbon exposure was assessed by an HPLC-based analysis of fluorescing compounds in the bile. Compounds fluorescing at wavelengths of naphthalene were significantly elevated in bile of rainbow surfperch (~3×), but not rubberlip surfperch, from the seep. Compounds fluorescing at wavelengths of phenanthrene were significantly elevated in bile of both species (~2× to 3×) relative to those from the comparison areas. Content of cytochrome 4501A (CYP1A) in hepatic microsomes of both species from the petroleum seep was significantly greater than in individuals from the reference areas (~10× in rainbow surfperch and ~2× in rubberlip surfperch). Immunohistochemical analysis also showed greater content of CYP1A in both species from the petroleum seep. The CYP1A content of gill epithelia in particular was greatly different between fish from the seep and reference areas. A variety of histopathological lesions were documented in gills, livers and kidneys of both species. Total lesion scores were not different between the two groups of rubberlip surfperch. However, in the rainbow surfperch total lesion scores from petroleum seep fish were approximately twice as high in gills and one and one-half times as high in liver as those from the comparison area. In the latter species liver lesions were relatively mild, but in gills relatively severe lesions occurred, including cartilage dysplasia, abnormal branching and fusion of lamellae, various sorts of inflammation, aneurysms, and epithelial hyperplasia. Such interspecific differences in hydrocarbon exposure and response are consistent with the greater reliance on benthic feeding and more limited movements of the rainbow surfperch. It is suggested that cartilage displaysia and abnormal branching of gill filaments and lamellae are biological markers for xenobiotic compounds that induce CYP1A.}, number={3}, journal={Aquatic Toxicology}, author={Spies, R.B. and Stegeman, J.J. and Hinton, D.E. and Woodin, B. and Smolowitz, R. and Okihiro, M. and Shea, D.}, year={1996}, pages={195–219} } @article{penmetsa_leidy_shea_1996, title={Herbicide analysis by micellar electrokinetic capillary chromatography}, volume={745}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0030595296&partnerID=MN8TOARS}, DOI={10.1016/0021-9673(96)00185-9}, abstractNote={Capillary electrophoresis with ultraviolet detection (CE-UV) and laser-induced fluorescence detection (CE-LIF) was used for analysis of a group of herbicides that have widespread use in the USA. CE-UV was employed for simultaneous determination of atrazine, simazine, alachlor and metolachlor in water. In addition, CE-UV was also suitable for analysis of dicamba, 2,4-D and chlorimuron ethyl. Dicamba, 2,4-D and chlorimuron ethyl were also analyzed using CE-LIF following derivatization with fluorescent reagents. Dicamba and 2,4-D were derivatized with 4-bromomethyl-7-methoxycoumarin and chlorimuron ethyl was derivatized with dansyl chloride following hydrolysis. The detection limit with CE-UV for atrazine, simazine and metolachlor was 0.1 μg/l and for alachlor was 1.0 μg/l. The estimated detection limit with CE-LIF for dicamba, 2,4-D and chlorimuron ethyl was 10 ng/l. Our results demonstrate that CE provides a powerful new analytical tool for herbicide analysis.}, number={1-2}, journal={Journal of Chromatography A}, author={Penmetsa, K.V. and Leidy, R.B. and Shea, D.}, year={1996}, pages={201–208} } @article{moore_shea_hillman_stegeman_1996, title={Trends in hepatic tumours and hydropic vacuolation, fin erosion, organic chemicals and stable isotope ratios in winter flounder from Massachusetts, USA}, volume={32}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0029668929&partnerID=MN8TOARS}, DOI={10.1016/0025-326X(96)84962-9}, abstractNote={Liver lesions including neoplasia and hydropic vacuolation have been described in winter flounder (Pleuronectes americanus) from sites in Boston Harbor, and were highly prevalent near the Deer Island sewage outfall. A marked decline in prevalence of neoplasia has been seen over the period 1987 to 1993 in fish from near the Deer Island outfall. This decline in disease in Deer Island fish correlated with and probably resulted from reported reduced chemical input over that time. Stable isotope ratios suggest that Deer Island winter flounder, in contrast to fish from elsewhere, fed significantly on sewage sludge-derived organic matter prior to 1992 and that their along-shore movement is slight. Between 1991 and 1993 hydropic vacuolation remained much more prevalent in flounder taken near Deer Island and another sewage outfall, than at sites distant (≤45 miles) from the outfalls. Hydropic vacuolation prevalence correlated closely with content of chlorinated hydrocarbon residues in the liver, and in particular with DDT/DDD/DDE. This suggests that between 1991 and 1993 there was a persistent chemical-associated difference in fish from the planned and current outfall sites, and that monitoring of winter flounder will provide necessary assessment of altered chemical carcinogenesis risk during and after the switch to the offshore outfall planned for 1998.}, number={6}, journal={Marine Pollution Bulletin}, author={Moore, M.J. and Shea, D. and Hillman, R.E. and Stegeman, J.J.}, year={1996}, pages={458–470} } @article{penmetsa_shea_leidy_bond_1995, title={Analysis of benzo[a]pyrene‐DNA adducts by capillary electrophoresis with laser‐induced fluroescence detection}, volume={18}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0029197402&partnerID=MN8TOARS}, DOI={10.1002/jhrc.1240181110}, abstractNote={Journal of High Resolution ChromatographyVolume 18, Issue 11 p. 719-720 Short Communication Analysis of benzo[a]pyrene-DNA adducts by capillary electrophoresis with laser-induced fluroescence detection Kumar V. Penmetsa, Kumar V. Penmetsa Department of Toxicology, 3709 Hillsborough Street, North Carolina State University, Raleigh, NC 27607, USASearch for more papers by this authorDamian Shea, Corresponding Author Damian Shea Department of Toxicology, 3709 Hillsborough Street, North Carolina State University, Raleigh, NC 27607, USADepartment of Toxicology, 3709 Hillsborough Street, North Carolina State University, Raleigh, NC 27607, USASearch for more papers by this authorRoss B. Leidy, Ross B. Leidy Department of Toxicology, 3709 Hillsborough Street, North Carolina State University, Raleigh, NC 27607, USASearch for more papers by this authorJames A. Bond, James A. Bond Chemical Industry Institute of Toxicology, 6 Davis Drive, P.O. Box 12137, Research Triangle Park, NC 27709, USASearch for more papers by this author Kumar V. Penmetsa, Kumar V. Penmetsa Department of Toxicology, 3709 Hillsborough Street, North Carolina State University, Raleigh, NC 27607, USASearch for more papers by this authorDamian Shea, Corresponding Author Damian Shea Department of Toxicology, 3709 Hillsborough Street, North Carolina State University, Raleigh, NC 27607, USADepartment of Toxicology, 3709 Hillsborough Street, North Carolina State University, Raleigh, NC 27607, USASearch for more papers by this authorRoss B. Leidy, Ross B. Leidy Department of Toxicology, 3709 Hillsborough Street, North Carolina State University, Raleigh, NC 27607, USASearch for more papers by this authorJames A. Bond, James A. Bond Chemical Industry Institute of Toxicology, 6 Davis Drive, P.O. Box 12137, Research Triangle Park, NC 27709, USASearch for more papers by this author First published: November 1995 https://doi.org/10.1002/jhrc.1240181110Citations: 5AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article.Citing Literature Volume18, Issue11November 1995Pages 719-720 RelatedInformation}, number={11}, journal={Journal of High Resolution Chromatography}, author={Penmetsa, K.V. and Shea, D. and Leidy, R.B. and Bond, J.A.}, year={1995}, pages={719–720} } @inbook{maccrehan_shea_1995, place={Washington, DC}, series={ACS Symposium}, title={Temporal relationship of thiols to inorganic sulfur compounds in anoxic Chesapeake Bay sediment porewater}, ISBN={‍9780841233287 ‍9780841215474}, DOI={10.1021/bk-1995-0612.ch016}, abstractNote={Seasonal variations in the sediment porewater concentration profiles of organic and inorganic sulfur species at a Chesapeake Bay channel site provide new insight into an esturarine sulfur cycle. Oxidation of sulfide, as evidenced by the presence of zero-valent sulfur, occurs in this sulfidic sediment despite bottom water column and sediment anoxia. Thiosulfate shows a bimodal occurrence profile with a maximum in the late spring and fall, and is absent in midsummer. Two thiols, cysteine and glutathione, show maximal concentrations at 4 cm in mid-summer, which overlaps the highest gradient of sulfide and zero-valent sulfur occurrence patterns, suggesting a role in elemental sulfur redox or transport processes. Mercaptoacetate and mercaptopyruvate, were found in much lower concentrations and appear to be linked to the diagenesis of cysteine. Two mercaptopropanoic acids show temporal profiles increasing with sediment depth and may be linked to deeper sediment methanogenic bacterial activities.}, booktitle={Geochemical Transformations of Sedimentary Sulfur}, publisher={American Chemical Society}, author={MacCrehan, W.A. and Shea, D.}, editor={Vairavamurthy, M.A. and Schooner, M.A.A. and Eglinton, T.I. and Luther, G.W. and Manowitz, B.Editors}, year={1995}, pages={294–310}, collection={ACS Symposium} } @article{hunt_mcdowell_shea_hillman_trulli_berger_redford_pabst_1992, title={Transport of sewage sludge from the 106-mile site - results from an october survey}, volume={7}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0027070243&partnerID=MN8TOARS}, DOI={10.1080/02757549208055441}, abstractNote={Abstract Approximately 8 million tons of sewage sludge were disposed of annually at the 106-Mile Deepwater Municipal Sludge Dump Site (106-Mile Site) between 1987 and 1990. Beginning in 1988 and continuing to the present, the focus of monitoring at the 106-Mile Site moved towards improved understanding of the fate of the sludge. A survey conducted in October 1989 was designed to (1) detect the presence of any sludge particles that settle rapidly following disposal, (2) determine if sludge could be detected in the surface waters at locations away from the immediate disposal site, and (3) determine if water quality was degraded, by assessing whether the Environmental Protection Agency's marine water quality criteria were being exceeded. The survey showed that the sludge does have a rapidly settling component composed of organic floc. mineral grains, and other heavy, gritlike particles, all of which are relatively large. These particles may settle at rates of between 8 and 180 m h−1 and may reach the sea flo...}, number={1-4}, journal={Chemistry and Ecology}, author={Hunt, C.D. and McDowell, S.E. and Shea, D. and Hillman, R. and Trulli, W. and Berger, T. and Redford, D. and Pabst, D.}, year={1992}, pages={195–231} } @article{shea_helz_1989, title={Solubility product constants of covellite and a poorly crystalline copper sulfide precipitate at 298 K}, volume={53}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-50849147943&partnerID=MN8TOARS}, DOI={10.1016/0016-7037(89)90375-X}, abstractNote={The equilibrium constant at 25°C for the following reaction has been measured in NaCl media by an indirect method: CuS(cov) + H+(aq) ⇄ Cu2+(aq) + HS−(qa), Ksp = MCu2+MHS−(10+pH) where CuS(cov) designates synthetic covellite. Values of pKsp are 21.39, 21.04 and 20.95 at NaCl = 0.2, 0.7 and 1.0 M, respectively; the uncertainty in these Ksp values is ±0.15. The free energy of formation of covellite, for which published values are discordant, is calculated to be −11.83±0.4 kcal/mole at 298 K (−49.50 ± 1.7 kJ/mole). This value is obtained by extrapolating the meaured pKsp values to infinite dilution with corrections for Cl− complexing. Applying similar Cl− complexing corrections, based on recent measurements by Seward, to previously published solubility data for galena yields a revised pKsp0 for galena of 12.78. A poorly crystalline precipitate, obtained by mixing Cu2+ and HS− solutions, yielded a reversible solubility product 3 orders of magnitude greater than that of covellite but about 3 orders of magnitude less than that of a truly amorphous phase, super-cooled liquid CuS. The poorly crystalline phase has not been studied previously. Its bulk composition was Cu1.18S, but microprobe analysis revealed that it was a partially exsolved mixture of roughly Cu1.11S and Cu1.32S (similar to known blaubleibender covellites). It was kinetically unstable, and converted to covellite when thermally annealed or when exposed to polysulfide solutions. Because of its instability, a material of this nature is unlikely to account for the amorphous copper sulfide alleged to occur in the Red Sea Brine deposits. However, it is possible that on short time scales dissolved Cu in sulfidic waters is controlled by metastable, rather than stable phases, as is known to be the case with dissolved Fe.}, number={2}, journal={Geochimica et Cosmochimica Acta}, author={Shea, D. and Helz, G.R.}, year={1989}, pages={229–236} } @article{shea_maccrehan_1988, title={Determination of Hydrophilic Thiols in Sediment Porewater Using Ion-Pair Liquid Chromatography Coupled to Electrochemical Detection}, volume={60}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0023771009&partnerID=MN8TOARS}, DOI={10.1021/ac00165a020}, abstractNote={Twelve hydrophilic thiols in sediment pore water samples from the Chesapeake Bay were determined by reversed-phase high-performance liquid chromatography using trihaloacetate ion-pairing agents with amperometric detection at a mercury-film/gold electrode. The detection limit is about 2 pmol, and the precision is better than 3% at the 100-pmol level. Glassy carbon and bare gold electrodes were also examined but were found to have higher residual currents and were subject to more interferences than the mercury-film/gold electrode. The stability of thiols with respect to oxidation, in both standard solutions and samples, was also investigated under various conditions.}, number={14}, journal={Analytical Chemistry}, author={Shea, D. and Maccrehan, W.A.}, year={1988}, pages={1449–1454} } @article{shea_1988, title={Developing national sediment quality criteria}, volume={22}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0024110521&partnerID=MN8TOARS}, DOI={10.1021/es00176a002}, abstractNote={La methode faisant intervenir les coefficients de partition est utilisee pour controler les teneurs en composes hydrophobes dans les sediments}, number={11}, journal={Environmental Science and Technology}, author={Shea, D.}, year={1988}, pages={1256–1261} } @article{shea_maccrehan_1988, title={Role of biogenic thiols in the solubility of sulfide minerals}, volume={73}, ISSN={0048-9697}, url={http://dx.doi.org/10.1016/0048-9697(88)90194-5}, DOI={10.1016/0048-9697(88)90194-5}, abstractNote={Efforts to account for observed trace metal concentrations in anoxic marine waters have had only limited success due in part to the lack of knowledge of the identity and concentration of the organic sulfur compounds that are present. There have been no previous attempts to measure trace metals concentrations simultaneously with the inorganic and organic sulfur species in marine waters. In addition to the conventional methods for the determination of the inorganic species, we are developing methods for the determination of the biogenic thiols and disulfides using an HPLC separation coupled to selective electrochemical detection. Preliminary results on the analysis from anoxic sediment pore waters will be presented. Current thermodynamic models describing the solubility of sulfide minerals in anoxic marine waters will be refined to include complexation of chalcophile trace metals by organic thiols.}, number={1-2}, journal={Science of The Total Environment}, publisher={Elsevier BV}, author={Shea, Damian and MacCrehan, William A.}, year={1988}, month={Jul}, pages={135–141} } @article{maccrehan_shea_1988, title={Separation of hydrophilic thiols using reversed-phase chromatography with trihaloacetate buffers}, volume={457}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0343082758&partnerID=MN8TOARS}, DOI={10.1016/S0021-9673(01)82059-8}, abstractNote={The reversed-phase retention behavior of several neutral and cationic hydrophilic thiols using trihaloacetic acid pairing agents is studied. Retention of cationic compounds increases with the size of the halogen substituent in the order: trifluoro- < trichloro- < tribromoacetic acid. The effect of pH, ionic strength, pairing ion and counter ion concentration on retention of cysteine and other thiols is measured. The formation of mobile phase ionic interactions is proposed as the mechanism of retention enhancement.}, number={C}, journal={Journal of Chromatography A}, author={MacCrehan, W.A. and Shea, D.}, year={1988}, pages={111–125} } @article{shea_helz_1988, title={The solubility of copper in sulfidic waters: Sulfide and polysulfide complexes in equilibrium with covellite}, volume={52}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0024265749&partnerID=MN8TOARS}, DOI={10.1016/0016-7037(88)90005-1}, abstractNote={The solubility of covellite has been measured in 0.5–2.0 M NaCl at 25°C. Solutions containing various concentrations of total sulfide and zerovalent sulfur have been studied over the pH range 6–11. The data are interpreted in terms of the following complexes, for which stability constants are presented: CuS(HS)22−, CuS(HS)33−, Cu(S5)23−, Cu(S4)(S5)3−, and CuS(S5)2−. Three of these five species have not been reported before and are probably of importance in anoxic natural waters. The three complexes with the general formula, CuS(X)n, do not display optical absorption spectra characteristic of Cu(II) even though the oxidation state of copper, by convention, is divalent. When Cu2+ and S2− combine to form the CuS moiety in these complexes, internal electron transfer from S to Cu occurs. Because polysulfide complexes are extremely stable, the solubility of copper in sulfidic waters is strongly dependent on the activity of solid sulfur, as0. For natural waters, as0 can be calculated from measurements of pH, total zerovalent and total divalent sulfur. At as0 > 0.1, polysulfide complexes (especially CuS(S5)2−) are probably the predominant copper species in most sulfidic marine waters. Calculated total copper concentrations in equilibrium with covellite agree satisfactorily with published measurements for some Delaware salt marsh pore waters. This agreement is achieved by postulating that Cu-Fe-S phases, such as chalcopyrite, fail to nucleate at low temperatures in nature.}, number={7}, journal={Geochimica et Cosmochimica Acta}, author={Shea, D. and Helz, G.R.}, year={1988}, pages={1815–1825} } @article{shea_helz_1987, title={Kinetics of inhibited crystal growth: Precipitation of CuS from solutions containing chelated copper(II)}, volume={116}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0023324681&partnerID=MN8TOARS}, DOI={10.1016/0021-9797(87)90133-0}, abstractNote={Abstract Precipitation of crystalline CuS (covellite) is kinetically inhibited in the presence of aminocarboxylate chelating agents, EDTA and DCTA, even in highly supersaturated solutions. At millimolar concentrations at pH 8.1, these chelating agents adsorb strongly enough to CuS surfaces to approach monolayer coverage, reaching a density of about one molecule per 80 A 2 . Bisulfide competes with the chelators for surface sites. Growth of CuS was studied turbidimetrically by mixing solutions of chelated copper with bisulfide solutions in a stopped-flow spectrophotometer. The data were well fit by a rate law d[ CuS ] dt = kaθ HS [ Cu Y] , where k = rate constant, A = particle surface area per unit volume of solution, θ HS = fractional coverage of surface sites by sulfide, rather than chelator, and [Cu Y ] = concentration of copper chelate in solution. This rate law suggests that growth is controlled by encounters between HS − bound to the surface and chelated copper from the solution. Growth is diffusion limited. Differences in k obtained when Y = EDTA and DCTA suggest that only forms of the chelated copper with coordination number less than 6 are kinetically active.}, number={2}, journal={Journal of Colloid And Interface Science}, author={Shea, D. and Helz, G.R.}, year={1987}, pages={373–383} } @inproceedings{barnett_shea_1982, title={EFFECTS OF WOODSTOVE DESIGN AND OPERATION ON CONDENSABLE PARTICULATE EMISSIONS.}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-0019899949&partnerID=MN8TOARS}, author={Barnett, Stockton G. and Shea, Damian}, year={1982}, pages={227–266} }