Article

Reproductive health of bass in the Potomac, USA, drainage: Part 2. Seasonal occurrence of persistent and emerging organic contaminants

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Abstract

The seasonal occurrence of organic contaminants, many of which are potential endocrine disruptors, entering the Potomac River, USA, watershed was investigated using a two-pronged approach during the fall of 2005 and spring of 2006. Passive samplers (semipermeable membrane device and polar organic chemical integrative sampler [POCIS]) were deployed in tandem at sites above and below wastewater treatment plant discharges within the watershed. Analysis of the samplers resulted in detection of 84 of 138 targeted chemicals. The agricultural pesticides atrazine and metolachlor had the greatest seasonal changes in water concentrations, with a 3.1- to 91-fold increase in the spring compared with the level in the previous fall. Coinciding with the elevated concentrations of atrazine in the spring were increasing concentrations of the atrazine degradation products desethylatrazine and desisopropylatrazine in the fall following spring and summer application of the parent compound. Other targeted chemicals (organochlorine pesticides, polycyclic aromatic hydrocarbons, and organic wastewater chemicals) did not indicate seasonal changes in occurrence or concentration; however, the overall concentrations and number of chemicals present were greater at the sites downstream of wastewater treatment plant discharges. Several fragrances and flame retardants were identified in these downstream sites, which are characteristic of wastewater effluent and human activities. The bioluminescent yeast estrogen screen in vitro assay of the POCIS extracts indicated the presence of chemicals that were capable of producing an estrogenic response at all sampling sites.

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... Point sources (e.g., wastewater treatment plants [WWTPs] and industrial facilities) are permitted for direct discharge of effluent into water systems, whereas nonpoint sources (e.g., concentrated animal feeding operations [CAFOs] and agricultural waste sources) have the potential for indirect diffusion of EACs into water systems through runoff. Of great concern are the numerous findings of EACs in surface waters throughout the globe [2,7,8] and the issue of elevated estrogenic EACs downstream of WWTP effluent discharge points [2,9,10] and CAFOs [11,12]. Estrogenic EACs released into the environment can vary temporally as a result of seasonal output from agricultural pesticide application, land application of CAFO waste, and variability in the load and efficiency of WWTPs [13]. ...
... Kolpin et al. documented links between intersex and several EACs in smallmouth bass (Micropterus dolomieu) [24]. However, EACs typically occur as complex mixtures in surface waters throughout the United States [2,7,8]. To better understand the relationship between EACs and intersex, the objective of the present study was to conduct a statewide reconnaissance of the presence of EACs and intersex within fish populations inhabiting North Carolina water bodies. ...
... Industrial EACs and estrogens in water, which typically enter aquatic systems through WWTP effluent [2,13], were more prevalent at point source sites than nonpoint source and reference sites. Similarly, PAHs and PCBs in the sediment were more abundant at point source sites, consistent with previous work in the Potomac River drainage, USA [7]. Despite the source-specific variations observed in EAC concentrations, there was no similar variation in intersex within the species assessed. ...
Article
Male fish are susceptible to developing intersex, a condition characterized by the presence of testicular oocytes. In the present study, the relationship between intersex and exposure to estrogenic endocrine active contaminants (EACs) was assessed for 2 genera of sport fish, Micropterus and Lepomis, at 20 riverine sites. Seasonal trends and relationships between EACs and intersex (prevalence and severity) were examined at varying putative sources of EACs throughout North Carolina, identified as 'point', 'non-point' and 'reference' sites. Intersex was identified in both genera, where we documented it for the first time in wild-caught Lepomis. Intersex was more prevalent (59.8%) and more severe (1.6 mean rank) in Micropterus, which was highly correlated to EACs in sediment. In contrast, intersex was less common (9.9%) and less severe (0.2 mean rank) in Lepomis and was highly correlated to EACs in the water column. We found that concentrations of polycyclic aromatic hydrocarbons, polychlorinated biphenyls, industrial EACs and estrogens were highest at point source sites, but identified no source type variation in the prevalence or severity of intersex; nor were there seasonal trends in intersex or EAC concentrations. Our results associate genus-specific prevalence of intersex with specific EAC classes in common sport fishes with biological, ecological and conservation implications. This article is protected by copyright. All rights reserved.
... They are more adapted than classical devices to wastewater sampling allowing covering a much longer period of monitoring. Alvarez et al. 2009;Battaglin et al. 2014;Belles 2012;Botta et al. 2009;Campo et al. 2013;Cruz 2015;Griffini et al. 1997;Hladik and Kolpin 2015;House et al. 1997;Köck-Schulmeyer et al. 2012;Kolpin et al. 2006;Loos et al. 2009;Miège et al. 2012;Ollers et al. 2001;Schäfer et al. 2008 . Devenir des biocides, adapté de Majewski et Capel (1995), U.S. Geological Survey (2014) et Grandcoin et al. (2017), avec : 1-traitement de surface ou application d'une peinture protectrice ; 2-lessivage par les précipitations ; 3-infiltration dans les sols jusqu'aux nappes de surface ; 4-prise en charge par le réseau pluvial et rejets vers le milieu naturel ; 5-contamination des nappes en cas de canalisations endommagées ; 6-transfert de contamination entre les eaux de surface et les nappes phréatiques .......... 71 Figure 17. ...
... De nombreuses études rapportent la présence de pesticides dans les eaux naturelles (Alvarez et al., 2009;Campo et al., 2013;Gonzalez-Rey et al., 2015;Tapie et al., 2011;Van Metre et al., 2017;Zhang et al., 2016). En France, les eaux de surface sont en grande majorité contaminées avec des concentrations totales en pesticides supérieures à 100 ng.L -1 , certains points chauds pouvant être contaminés à plus de 5 000 ng.L -1 . ...
... Les pesticides étudiés au cours de ces travaux ont été sélectionnés en tenant compte de plusieurs paramètres : la présence de ces molécules dans la littérature scientifique internationale concernant les différents compartiments étudiés (House et al., 1997;Planas et al., 1997;Griffini et al., 1997;Bucheli et al., 1998;Ollers et al., 2001;Quaghebeur et al., 2004;Kolpin et al., 2006;Kahle et al., 2008;Alvarez et al., 2009;Botta et al., 2009;Weston et Lydy, 2010;Rasmussen et al., 2011;Köck-Schulmeyer et al., 2012Belles, 2012;Loos et al., 2013;Campo et al., 2013;Battaglin et al., 2014;Bollmann et al., 2014b;Gasperi et al., 2014;Hladik et Kolpin, 2015;Weston et al., 2015;Cruz, 2015;Mailler et al., 2016), des résultats de projets de recherches nationaux ou locaux (AMPERES, ARMISTIQ, ETIAGE), ainsi que des données de consommation à l'échelle et locale (Agence de l'eau Adour-Garonne, 2012; Agence Française pour la Biodiversité, ANSES). ...
Thesis
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L’augmentation globale de la démographie couplée à une amélioration du niveau de vie conduit à l’augmentation de la pression anthropique pesant sur les ressources en eau. Cette pression passe entre autre par une consommation et donc un rejet de multiples molécules organiques, parmi lesquelles les pesticides représentent des contaminants emblématiques. Longtemps utilisés en agriculture afin d’en augmenter la productivité, ces substances sont aujourd’hui utilisées également de façon importante dans notre quotidien (traitements vétérinaires, protection des matériaux de construction, peintures, papier, textiles, etc.). Cela conduit à identifier les rejets urbains comme des vecteurs de pesticides au travers des effluents de station de traitement des eaux usées ou des effluents d’exutoires pluviaux, qui viennent s’ajouter aux apports induits par l’agriculture. Cette multiplicité de sources couplée à une toxicité intrinsèque avérée en font des molécules à fort enjeu environnemental dont il est essentiel de hiérarchiser les apports afin de pouvoir mettre en place des mesures de réduction.Dans ce cadre, un continuum péri-urbain situé sur la Métropole de Bordeaux (France) a permis de mettre en évidence des profils de contamination différents entre les eaux naturelles, les effluents urbains et les exutoires pluviaux, tant sur l’aspect qualitatif que sur l’aspect quantitatif. Si les eaux de surface sont principalement quantitativement marquées par des phytopharmaceutiques (métolachlore, glyphosate), les molécules identifiées comme potentiellement impactantes (en termes d’effets potentiels) proviennent d’avantage d’effluents urbains (fipronil, imidaclopride). En effet, les stations de traitement des eaux usées sont identifiées comme d’importants vecteurs en biocides et antiparasitaires à usages vétérinaires en raison de leur faible capacité de traitement vis-à-vis de ces contaminants. Toutefois, ces effluents ne sont que le reflet des utilisations en amont du réseau. L’investigation de ce dernier a conduit à identifier les usages domestiques comme responsables de l’introduction de certaines molécules préoccupantes tels les antiparasitaires à usages vétérinaires (fipronil et imidaclopride). En parallèle, bien que non majoritaires en ce qui concerne les apports en pesticides, les exutoires pluviaux ne sont toutefois pas négligeables et apportent en quantités conséquentes des biocides de protection (comme la carbendazime, le diuron, le propiconazole ou la terbutryne) de par le lessivage de surfaces traitées en zones urbaines. Le cas du glyphosate semble complexe puisque aucune des voie d’apport n’est clairement identifiée comme majoritaire. L’apport est très global, probablement du fait de sa multiplicité d’usages, tant en agriculture que par certains professionnels ou par les particuliers.L’échantillonnage passif par les POCIS (Polar Organic Chemicals Integrative Sampler) a été appliqué avec succès afin de calculer des flux plus précis dans les eaux de surfaces, permettant ainsi une identification plus fine des sources majoritaires. Cet outil montre toutefois ses limites en ce qui concerne le suivi d’échantillons complexes telles que les eaux brutes, en présentant des cinétiques d’accumulation trop courtes pour permettre un suivi quantitatif du réseau d’assainissement sur de longues périodes. Ces observations ont été confirmées à l’occasion de calibrations in-situ en rivière et en entrée de station de traitement des eaux usées et qui ont donné lieu au développement de nouveaux outils. Les mini-POCIS et les POCIS-T, plus légers et plus petits ont été calibrés à la fois en laboratoire et en station de traitement des eaux usées. Ils se sont révélés plus adaptés que la forme classique pour suivre la contamination des eaux usées car ils permettent d’augmenter la durée du suivi. Ils représentent une alternative intéressante pour le suivi du réseau d’assainissement.
... Methods for processing and analyzing SPMDs and POCIS have been previously reported (Alvarez et al. 2008(Alvarez et al. , 2009(Alvarez et al. , 2014(Alvarez et al. , 2021Supplemental Data). Briefly, analytes of interest were recovered from the SPMDs using a dialysis process and then fractionated to isolate the chemicals from potential interferences using a combination of size exclusion chromatography and various gravity flow adsorptive column separations. ...
... Briefly, analytes of interest were recovered from the SPMDs using a dialysis process and then fractionated to isolate the chemicals from potential interferences using a combination of size exclusion chromatography and various gravity flow adsorptive column separations. The organochlorine pesticides, PCBs, and PBDEs were analyzed using gas chromatography with electron capture; and the PAHs were analyzed using gas chromatography/mass spectrometry (GC/MS; Alvarez et al. 2008Alvarez et al. , 2009). The OWCs were extracted from the POCIS sorbent prior to analysis using GC/MS (Alvarez et al. 2009(Alvarez et al. , 2014. ...
... The organochlorine pesticides, PCBs, and PBDEs were analyzed using gas chromatography with electron capture; and the PAHs were analyzed using gas chromatography/mass spectrometry (GC/MS; Alvarez et al. 2008Alvarez et al. , 2009). The OWCs were extracted from the POCIS sorbent prior to analysis using GC/MS (Alvarez et al. 2009(Alvarez et al. , 2014. Time-weighted average water concentrations of chemicals were estimated from residues measured in the SPMD and POCIS using uptake models (Huckins et al. 2006;Alvarez 2010) and either experimentally or theoretically derived sampling rates (R s ; Supplemental Data, Table SI-2). ...
Article
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Water‐borne contaminants were monitored in 69 tributaries of the Laurentian Great Lakes in 2010 and 2014 using semipermeable membrane devices (SPMDs), and polar organic chemical integrative samplers (POCIS). A risk‐based screening approach was used to prioritize chemicals and chemical mixtures, identify sites at greatest risk for biological impacts, and identify potential hazards to monitor at those sites. Analyses included 185 chemicals (143 detected) including polycyclic aromatic hydrocarbons (PAHs), legacy and current‐use pesticides, fire retardants, pharmaceuticals, fragrances, and others. Hazard quotients were calculated by dividing detected concentrations by biological effect concentrations reported in the ECOTOX Knowledgebase (Toxicity quotients, TQs) or ToxCast database (Exposure Activity Ratios, EARs). Mixture effects were estimated by summation of EAR values for chemicals that influence ToxCast assays with common gene targets. Nineteen chemicals, including atrazine, DEET, di(2‐ethylhexyl)phthalate, dl‐menthol, galaxolide, p‐tert‐octylphenol, three organochlorine pesticides, three PAHs, four pharmaceuticals, and three phosphate flame retardants, had TQs greater than 0.1 or EARs for individual chemicals (EARchem) greater than 10‐3 at 10% or more of the sites monitored. An additional four chemicals (tributyl phosphate, triethyl citrate, benz(a)anthracene, and benzo(b)fluoranthene) were present in mixtures with EAR (EARmixture) greater than 10‐3. To evaluate potential apical effects and biological endpoints to monitor in exposed wildlife, in vitro bioactivity data were compared to adverse outcome pathway (AOP) and gene ontology information. Endpoints and effects associated with endocrine disruption, alterations in xenobiotic metabolism, and potentially neuronal development would be relevant to monitor at the priority sites. The EAR threshold exceedance for many chemical classes was correlated with urban land cover and wastewater effluent influence, while herbicides and fire retardants were also correlated to agricultural land cover. This article is protected by copyright. All rights reserved.
... Multiple chemical contaminants have been documented in these sources (Jelic et al., 2011; Pal et al., 2010; Rostkowski et al., 2011; Sim et al., 2011; Weyrauch et al., 2010; Phillips et al., 2012). Previous research explored the possible relation between fish health and chemical exposures in the Potomac basin (Alvarez et al., 2009; Blazer et al., 2010; Iwanowicz et al., 2009). Expanding upon this earlier work, a network of six stream sites (plus one reference stream) was sampled to provide a more comprehensive assessment of chemical contaminants in water and bed sediment in the Potomac basin. ...
... A total of 161 target chemicals were measured in single, passivewater samples collected at five sites. All extracts from the passivewater samplers were prepared using established procedures (Alvarez et al., 2008, 2009). Extracts were analyzed for antibiotics (Meyer et al., 2007); synthetic and biogenic hormones (Foreman et al., 2012); pharmaceuticals (Furlong et al., 2008; Schultz and Furlong, 2008); wastewater indicator compounds (Zaugg et al., 2006); agricultural pesticides , halogenated insecticides, polychlorinated biphenyls (PCBs); and polycyclic aromatic hydrocarbons (PAHs) (Alvarez et al., 2008). ...
... In addition, POCIS extracts were screened for total estrogenicity using the yeast estrogen screen (YES) (Alvarez et al., 2009). One issue in using passive samplers in a quantitative approach is having a method available to correct for in situ exposure conditions (e.g. ...
Article
The Potomac River basin is an area where a high prevalence of abnormalities such as testicular oocytes (TO), skin lesions, and mortality has been observed in smallmouth bass (SMB, Micropterus dolomieu). Previous research documented a variety of chemicals in regional streams, implicating chemical exposure as one plausible explanation for these biological effects. Six stream sites in the Potomac basin (and one out-of-basin reference site) were sampled to provide an assessment of chemicals in these streams. Potential early life-stage exposure to chemicals detected was assessed by collecting samples in and around SMB nesting areas. Target chemicals included those known to be associated with important agricultural and municipal wastewater sources in the Potomac basin. The prevalence and severity of TO in SMB were also measured to determine potential relations between chemistry and biological effects.
... A strain of Saccharomyces cerevisiae was inserted with estrogen response elements and a luciferase gene, so that when the yeast is exposed to estrogen or EEDCs it fluoresces and can be read on a fluorescent plate reader (Sanseverino et al., 2005). Alvarez et al. (2009) used the BLYES assay to detect estrogenicity in the POCIS samples (Table 1) ...
... POCIS deployment, extractions and analysis were all completed by Alvarez et al. (2009). For this experiment, POCIS were deployed in Conococheague Creek in Maryland, just upstream (in 2005Maryland, just upstream (in , 2006 and downstream (in 2005, 2006) Carlsbad, CA). ...
... In female rainbow trout, Table 1 were previously screened for estrogenicity using BLYES and all of the samples were shown to have estrogenicity. Known estrogenic compounds were found to be present in the samples by Alvarez et al. (2009), as indicated by chemical analysis (Table 4). Normalized data from 2005 were compared and no statistically significant differences were seen from the Kruskal-Wallis nonparametric test (p=0.1; ...
... Samplers were deployed at the Juniata River site for 42 days (April 21, 2010 to June 1, 2010) and at the Allegheny River site for 41 days (April 28, 2010 to June 7, 2010). Samplers were extracted using established procedures previously described (Alvarez et al. 2009). Extracts of the POCIS were screened for total estrogenicity using the bioluminescent yeast-based estrogen screen (Sanseverino et al. 2009 as modified in Alvarez et al. 2009), synthetic and biogenic hormones by adaptation of a water method (Foreman et al. 2012), and agricultural pesticides (Alvarez et al. 2009 ). ...
... Samplers were extracted using established procedures previously described (Alvarez et al. 2009). Extracts of the POCIS were screened for total estrogenicity using the bioluminescent yeast-based estrogen screen (Sanseverino et al. 2009 as modified in Alvarez et al. 2009), synthetic and biogenic hormones by adaptation of a water method (Foreman et al. 2012), and agricultural pesticides (Alvarez et al. 2009 ). Extracts from the SPMDs were screened for total PCBs, polycycl ic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (Alvarez et al. 2009). ...
... Extracts of the POCIS were screened for total estrogenicity using the bioluminescent yeast-based estrogen screen (Sanseverino et al. 2009 as modified in Alvarez et al. 2009), synthetic and biogenic hormones by adaptation of a water method (Foreman et al. 2012), and agricultural pesticides (Alvarez et al. 2009 ). Extracts from the SPMDs were screened for total PCBs, polycycl ic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (Alvarez et al. 2009). Chemicals measured in the passive samplers and their method detection limits (MDL) and reporting levels (RL) are presented in Supplementary Tables 1 and 2. ...
Article
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Fishes were collected at 16 sites within the three major river drainages (Delaware, Susquehanna, and Ohio) of Pennsylvania. Three species were evaluated for biomarkers of estrogenic/antiandrogenic exposure, including plasma vitellogenin and testicular oocytes in male fishes. Smallmouth bass Micropterus dolomieu, white sucker Catostomus commersonii, and redhorse sucker Moxostoma species were collected in the summer, a period of low flow and low reproductive activity. Smallmouth bass were the only species in which testicular oocytes were observed; however, measurable concentrations of plasma vitellogenin were found in male bass and white sucker. The percentage of male bass with testicular oocytes ranged from 10 to 100 %, with the highest prevalence and severity in bass collected in the Susquehanna drainage. The percentage of males with plasma vitellogenin ranged from 0 to 100 % in both bass and sucker. Biological findings were compared with chemical analyses of discrete water samples collected at the time of fish collections. Estrone concentrations correlated with testicular oocytes prevalence and severity and with the percentage of male bass with vitellogenin. No correlations were noted with the percentage of male sucker with vitellogenin and water chemical concentrations. The prevalence and severity of testicular oocytes in bass also correlated with the percent of agricultural land use in the watershed above a site. Two sites within the Susquehanna drainage and one in the Delaware were immediately downstream of wastewater treatment plants to compare results with upstream fish. The percentage of male bass with testicular oocytes was not consistently higher downstream; however, severity did tend to increase downstream. Electronic supplementary material The online version of this article (doi:10.1007/s10661-014-3868-5) contains supplementary material, which is available to authorized users.
... Because discrete (grab) water samples only represent conditions at the time of sampling and can miss episodic events such as surface runoff from agricultural fields after waste has been applied, we suggest that our samples may not be representative of the year-round concentrations occurring in waters surrounding nonpoint sources. Other studies have reported seasonal changes in EDCs in surface run-off associated with agricultural applications, with the highest levels usually occurring in spring after crop planting [38,39]. Of particular concern are the relatively high detectable levels of estrogenic EDCs in surface waters found during our fall sampling, when surface run-off would likely be less than during other times of the year (e.g., after spring crop planting and fertilization and during summer low flows). ...
... In other studies, runoff from sites with land application of manure and poultry litter resulted in elevated levels of estrogen in runoff and adjacent streams [43,44]. Despite the fact that these compounds degrade relatively quickly in surface waters (hours to months; [23,24]) and our samples were taken a few months following peak seasonal applications of waste [38,39], our map predictions were still reflective of the level of estrogenic compounds in the water. Environmental exposure of low estrogenic EDC concentrations to fish likely occur intermittently over a generation due to seasonal applications of waste to agricultural fields, changes in precipitation that can dilute or concentrate estrogenic EDCs, fish movement in and out of areas with estrogenic EDC contamination, or other temporal variation in source influxes. ...
Article
The presence of endocrine disrupting compounds (EDCs), particularly estrogenic compounds, in the environment has drawn public attention across the globe, yet we currently lack a clear understanding of the extent and distribution of estrogenic EDCs in surface waters and their relationship to potential sources. The objective of our study was to identify and examine the potential input of estrogenic EDC sources in North Carolina waterbodies using a Geographic Information Systems (GIS) mapping and analysis approach. Existing data from state and federal agencies were used to create point and nonpoint source maps depicting the cumulative contribution of potential sources of estrogenic EDCs to North Carolina surface waters. Water was collected from 33 sites (12 associated with potential point sources, 12 associated with potential nonpoint sources and 9 reference), to validate the predictive results of our GIS analysis. Estrogenicity (measured as 17β-estradiol equivalence; EEQ) ranged from 0.06 to 56.9 ng/L. However, the majority of our sites (88%) had water EEQ concentrations below 1 ng/L. Sites associated with point and nonpoint sources had significantly higher EEQ levels than reference sites. Results suggested that water EEQ was reflective of GIS predictions, confirming the relevance of landscape-level influences on water quality and validating our GIS approach to characterize such relationships. Environ Toxicol Chem © 2014 SETAC
... These biological changes have also been observed in relation to a variety of landscape types and containment sources Pow et al. 2017). Seasonal differences have been observed in the presence and prevalence of EDCs and estrogenic activity in surface waters (Alvarez et al. 2009) and intersex prevalence in fish (Blazer et al. 2007). Exposure models estimating total estrogenicity (E2 equivalents) of surface waters reveal correlations with high predicted exposures (> 10 ng/L) and severe intersex in the rainbow darter (Etheostoma caeruleum), a sentinel indicator species for environmental exposures (Arlos et al. 2018;Hicks and Servos, 2017). ...
... In the smallmouth bass (Micropterus dolomieu), pre-spawn and spawning season occurs annually around May, during which higher intersex prevalence and severity have been observed in several watersheds (Blazer et al. 2007). Spring spawn also coincides with increased concentrations of pesticides and other contaminants (Alvarez et al. 2008(Alvarez et al. , 2009) from run-off events which are an important environmental factor capable of transporting contaminants to local surface waters (Battaglin et al. 2005;Hladik et al. 2014;Thurman et al. 1991). These studies suggest that both duration and life stage of fish during exposure are important factors in inducing biological effects. ...
Article
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Endocrine-disrupting compounds (EDCs), specifically estrogenic endocrine-disrupting compounds, vary in concentration and composition in surface waters under the influence of different landscape sources and landcover gradients. Estrogenic activity in surface waters may lead to adverse effects in aquatic species at both individual and population levels, often observed through the presence of intersex and vitellogenin induction in male fish. In the Chesapeake Bay Watershed, located on the mid-Atlantic coast of the USA, intersex has been observed in several sub-watersheds where previous studies have identified specific landscape sources of EDCs in tandem with observed fish health effects. Previous work in the Potomac River Watershed (PRW), the largest basin within the Chesapeake Bay Watershed, was leveraged to build random forest regression models to predict estrogenic activity at unsampled reaches in both the Potomac River and larger Chesapeake Bay Watersheds (CBW). Model outputs including important variables, partial dependence plots, and predicted values of estrogenic activity at unsampled reaches provide insight into drivers of estrogenic activity at different seasons and scales. Using the US Environmental Protection Agency effects-based threshold of 1.0 ng/L 17 β-estradiol equivalents, catchments predicted to exceed this value were categorized as at risk for adverse effects from exposure to estrogenic compounds and evaluated relative to healthy watersheds and recreation access locations throughout the PRW. Results show immediate catchment scale models are more reliable than upstream models, and the best predictive variables differ by season and scale. A small percentage of healthy watersheds (< 13%) and public access sites were classified as at risk using the “Total” (annual) model in the CBW. This study is the first Potomac River Watershed assessment of estrogenic activity, providing a new foundation for future risk assessment and management design efforts, with additional context provided for the entire Chesapeake Bay Watershed.
... Chemicals were extracted from the two waste indicator POCIS using 25 mL of 80:20 (v:v) dichloromethane:methyl-tertbutyl ether, after which the two extracts were combined into a single sample to increase the amount of chemicals present for analysis. The combined extracts were reduced in volume using rotary evaporation and nitrogen blowdown prior to analysis by GC/MSD (Alvarez et al., 2009(Alvarez et al., , 2012. ...
... Similarily, Villa et al. (2012) observed increased concentrations in the Molgora River, Italy, during periods of the year where the river flows were reduced. Alvarez et al. (2009) did not observe seasonal differences in OWC concentrations in a WWTP effluent study; however, the ratio of WWTP effluent to mean stream flow remained largely unchanged between sampling periods therefore effects of dilution may not have been observed. ...
... The POCIS membranes were shipped to the USGS, Columbia Environmental Research Center for analyte recovery. The procedures used for preparing the POCIS samples for analysis were described earlier 8 . Briefly, chemicals of interest were recovered from the POCIS sorbent using 50 mL of 15158 (V5V5V) methanol:toluene:dichloromethane followed by 20 mL of ethyl acetate. ...
... All rights reserved (BWTS-0, BWTS-6). Thirty-four individual PAHs were analyzed including the priority pollutant PAHs and alkylated PAHs (Table S4), as described [28,29]. Detection limits for the PAHs differed for sample sets analyzed on different days, a reflection of higher method and instrument detection limits for the second set of samples. ...
Article
Non-native organisms in the ballast water (BW) of freshwater ships must be killed to prevent the spread of invasive species. The ideal BW treatment system (BWTS) would kill 100% of BW organisms with minimal residual toxicity to organisms in receiving waters. The residual toxicity and chemistry of a BWTS was evaluated: sodium hydroxide was added to elevate pH to > 11.5 to kill BW organisms, then reduced to pH<9 by sparging with wet-scrubbed diesel exhaust (the source of CO2 ). Cladocerans (Ceriodaphnia dubia), amphipods (Hyalella azteca), and fathead minnows (Pimephales promelas) were exposed for 2 days to BWTS water under an air atmosphere (pH drifted to ≥ 9), or a 2.5% CO2 atmosphere (pH 7.5 to 8.2) then transferred to control water for 5 days to assess potential delayed toxicity. Chemical concentrations in the BWTS water met vessel discharge guidelines with the exception of concentrations of copper. There was little to no residual toxicity to cladocerans or fish, but the BWTS water was toxic to amphipods. Maintaining a neutral pH and diluting BWTS water by 50% eliminated toxicity to the amphipods. Toxicity of BWTS water would likely be minimal due to rapid dilution in the receiving water with sub-surface release likely preventing pH rise. This BWTS has the potential to become a viable method for treating BW released into freshwater systems. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.
... In addition to SPMD, the studies used other passive sampling devices such as POCIS (Polar Organic Chemical Integrative Sampler), o-DGT (diffusive gradients in thin films for organics), and PU (polyurethane film), with exposure from 4 to 460 days in water (Table S2). Alvarez et al. (2009) used POCIS and SPMD to evaluate various pesticides in the Potomac River watershed, USA, and four other studies using this technique were carried out in the country. ...
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The objective of this study was to critically review studies published up to November 2021 that investigated the presence of pesticides in surface freshwater to answer three questions: (1) in which countries were the studies conducted? (2) which pesticides are most evaluated and detected? and (3) which pesticides have the highest concentrations? Using the Prisma protocol, 146 articles published from 1976 to November 2021 were included in this analysis: 127 studies used grab sampling, 10 used passive sampling, and 9 used both sampling techniques. In the 45-year historical series, the USA, China, and Spain were the countries that conducted the highest number of studies. Atrazine was the most evaluated pesticide (56% of the studies), detected in 43% of the studies using grab sampling, and the most detected in passive sampling studies (68%). The compounds with the highest maximum and mean concentrations in the grab sampling were molinate (211.38 µg/L) and bentazone (53 µg/L), respectively, and in passive sampling, they were oxyfluorfen (16.8 µg/L) and atrazine (4.8 μg/L), respectively. The levels found for atrazine, p,p′-DDD, and heptachlor in Brazil were higher than the regulatory levels for superficial water in the country. The concentrations exceeded the toxicological endpoint for at least 11 pesticides, including atrazine (Daphnia LC50 and fish NOAEC), cypermethrin (algae EC50, Daphnia and fish LC50; fish NOAEC), and chlorpyrifos (Daphnia and fish LC50; fish NOAEC). These results can be used for planning pesticide monitoring programs in surface freshwater, at regional and global levels, and for establishing or updating water quality regulations.
... The Potomac River basin comprises 38,000 km 2 or roughly 23% of the watershed land area (ICPRB, 2008). Evidence of estrogenic endocrine disruption and the presence of testicular oocytes in fish species have been noted in the Potomac River basin (Alvarez et al., 2009; Iwanowicz et al., 2009) The larger South Fork of the Shenandoah River is included as a reference point. The second region is Cedar Run, a smaller tributary of the Potomac River. ...
... Severity has also been found to be more informative when investigating correlations with watershed land use characteristics (Blazer et al., 2012) and contaminant exposures (Alvarez et al., 2009). Collectively, the literature suggests that fish with low TO severity maintain normal reproductive function while those with higher severity are more likely to suffer adverse reproductive effects (Blazer et al., 2012; Harris et al., 2010; Jobling, 2002). ...
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The appearance of testicular oocytes (TO) in wild fish populations has received considerable attention in the scientific literature and public media. Current methods to quantify TO are lethal; instead, a non-lethal alternative was examined. Laparoscopic insertion into the genital pore allowed internal visualization of the gonad and detection of TO by collecting five testis biopsies in smallmouth bass Micropterus dolomieu and largemouth bass Micropterus salmoides. Overall, biopsies quantified similar levels of TO detection and severity to conventional transverse sectioning with less than 10% mortality. Suitability of surgical anesthetics, tricaine methanesulfonate and electronarcosis were examined in laboratory and field applications. Electronarcosis had the added benefit of rapid sex identification and immediate release of female fish with minimal trauma, representing significant benefits when sampling small or compromised populations. Laparoscopy may be useful for monitoring the prevalence and severity of TO in these fish species when lethal sampling is not a desired outcome.
... Analyses were performed using an Agilent 6890 GC coupled to a 5973 N quadrupole mass selective detector (MSD) operated in full scan positive ion electron ionization (EI) mode. Details on the instrument conditions have been previously reported (Alvarez et al., 2009). The two POCIS for the pharmaceuticals were each extracted with 25 mL of methanol (Optima grade, Fisher Scientific), which was subsequently evaporated to 2–3 mL by rotary evaporation prior to being combined into a single sample. ...
... Size exclusion chromatography was used to isolate EPOCs and POCs from other co-extracted chemicals in the dialysate. Additional chromatographic techniques were used to further enrich the sample, isolating the EPOCs from other potentially interfering chemicals (Alvarez et al., 2008(Alvarez et al., , 2009. ...
Article
Coral, fish, plankton, and detritus samples were collected from coral reefs in Virgin Islands National Park (VIIS) and Virgin Islands Coral Reef National Monument (VICR) to assess existing contamination levels. Passive water sampling using polar organic chemical integrative samplers (POCIS) and semi-permeable membrane devices found a few emerging pollutants of concern (DEET and galaxolide) and polynuclear aromatic hydrocarbons. Very little persistent organic chemical contamination was detected in the tissue or detritus samples. Detected contaminants were at concentrations below those reported to be harmful to aquatic organisms. Extracts from the POCIS were subjected to the yeast estrogen screen (YES) to assess potential estrogenicity of the contaminant mixture. Results of the YES (estrogen equivalency of 0.17-0.31ng/L 17-β-estradiol) indicated a low estrogenicity likelihood for contaminants extracted from water. Findings point to low levels of polar and non-polar organic contaminants in the bays sampled within VICR and VIIS.
... Thus, effluent discharges are potentially a major source of CECs in aquatic environments. Once released to the environment, some CECs, such as nonyphenol and fire retardants, may accumulate in fish tissue [11] and cause adverse biological effects12131415. A 2006 study conducted by Rempel et al. in southern California showed biological responses indicative of exposure to endocrine disruptors in marine flatfish living near POTW outfall discharges [16]. ...
... The POCIS devices were deployed during April and May because these months were previously identified as periods of high estrogenicity in the Virginia watershed (Ciparis et al. 2012). After 31-45 days, the sampling devices were retrieved as described by Alvarez (2010), and POCIS membranes were shipped to the USGS Columbia Environmental Research Center for analyte recovery as previously described (Alvarez et al. 2009). Briefly, the POCIS membranes were extracted using 50 mL of 1:1:8 (vol:vol:vol) methanol:toluene:dichloromethane followed by 20 mL ethyl acetate. ...
Article
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Environmental endocrine disruptors (EED) are exogenous chemicals that mimic endogenous hormones, such as estrogens. Previous studies using a zebrafish transgenic reporter demonstrated that the EEDs bisphenol A and genistein preferentially activate estrogen receptors (ER) in the larval heart compared to the liver. However, it was not known whether the transgenic zebrafish reporter was sensitive enough to detect estrogens from environmental samples, whether environmental estrogens would exhibit similar tissue-specific effects as BPA and genistein or why some compounds preferentially target receptors in the heart. We tested surface water samples using a transgenic zebrafish reporter with tandem estrogen response elements driving green fluorescent protein expression (5xERE:GFP). Reporter activation was colocalized with tissue-specific expression of estrogen receptor genes by RNA in situ hybridization. Selective patterns of ER activation were observed in transgenic fish exposed to river water samples from the Mid-Atlantic United States, with several samples preferentially activating receptors in embryonic and larval heart valves. We discovered that tissue-specificity in ER activation is due to differences in the expression of estrogen receptor subtypes. ERα is expressed in developing heart valves but not in the liver, whereas ERβ2 has the opposite profile. Accordingly, subtype-specific ER agonists activate the reporter in either the heart valves or the liver. The use of 5xERE:GFP transgenic zebrafish has revealed an unexpected tissue-specific difference in the response to environmentally relevant estrogenic compounds. Exposure to estrogenic EEDs in utero is associated with adverse health effects, with the potentially unanticipated consequence of targeting developing heart valves.
... The POCIS membranes were shipped to the USGS, Columbia Environmental Research Center for analyte recovery. The procedures for preparing the POCIS samples for analysis deviated slightly from those described earlier (Alvarez et al., 2009). Briefly, chemicals were extracted from the POCIS sorbent using 25 ml of 80:20 (V:V) dichloromethane:methyl-tert-butyl-ether. ...
Article
Even though the presence of endocrine disrupting chemicals (EDCs) with thyroid hormone (TH)-like activities in the environment is a major health concern, the methods for their efficient detection and monitoring are still limited. Here we describe a novel cell assay, based on the translocation of a green fluorescent protein (GFP)—tagged chimeric molecule of glucocorticoid receptor (GR) and the thyroid receptor beta (TRβ) from the cytoplasm to the nucleus in the presence of TR ligands. Unlike the constitutively nuclear TRβ, this GFP-GR-TRβ chimera is cytoplasmic in the absence of hormone while translocating to the nucleus in a time- and concentration-dependent manner upon stimulation with triiodothyronine (T3) and thyroid hormone analogue, TRIAC, while the reverse triiodothyronine (3,3′,5′-triiodothyronine, or rT3) was inactive. Moreover, GFP-GR-TRβ chimera does not show any cross-reactivity with the GR-activating hormones, thus providing a clean system for the screening of TR beta −interacting EDCs. Using this assay, we demonstrated that Bisphenol A (BPA) and 3,3′,5,5′-Tetrabromobisphenol (TBBPA) induced GFP-GR-TRβ translocation at micro molar concentrations. We screened over 100 concentrated water samples from different geographic locations in the United States and detected a low, but reproducible contamination in 53% of the samples. This system provides a novel high-throughput approach for screening for endocrine disrupting chemicals (EDCs) interacting with TR beta.
... Exposure of humans and aquatic species through water to substances that cause disruption of the endocrine system, called endocrine disrupting chemicals (EDCs), is becoming a serious environmental and health problem [1,2]. Scientific research studies have for instance linked the intersex in male fish condition to exposure of fish to estrogens in the aquatic environment [3][4][5][6]. ...
Article
The removal and recovery of highly potent endocrine disrupting chemicals (EDCs) estrone (E1), 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) and the oxidation product 2-hydroxyestradiol (2OHE2) in water was achieved on Polyamide 6 (PA6) particles. Hydrogen bonding was the main mechanism driving the adsorption of these EDCs on PA6 at pHs lower than the EDCs pKas (∼10.5) and their adsorption was not affected by the water matrix nor by solute-solute interaction. The adsorption isotherms were linear and the values of the linearity constants for E2 and EE2 were almost double those for E1 and 2OHE2. This was correlated to the number of intermolecular hydrogen bonds via –OH groups of the EDCs (H-bond donors) available for interaction with PA6’s surface via the amide groups (H-bond acceptors). The effect of pH on the adsorption of the EDCs on PA6 was significant only at pHs > EDCs pKa (∼10.5). The breakthrough curves of the EDCs on PA6 particles in a fixed-bed column were successfully modelled using a linearised mass transfer model. This study shows that PA6 appears an effective sorbent for the removal as well as the enrichment and pre-concentration of EDCs in wastewater samples.
... Increasing incidents of disorders such as obesity, diabetes, metabolic syndrome, reproductive dysfunction, and neuro-developmental abnormalities in some human populations have raised concern that disruption of key endocrine-signaling pathways by exposure to environmental chemicals may be involved (Heindel and Blumberg, 2019;LeBlanc et al., 2012;Lupu et al., 2020;Mimoto et al., 2017;Papalou et al., 2019;Repouskou et al., 2020). Similarly, many endocrine active chemicals have been identified in surface waters globally which has raised significant concern over the past few decades regarding their impacts on wildlife populations (Alvarez et al., 2009;Cotter et al., 2015;Jeffries et al., 2010;Kolpin et al., 2002). Aquatic environments contaminated with endocrine disrupting chemicals (EDC), particularly estrogenic EDC's, have been linked to a number of adverse effects in wildlife, including the aberrant expression of vitellogenin (VTG), a female specific egg yolk protein, in male fish (Cotter et al., 2015;Hutchinson et al., 2013;White et al., 1994), and feminization and/or demasculinization within oviparous populations, which may be linked to decreased reproductive output, compromised immunity, altered sex ratios, and ultimately population collapse (Kidd et al., 2007;Nash et al., 2004;Woodling et al., 2006). ...
Article
The 20th Pollutant Responses in Marine Organisms (PRIMO 20) conference provided a forum for scientists from around the world to communicate novel toxicological research findings specifically focused on aquatic organisms, by combining applied and basic research at the intersection of environmental and mechanistic toxicology. The work highlighted in this special issue of Aquatic Toxicology, a special issue of Marine Environmental Research, and presented through posters and presentations, encompass important and emerging topics in freshwater and marine toxicology. This includes multiple types of emerging contaminants including microplastics and UV filtering chemicals. Other studies aimed to further our understanding of the effects of endocrine disrupting chemicals, pharmaceuticals, and personal care products. Further research presented in this virtual issue examined the interactive effects of chemicals and pathogens, while the final set of manuscripts demonstrates continuing efforts to combine traditional biomonitoring, data from -omic technologies, and modeling for use in risk assessment and management. An additional goal of PRIMO meetings is to address the link between environmental and human health. Several articles in this issue of Aquatic Toxicology describe the appropriateness of using aquatic organisms as models for human health, while the keynote speakers, as described in the editorial below, presented research that highlighted bioaccumulation of contaminants such as PFOS and mercury from fish to marine mammals and coastal human populations such as the Gullah/GeeChee near Charleston, South Carolina, USA.
... Co-infections of bacterial, viral, as well as parasitic infections have been associated with these events [4,6,7] suggesting immunosuppression. Estrogenic endocrine disruption as evidenced by testicular oocytes (intersex), vitellogenin in male fish [8][9][10] and the occurrence of contaminants linked to intersex [4,7,11,12] has been confirmed within the areas of the Chesapeake watershed where disease events occur. The observation of a complex disease etiology that includes multiple obligate and opportunistic pathogens and parasites as well as endocrine disruption necessitates laboratory investigations into the potential changes in physiologic functions including the immune response. ...
Article
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Smallmouth bass (Micropterus dolomieu) are used as an indicator species in environmental monitoring and assessment studies. However, laboratory-based studies for methods development and effector assessment are limited for this species. Nutrition, a known modulator of teleost physiological responses including immune function, is a critical knowledge-gap sometimes overlooked in the design of laboratory studies. We report the results from a study evaluating a commercially available artificial pelleted diet for bass and live feed (fathead minnows). Following a six-month diet-acclimation period, age-0 smallmouth bass were assessed using morphometric measures, histologic and immune-function end points using conventional methods, miniaturized cell isolation and assay methods as well as imaging flow cytometry. Fish on the two diets did not significantly differ in length, weight, or condition factor, indicating that growth was similar in the two groups. Histologic examination revealed relatively higher levels of macrophage aggregates and accumulation of ceroid/lipofuscin in the spleen as well as hepatocyte changes in the pellet-fed group. Leukocytes from the pellet-fed group exhibited significantly elevated bactericidal activity and significantly depressed mitogen response compared to fish fed live feed. Following exposure to a known inducer of inflammatory responses, bacterial lipopolysaccharide, responses including the transition of leukocytes to an apoptotic/necrotic condition differed significantly based on diet. Histologic findings were consistent with the occurrence of diet-related oxidative stress in the pellet-fed fish. Oxidative stress can be induced by multiple factors including environmental pollutants. For a diet to be useful in laboratory-based studies, it cannot elicit response that could also be induced by experimental treatments. To do so greatly complicates the detection of experimental effects. Until an artificial diet is developed for smallmouth bass that does not produce potentially confounding conditions for laboratory-based studies, use of a live feed appears to be the best option.
... In the six tributaries we assessed, all but one of them had multiple EDCs present at detectable levels ( Table 2). While extensive EDC overlap is not uncommon, a chemical-by-chemical approach to EDCs has been largely criticized, and a more cumulative approach is advised for EDC risk assessment (Kortenkamp 2007;Alvarez et al. 2009;Van den Brink et al. 2019). Further, the lack of field research on the 'potency' of individual EDCs on individual fish species therefore makes it difficult to justly determine the biological risk of overlapping EDCs on SMB. ...
Article
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The Susquehanna River basin is one of the largest and most diverse watersheds in the northeastern United States, however, its historically renowned Micropterus dolomieu (smallmouth bass-SMB) fishery has been in decline since the mid-2000s. Agricultural herbicide runoff has been identified as a major risk for Susquehanna basin SMB populations given their effects as endocrine disrupting compounds (EDCs). During the summers of 2016 and 2017, we assessed potential threats to SMB populations in 11 tributaries to the Juniata River, the second largest tributary to the Susquehanna River. Passive water samplers were installed for 38-39 days in ecologically important tributaries to quantify six common herbicides, and SMB were collected from nine sites in 2016 and 2017 to assess their health and morphology. Our passive water samplers showed markedly higher EDC concentrations than has previously been documented in the Juniata basin, with atrazine occurring at all sites and in the highest concentrations (11.09-91.02 ng/L). SMB blood samples revealed complete prevalence (100%) of vitellogenin, an egg protein precursor, in male fishes further confirming previous rates male vitellogenisis. Additionally, SMB hepatosomatic index (HSI) was statistically higher in female SMB than in male SMB (P < 0.001), and higher than many previous regional SMB studies further highlighting a contaminant-based stressor. Finally, a geometric morphometric analysis of SMB body shape indicated morphologies to be significantly site-based. Morphological differences were in line with the ram-suction feeding continuum, further revealing potential vulnerability in SMB sub-populations where EDCs may alter food web dynamics and prey availability. Overall, our study of the Juniata River Basin highlights high EDC concentrations alongside high rates of male vitellogenisis and elevated HSI, and proposes novel theory for morphological vulnerability in SMB sub-populations.
... Sixty-six percent (78) of the 118 analytes examinedwhich included congeners, metabolites, and degradateswere detected in passive sampler extracts; 19 in OA, 35 in BB, and 70 in LVB. Estimated time-weighted average water concentrations over the sampling period (~30 days) were calculated at the three sites using the method described by Alvarez et al. (2009). There was a clear gradient of detections and analyte concentrations between sites (LVB > BB > OA, Fig. 3), which reflects contaminant loadings from upstream land use in LVB and OA and the mixing of these sources in BB. ...
Article
Introductions of dreissenid mussels in North America have been a significant concern over the last few decades. This study assessed the distribution of synthetic organic compounds (SOCs) in the food web of Lake Mead, Nevada/Arizona, USA and how this distribution was influenced by the introduction of invasive quagga mussels. A clear spatial gradient of SOC concentrations in water was observed between lake basins downstream of populated areas and more rural areas. Within the food web, trophic magnification factors (TMF) indicated statistically significant biomagnification for nine, and biodilution for two, of 22 SOCs examined. The highest value recorded was for PCB 118 (TMF, 5.14), and biomagnification of methyl triclosan (TMF, 3.85) was also apparent. Biodilution was observed for Tonalide® (0.06) and Galaxolide® (0.38). Total SOC concentration in quagga mussels was higher than in three pelagic fishes. Also, 19 of 20 SOC examined in Largemouth Bass (Micropterus salmoides) had substantially lower concentrations in 2013, when quagga mussels had become well established, than in 2007/08, soon after quagga mussels were introduced. Estimates of SOC concentrations in the water column and quagga mussels suggest that a considerable portion (~10.5%) of the SOC mass in the lake has shifted from the pelagic to the benthic environments due to quagga mussel growth. These observations suggest that benthic species, such as the endangered Razorback Sucker, may be experiencing increased risk of SOC exposure. In addition, stable isotope analysis (carbon and nitrogen) indicated a decrease in the nutritional value of zooplankton to consumers (e.g., Razorback Sucker larvae) since quagga mussels became established. These changes could affect Razorback Sucker larval survival and recruitment. Results from this study strongly suggest that the introduction of quagga mussels has greatly altered the dynamics of SOCs and other processes in the food web of Lake Mead.
... Most of the previous studies on the determination of musk compounds have been conducted using SPMD (Li et al. 2010;Helm et al. 2012;Allan et al. 2013;Hoque et al. 2014). To the best of our knowledge, only in a few studies, the POCIS sampler was used for monitoring of musk compounds, namely tonalide and galaxolide (Alvarez et al. 2005(Alvarez et al. , 2008(Alvarez et al. , 2009Rosen et al. 2010;Morin et al. 2012). ...
Article
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Synthetic musk compounds are extensively used in personal care and cosmetic products all over the world. Afterwards, they are discharged into the environment mainly because they are not completely removed in wastewater treatment plants. The aim of this study was to investigate if a passive sampler is applicable for the monitoring of tonalide, a polycyclic musk compound, in the aquatic environment and to compare the levels of tonalide in pesticide-polar organic chemical integrative sampler (POCIS) and biota. For this purpose, four sampling localities on the three biggest rivers in the Czech Republic were selected. Tonalide was determined in POCIS at all sampling sites in the concentration ranging from 9 ng/POCIS (Labe River, Hradec Králové) to 25 ng/POCIS (Morava River, Blatec). The locality with the most frequent occurrence of tonalide in biota samples was the Morava River which well corresponded with the highest tonalide concentration in POCIS among sampling sites. The highest number of positive tonalide detections among all studied biota samples was found in fish plasma. To the best of our knowledge, this is the first evidence that tonalide bioaccumulates in fish blood. Tonalide levels were below the limit of quantification in benthos samples at all sampling sites.
... The relative GSI increase in fish collected from the downstream site was against our expectations, as numerous studies have previously reported a reduction in GSI in response to WWTP effluent exposure (Hecker et al., 2002;Vajda et al., 2008;Tetreault et al., 2011). However, WWTP effluent is composed of a complex mixture of chemicals that varies spatially and temporally, and as a result, its effect on fishes varies as well (Alvarez et al., 2009). HSI was higher in males from the downstream site, which is consistent with previous studies that indicated higher energy storage in darters (as indicated by a higher HSI) collected from downstream sites compared to reference sites (Tetreault et al., 2011). ...
Article
The objective of this study was to assess the effects of municipal wastewater treatment plant effluent on the energetics and stress response of rainbow darter (Etheostoma caeruleum). Male and female rainbow darter were collected upstream and downstream of the Waterloo WWTP in the Grand River watershed, ON, Canada. To assess the effects of wastewater treatment plant effluent on whole-body and tissue specific metabolic capacity, closed-chamber respirometry and muscle-enzyme activity analyses were performed. Plasma cortisol was also collected from fish before and after an acute air-exposure stressor to evaluate the cortisol stress response in fish exposed to additional stressors. Male and female rainbow darter collected downstream of the effluent had higher oxygen consumption rates, while differences in enzyme activities were primarily associated with sex rather than collection site. No impairment in the cortisol stress response between downstream and upstream fish was observed, however baseline cortisol levels in female fish from the downstream site were significantly higher compared to other baseline groups. Stress-induced cortisol levels were also higher in female fish from both sites when compared to their male counterparts. Overall, this study demonstrates that chronic exposure to WWTP effluent impacts whole-body metabolic performance. This study was also able to demonstrate that sex-differences are a key determinant of various metabolic changes in response to physiological stress, thereby, providing a novel avenue to be considered and further explored.
Article
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Reports of water quality research and management pertaining to emerging pollutants, either chemical or biological, for which discussion of occurrence surveys, fate investigations, treatment methodologies, modeling, and/or toxicity/risk assessment appearing in the peer-reviewed literature during 2009, are presented.
Article
Smallmouth bass in the Susquehanna River Basin, Chesapeake Bay Watershed, USA, have been exhibiting clinical signs of disease and reproductive endocrine disruption (e.g., intersex, male plasma vitellogenin) for over fifteen years. Previous histological and targeted chemical analyses have identified infectious agents and pollutants in fish tissues including organic contaminants, mercury, and perfluorinated compounds, but a common causative link for the observed signs of disease across this widespread area has not been determined. This study examines 146 young-of-year smallmouth bass collected from 14 sampling sites in the Susquehanna River Basin, Pennsylvania, USA with varying levels of disease prevalence. Whole fish were extracted by a recently developed modification to the quick, easy, cheap, effective, rugged, and safe extraction method and analyzed by comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry. A targeted analysis was conducted to identify the presence and quantity of 127 known contaminants, including polychlorinated biphenyls, brominated diphenyl ethers, organochlorinated pesticides, and pharmaceutical and personal care products. A non-targeted analysis was conducted on the same data set to identify analytes of interest not included on routine target compound lists. Chromatographic alignment through Statistical Compare (ChromaTOF GC) was followed by Fisher ratio and principal component analysis to reduce the data set from thousands of peaks per sample to a final data set of 65 analytes of interest. Comparisons of these 65 compounds between Normal (no observed health anomalies) and Lesioned (observed health anomaly at time of collection) fish revealed increased levels of three chemical families in Lesioned fish including esters, ketones, and nitrogen containing compounds.
Article
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Contamination of the environment with endocrine disrupting chemicals (EDCs) is a major health concern. The presence of estrogenic compounds in water and their deleterious effect are well documented. However, detection and monitoring of other classes of EDCs is limited. Here we utilize a high-throughput live cell assay based on sub-cellular relocalization of GFP-tagged glucocorticoid and androgen receptors (GFP-GR and GFP-AR), in combination with gene transcription analysis, to screen for glucocorticoid and androgen activity in water samples. We report previously unrecognized glucocorticoid activity in 27%, and androgen activity in 35% of tested water sources from 14 states in the US. Steroids of both classes impact body development, metabolism, and interfere with reproductive, endocrine, and immune systems. This prevalent contamination could negatively affect wildlife and human populations.
Article
Ecological risk assessments play an important role in environmental management and decision-making. Although empirical measurements of the effects of habitat changes and chemical exposure are often made at molecular and individual levels, environmental decision-making often requires the quantification of management-relevant, population-level outcomes. In this study, we generalized a modeling framework to evaluate population-level ecological risk of environmental stress and bioactive chemicals. The modeling framework includes (1) a biological model module that incorporates complex and interacting biological and ecological processes, and environmental stochasticity, (2) an effect module that links the impacts of environmental changes and chemical exposure to individual characteristics, and (3) a population module that makes decisions on the choice of population-level properties to best capture the effects and thus to track in the model based on the target species and the research and management interest. This framework is a 3-module procedure that provides an alternative way for researchers to organize, present and communicate the risk assessment modeling studies. To demonstrate this framework, we used a socioeconomically important riverine fish species, smallmouth bass Micropterus dolomieu, as the model species. We developed an individual-based model as the biological model module. We evaluated the impacts of changing water temperature and flow regimes, and the impacts of exposure to estrogenic endocrine disrupting compounds (EEDC) on smallmouth bass populations in the Chesapeake Bay Watershed, USA. Warm summer water temperatures and year-round high flows had the most severe impacts on the smallmouth bass population. An increase in exposure level to EEDC, both year-round and in summer months, substantially reduced population size, spawner and recruit abundance, and the proportion of quality-length individuals. Acute exposure to EEDC was more detrimental to the population than chronic exposure. Acute exposure during spawning season had the most severe impacts. This modeling framework can be extended to other species, environmental factors and chemicals, and can be used to inform management and conservation decisions.
Article
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The Chesapeake Bay is the largest estuary in the United States and its watershed includes river drainages in six states and the District of Columbia. Sportfishing is of major economic interest, however, the rivers within the watershed provide numerous other ecological, recreational, cultural and economic benefits, as well as serving as a drinking water source for millions of people. Consequently, major fish kills and the subsequent finding of estrogenic endocrine disruption (intersex or testicular oocytes and plasma vitellogenin in male fishes) raised public and management concerns. Studies have occurred at various sites within the Bay watershed to document the extent and severity of endocrine disruption, identify risk factors and document temporal and spatial variability. Data from these focal studies, which began in 2004, were used in CART (classification and regression trees) analyses to better identify land use associations and potential management practices that influence estrogenic endocrine disruption. These analyses emphasized the importance of scale (immediate versus upstream catchment) and the complex mixtures of stressors which can contribute to surface water estrogenicity and the associated adverse effects of exposure. Both agricultural (percent cultivated, pesticide application, phytoestrogen cover crops) and developed (population density, road density, impervious surface) land cover showed positive relationships to estrogenic indicators, while percent forest and shrubs generally had a negative association. The findings can serve as a baseline for assessing ongoing restoration and management practices.
Article
A review of the literature published in 2009 on topics relating to the health effects associated with wastewater treatment, reuse, and disposal is presented. The following topics are covered: wastewater management, microbial and chemical contaminants, ecotoxicity and ecotoxicology, contamination of recreational water, water reclamation and reuse, risk assessment and management, industrial wastewater, wastewater treatment plants, and other miscellaneous issues.
Chapter
AbstrAct The occurrence and concentrations of contami-nants of emerging concern (CECs) were investigated in municipal effluents and in marine receiving water. Final effluent from four large Publicly Owned Treatment Works (POTWs), seawater collected near the respective POTW outfall discharges and a refer-ence station were collected quarterly, over a year, and analyzed for 56 CECs. Several CECs were detected in effluents; naproxen, gemfibrozil, atenolol, and TCPP were the compounds most frequently found and with the highest concentrations (>1 µg/L). Gemfibrozil and naproxen had the highest seawater concentrations (0.0009 and 0.0007 µg/L) and also were among the most frequently detected compounds. Effluent dilution factors ranged from >400 to ~1000. Fewer CECs were detected, and at lower concentrations, in seawater collected from the reference station than at the outfall sites. Effluent concentrations for some CECs (e.g., pharmaceuticals) were inversely related to the degree of wastewater treatment. This trend was not found in seawater samples. Few temporal differences were observed in effluent or seawater samples. Effluent CEC concentrations were lower than those currently known for chronic toxicity thresholds. Nevertheless, the evaluation of potential chronic effects for CECs is uncertain because aquatic life toxicity thresholds have only been developed for a few compounds. Additional data are needed to further understand the significance of the CECs presence and concentrations in marine environments.
Article
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The polar organic chemical integrative sampler (POCIS) was relatively recently developed to trap hydrophilic organic micropollutants in aquatic environments.The aim of this article is to compile information from numerous references involving the POCIS in order to discuss the evaluation of time-weighted average concentrations (e.g., calibration methods, sampling rates, performance and reference compounds) and to review critically the different in situ applications (e.g., screening or quantifying micropollutants, and coupling to toxicity tests), application domains (e.g., molecules analyzed, and sampling media) and analytical protocols (e.g., processing, analysis, and exposure duration).
Conference Paper
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Simply and perhaps intuitively defined, endocrine disruption is the abnormal modulation of normal hormonal physiology by exogenous chemicals. In fish, endocrine disruption of the reproductive system has been observed worldwide in numerous species and is known to affect both males and females. Observations of biologically relevant endocrine disruption most commonly occurs near waste water treatment plant outfalls, pulp and paper mills, and areas of high organic loading sometimes associated with agricultural practices. Estrogenic endocrine disrupting chemicals (EEDCs) have received an overwhelmingly dispro-portionate amount of scientific attention compared to other EDCs in recent years. In male fishes, exposure to EEDCs can lead to the induction of testicular oocytes (intersex), measurable plasma vitellogenin protein, altered sex steroid profiles, abnormal spawning behavior, skewed population sex ratios, and lessened reproductive success. Interestingly, contemporary research purports that EDCs modulate aspects of non-reproductive physiology including immune function. Here we present an overview of endocrine disruption in fishes associated with estrogenic compounds, implications of this phenomenon, and examples of EDC related research findings by our group in the Potomac River Watershed, USA.
Article
Signs of disease, such as external lesions, have been prevalent in smallmouth bass throughout the Susquehanna River Basin, USA. Previous targeted chemical studies in this system have identified known persistent organic pollutants, but a common explanatory link across multiple affected sites remains undetermined. A fast and robust extraction method that can be applied to young-of-year fish is needed to effectively screen for target and non-target compounds that may be impacting organism health. The quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction methodology was optimized to perform both targeted and non-targeted chemical analyses from a single extraction of whole young-of-year fish. Comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOFMS) was used for extract analysis. Sample extraction was performed using the solvent ethyl acetate, followed by a two-step cleanup in which samples were frozen for lipid removal and subjected to dispersive solid phase extraction using Florisil. A sample of 21 young-of-year smallmouth bass collected from areas with disease and exhibiting different types of external lesions were evaluated for 233 target compounds. A total of 34 organic contaminants, including polychlorinated biphenyls, brominated diphenyl ethers, organochlorinated pesticides, and personal care products, were detected. Data from this sample set was then analyzed for non-targets. Using the Fisher ratio method and multivariate analysis, an additional 10 significant features were identified specific to either fish with visible lesions or with no visible disease characteristics.
Article
Estrogens and estrogen mimics are commonly found in surface waters and are associated with deleterious effects in fish populations. Impaired fertility and fecundity in fish following chronic exposures to estrogens and estrogen mimics during critical windows in development are well documented. However, information regarding differential reproductive effects of exposure within defined developmental stages remains sparse. In this study, reproductive capacity was assessed in Japanese medaka (Oryzias latipes) after exposure to two concentrations of 17β-estradiol (E2β; 2 ng/L and 50 ng/L) during four distinct stages of development: gonad development, gonad differentiation, development of secondary sex characteristics (SSC) and gonad maturation. Exposure to E2β did not adversely impact survival, hatch success, growth, or genotypic ratios. In contrast, exposure to 50 ng/L E2β during SSC development altered phenotypic ratios and SSC. Exposure to both E2β treatments reduced reproductive capacity (fertility, fecundity) by 7.3-57.4% in adult medaka breeding pairs, with hindrance of SSC development resulting in the largest disruption in breeding capacity (51.6-57.4% decrease) in the high concentration. This study documents differential effects among four critical stages of development and provides insight into factors (window of exposure, exposure concentration and duration of exposure period) contributing to reproductive disruption in fish.
Thesis
Le POCIS (Polar Organic Chemical Integrative Sampler) est un outil d’échantillonnage intégratif alternatif aux techniques d’échantillonnages classiques (ponctuelle ou automatisée) dédié à la mesure de micropolluants organiques relativement hydrophiles dans les eaux. Cet outil permet d’intégrer les concentrations dans le temps (CTWA, Time-Weighted Average Concentration) et, dans certains cas, d’abaisser les limites de quantification. Une revue bibliographique détaillée a montré la forte variabilité des données de performances du POCIS mesurées en laboratoire (notamment les taux d’échantillonnage ou Rs). Cette variabilité résulte en majeure partie de systèmes expérimentaux d’étalonnage différents selon les études et pas toujours renseignés. Dans la littérature, les CTWA obtenues in situ sont comparées aux concentrations obtenues après échantillonnage classique, tel que mis en oeuvre actuellement dans les programmes de surveillance européens ; ces concentrations sont dans la plupart des cas du même ordre de grandeur, même si elles ne représentent pas tout à fait la même information. Avec comme objectif d’obtenir des CTWA les plus justes et robustes possible, nous avons étudié le comportement du POCIS « pharmaceutique » en laboratoire vis-à-vis de 56 micropolluants (hormones, pharmaceutiques, alkylphénols, pesticides, filtre UV), dans un système expérimental d’étalonnage conçu spécifiquement pour contrôler l’ensemble des conditions expérimentales ayant une influence sur les Rs. Nous avons ainsi déterminé 43 Rs robustes et démontré que le POCIS est bien adapté à l’échantillonnage de la plupart des molécules étudiées. De plus, l’allure des cinétiques d’accumulation est expliquée à l’aide des propriétés physico-chimiques des molécules (log D, surface polaire). Cinq homologues deutérés ont été identifiés en tant que PRC (Performance Reference Compounds), c'est-à-dire qu’ils peuvent être utilisés pour corriger les différences de conditions entre le laboratoire et le terrain. Nous avons également comparé le POCIS au Chemcatcher « polaire » en laboratoire et montré qu’en terme de domaine d’application et de performances, le POCIS est mieux adapté pour les micropolluants étudiés. Enfin, nous avons testé la justesse et la robustesse du POCIS lors de deux essais inter-laboratoires (EIL). Le premier EIL, portant sur l’étalonnage de l’outil en laboratoire, a démontré la robustesse de ses performances pour 3 pesticides. Le deuxième EIL in situ a démontré la pertinence du POCIS pour échantillonner des hormones, des pharmaceutiques et des pesticides dans un effluent de station d’épuration. Cette thèse permet d’avancer dans le domaine des connaissances sur l’outil POCIS et de favoriser son application dans le cadre de la directive cadre sur l’eau.
Chapter
The requirements of environmental monitoring programs such as the European Water Framework Directive demand for holistic methodological approaches that address the problems of concern or reasons for sampling unambiguously and specify the objectives of the program and the indicators to be sampled clearly. In this context, the sampling strategies and methods used are of essential importance, because they are an inherent part of the entire analytical and assessment process. In this chapter, the scope, purposes, and requirements of the sampling process are discussed with a focus on water types such as surface water (lakes, streams, and rivers), groundwater, and wastewater regarding to an integrative approach.
Article
Nowadays, pesticides are recognized as having adverse effects on the environment and human health. Monitoring the level of pesticides pollution in aquatic ecosystems involves the establishment of a sampling strategy based on a water spot sampling, followed by a stage of processing and analysis of samples. Furthermore, the concentration of these pollutants can fluctuate over time and therefore a low sampling frequency does not give a representative picture of the real level of pollution and cannot describe faithfully the changing of the quality of the water bodies.Thus, this work focuses on an alternative sampling method based on the use of passive samplers to monitor the level of contamination of surface and groundwater by pesticides. Two types of passive samplers, the polar Chemcatcher and the POCIS (Polar Organic Chemical Intégrative Sampler) were studied in order to compare the effectiveness of these tools for the diagnosis and the monitoring of aquatic pollution by polar pesticides.The first step of the study consists the validation of these two passive samplers, which is based on the laboratory and in-situ calibration of POCIS and polar Chemcatcher, to allow their use as tools for quantitative analysis for the assessment of the average concentration of pesticides in water bodies. The second part of the work is more focused on the applicability of these passive samplers for the study of the spatial distribution of pesticides, the identification of pollution sources and the assessment of pollutants transfer (surface water/groundwater).
Technical Report
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Thousands of chemicals are in daily use for which little is known about their fate and effects on aquatic life. These compounds include pharmaceuticals and personal care products (PPCPs), current use pesticides (CUPs), natural and synthetic hormones, and industrial and commercial compounds (ICCs). Collectively known as contaminants of emerging concern (CECs), many of these compounds are discharged into coastal waters from point and nonpoint sources and have the potential to cause adverse biological effects. There is little information to assess the ecological impacts of CECs, partly because environmental monitoring programs usually focus on priority pollutants such as trace metals, chlorinated pesticides, PCBs, and petroleum hydrocarbons that historically contaminated coastal waters. Concern over the environmental impacts of CECs has increased in recent years as a result of studies showing their common occurrence in waste discharges and receiving waters, and instances of biological effects such as endocrine disruption on fish and wildlife associated with some CECs. Over a billion gallons of treated municipal wastewater are discharged into southern California coastal waters every day. These discharges represent a potentially significant source of CEC exposure for marine life. However, only limited information is available regarding the types, concentrations, and fate of CECs discharged to the Southern California Bight (SCB) from treated wastewater discharges and their potential for ecological impacts. This 2006 Coastal Effects Study was a collaborative effort among SCCWRP, major southern California municipal wastewater agencies, and universities. This study was designed to investigate the impacts of CECs from ocean wastewater discharges on fish in the SCB. Samples of effluent, ocean water, sediment, and fish were collected from multiple locations and analyzed to address six key questions:  What types of CECs are discharged into the SCB from municipal wastewater outfalls?  Are SCB marine life exposed to CECs from municipal wastewater discharges?  Is there evidence of endocrine disruption or other physiological effects in SCB fish?  Are effects on fish related to historical contaminants or current municipal wastewater discharges?  Are specific chemicals responsible for the effects?  Are the physiological effects adversely impacting fish populations or communities?
Article
The Grand River watershed is the largest in southern Ontario and assimilates thirty wastewater treatment plants (WWTP) with varied degrees of treatment. Many WWTPs are unable to effectively eliminate several contaminants of emerging concern (CECs) from final effluent, leading to measurable concentrations in surface waters. Exposures to CECs have reported impacts on oxidative stress measured through antioxidative enzymes (SOD, CAT, GPX). This study focuses on the effects of WWTP effluent on four Etheostoma (Darter) species endemic to the Grand River, by investigating if increased antioxidative response markers are present in darter brains downstream from the effluent outfall compared to an upstream reference site relative to the Waterloo, ON WWTP across two separate years (Oct 2020 and Oct 2021). This was assessed using transcriptional and enzyme analysis of antioxidant enzymes and an enzyme involved in serotonin synthesis, tryptophan hydroxylase (tph). In fall 2020, significant differences in transcript markers were found between sites and sexes in GSD with SOD and CAT showing increased expression downstream, in JD with both sexes showing increased SOD downstream, and an interactive effect for tph in RBD. Changes in transcripts aligned with enzyme activity where interactive effects with sex-related differences were observed in fish collected fall 2020. In contrast, transcripts measured in fall 2021 were increased upstream compared to downstream species in RBD and GSD. This study additionally displayed yearly, species and sex differences in antioxidant responses. Continued investigation on the impacts of CECs in effluent in non-target species is required to better understand WWTP effluent impacts.
Article
Aquatic passive samplers have been extensively tested and deployed in the field over the past two decades. Among these devices is relatively recently developed the Polar Organic Chemical Integrative Sampler (POCIS) for isolation of hydrophilic organic micropollutants in aquatic environment. The use of POCIS allows the measurement of low and fluctuating trace concentrations of such micropollutants, which is often troublesome using classical sampling. In this review, POCIS applications based on numerous articles to assess the suitability of these devices for use in environmental analytics information were summarized. Additionally, the possibilities of using POCIS for the isolation of complex chemical mixtures in order to highlight the high potential of this devices were presented. The types of sorbents used in POCIS, exposure duration and sampling media are juxtapose in this review. Based on the existing literature, attention was paid to both promising opportunities but also to limitations of passive methods.
Article
This review includes works published in the general scientific literature during 2009 on the effects of anthropogenic pollutants on freshwater organisms. It begins with two broad sections: research reviews and broad field studies and surveys. This is followed by reviews of research categorized in sections to reflect the pollutant class. These sections include wastewater, stormwater and non-point source pollution, nutrients, metals, persistent organic pollutants, pharmaceuticals, endocrine disruptors, pesticides, petroleum hydrocarbons and polycyclic aromatic hydrocarbons (PAHs), ionic liquids, and nanomaterials. The final section includes works describing innovations in the field of freshwater pollution research.
Article
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A Basin-wide Index of Benthic Integrity (B-IBI) was developed to uniformly assess aquatic ecosystem health of non-tidal, wadeable streams in the multi-jurisdictional Potomac River basin (US). Multiple datasets were merged and used to identify stream classes and discriminating biological metrics. The index (aggregated metric scores) accurately identified 95% of impaired sites. A jackknife cross-validation procedure confirmed the accuracy of the B-IBI. B-IBI assessments generally compare favorably to basin states’ assessments derived from the same data. A habitat quality matrix which includes an indicator of anthropogenic alterations and disturbances is recommended. The Potomac B-IBI is more useful than existing state-specific indexes for stream health comparisons across jurisdictional boundaries and basin-wide. The Potomac B-IBI can improve understanding of water quality issues in the basin and enhance the abilities of water quality managers to make well-informed decisions concerning the basin's non-tidal waters.
Article
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Estrogens are defined by their ability to induce the proliferation of cells of the female genital tract. The wide chemical diversity of estrogenic compounds precludes an accurate prediction of estrogenic activity on the basis of chemical structure. Rodent bioassays are not suited for the large-scale screening of chemicals before their release into the environment because of their cost, complexity, and ethical concerns. The E-SCREEN assay was developed to assess the estrogenicity of environmental chemicals using the proliferative effect of estrogens on their target cells as an end point. This quantitative assay compares the cell number achieved by similar inocula of MCF-7 cells in the absence of estrogens (negative control) and in the presence of 17 beta-estradiol (positive control) and a range of concentrations of chemicals suspected to be estrogenic. Among the compounds tested, several "new" estrogens were found; alkylphenols, phthalates, some PCB congeners and hydroxylated PCBs, and the insecticides dieldrin, endosulfan, and toxaphene were estrogenic by the E-SCREEN assay. In addition, these compounds competed with estradiol for binding to the estrogen receptor and increased the levels of progesterone receptor and pS2 in MCF-7 cells, as expected from estrogen mimics. Recombinant human growth factors (bFGF, EGF, IGF-1) and insulin did not increase in cell yields. The aims of the work summarized in this paper were a) to validate the E-SCREEN assay; b) to screen a variety of chemicals present in the environment to identify those that may be causing reproductive effects in wildlife and humans; c) to assess whether environmental estrogens may act cumulatively; and finally d) to discuss the reliability of this and other assays to screen chemicals for their estrogenicity before they are released into the environment.
Article
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In vitro recombinant receptor-reporter gene assays have been used to assess and rank the potency of chemicals and complex mixtures suspected of possessing estrogen and (or) aryl hydrocarbon receptor (AhR) mediated activity. The environmental estrogen (E2) bioassay consists of a Gal4-human estrogen receptor chimeric construct (Gal4-HEGO) and a Gal4-regulated luciferase reporter gene (17m5-G-Luc) that have been stably integrated into HeLa cells. The assay exhibits 10-fold induction in luciferase reporter gene activity following treatment with 1 nM 17 beta-estradiol and has a detection limit of approximately 5 pg of 17 beta-estradiol/mL. The AhR bioassay uses Hepa 1c1c7 wild-type cells transiently transfected with a dioxin response element regulated luciferase reporter gene. These assays were used to assess the estrogen and dioxin-like activities of naringenin, atrazine, and simazine and complex mixtures such as pulp and paper mill black liquor and urban air particulates. The activities of these chemicals and complex mixtures are confirmed using the pure antiestrogen ICI 164,384 and in in vitro gel retardation assays. Results of this study demonstrate the utility of in vitro recombinant receptor-reporter gene assays in identifying and assessing the estrogenic and dioxin-like activities of chemicals and complex mixtures.
Article
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During the last three decades, the impact of chemical pollution has focused almost exclusively on the conventional "priority" pollutants, especially those acutely toxic/carcinogenic pesticides and industrial intermediates displaying persistence in the environment. This spectrum of chemicals, however, is only one piece of the larger puzzle in "holistic" risk assessment. Another diverse group of bioactive chemicals receiving comparatively little attention as potential environmental pollutants includes the pharmaceuticals and active ingredients in personal care products (in this review collectively termed PPCPs), both human and veterinary, including not just prescription drugs and biologics, but also diagnostic agents, "nutraceuticals," fragrances, sun-screen agents, and numerous others. These compounds and their bioactive metabolites can be continually introduced to the aquatic environment as complex mixtures via a number of routes but primarily by both untreated and treated sewage. Aquatic pollution is particularly troublesome because aquatic organisms are captive to continual life-cycle, multigenerational exposure. The possibility for continual but undetectable or unnoticed effects on aquatic organisms is particularly worrisome because effects could accumulate so slowly that major change goes undetected until the cumulative level of these effects finally cascades to irreversible change--change that would otherwise be attributed to natural adaptation or ecologic succession. As opposed to the conventional, persistent priority pollutants, PPCPs need not be persistent if they are continually introduced to surface waters, even at low parts-per-trillion/parts-per-billion concentrations (ng-microg/L). Even though some PPCPs are extremely persistent and introduced to the environment in very high quantities and perhaps have already gained ubiquity worldwide, others could act as if they were persistent, simply because their continual infusion into the aquatic environment serves to sustain perpetual life-cycle exposures for aquatic organisms. This review attempts to synthesize the literature on environmental origin, distribution/occurrence, and effects and to catalyze a more focused discussion in the environmental science community.
Article
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Atrazine is the most extensively used herbicide in the United States. Part-per-million concentrations of atrazine have been reported in agricultural runoff. It is detectable in surface waters and precipitation throughout the year, and it has been found in groundwater sources of drinking water. Recent studies indicate that atrazine may be a potent endocrine-disrupting compound in frogs exposed to part-per-billion (microg/L) concentrations. For these reasons, the effects of atrazine (5 and 50 microg/L) on several endpoints related to reproductive fitness were examined in fathead minnows (Pimephales promelas) in a 21-d static exposure. Estradiol (0.5 microg/L) was included as a positive-control treatment. Endpoints examined in adult fish during and after the exposures included survival, egg production, number of spawns, eggs/spawn, relative gonad weight, gonad histology, number of nuptial tubercles, and plasma vitellogenin concentration. Eggs produced during the exposures were hatched and reared in control water. The percentages of embryos fertilized and hatched as well as larval survival were evaluated. Decreasing trends were observed in relative testis weight, testis maturity, and percentage embryo fertilization. These trends suggest that further investigation is warranted, but the differences in these and other endpoints were not statistically significant in the atrazine-exposed fish. Nearly all endpoints concerning fish exposed to estradiol were significantly different from atrazine-exposed fish and control fish. These results suggest that atrazine did not have strong estrogenic effects in adult fathead minnows and did not cause overt reproductive toxicity at environmentally relevant concentrations.
Article
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Lake Shkodra/Skadar is the largest lake in the Balkans region and located on the border between Albania to the south and Montenegro to the north. Because of the wide range of endemic, rare or endangered plant and animal species it supports, Lake Shkodra/Skadar and its extensive associated wetlands are internationally recognised as a site of significance and importance (Ramsar site). In recent years, social and economic changes in both Albania and Montenegro have lead to unprecedented levels of urban and industrial effluent entering the lake. Of particular concern is the increasing input of toxic hydrophobic organic pollutants (HOPs) into the lake and the degree to which these compounds are available for uptake by aquatic biota. Semipermeable membrane devices (SPMDs) have been shown to sample the readily bioavailable fraction (dissolved phase) of waterborne HOPs and in doing so provide relevant data for exposure assessment. The aim of the current study was to use SPMD-based sampling in conjunction with appropriate bioassays and chemical analysis to identify readily bioavailable HOPs in the lake. SPMDs were constructed and deployed at three sites in the Albanian sector and three sites in the Montenegrin sector of Lake Skadar/Shkodra for 21 days. Following the dialytic recovery of target analytes and size exclusion chromatographic clean-up, aliquots of SPMD samples were subjected to GC-MS scan analysis for major components, GC-MS SIM analysis for 16 priority pollutant polycyclic aromatic hydrocarbons (PP-PAHs) and assayed for EROD-inducing, estrogenic and mutagenic potential using rainbow trout liver cells (RTL-W1), the yeast estrogen screen (YES) and the Ames Test, respectively. A total of 39 compounds were tentatively identified in SPMD samples from the six sampling sites. Alkylated PAHs were the most abundant and ubiquitous compounds present along with various sterols and sterol derivatives. Numerous other compounds remain unidentified. 15 of the 16 targeted PP-PAHs were present in samples from one or more of the sampling sites indicating these compounds are both readily bioavailable and widely distributed in Lake Shkodra/Skadar. Total PP-PAH concentrations ranged between 3991 ng/SPMD and 10695 ng/SPMD. Bioassays carried out on SPMD samples revealed significant EROD-inducing and estrogenic potential at five of the six sampling sites indicating toxicologically relevant compounds are readily available for uptake by resident aquatic biota. EROD-inducing potential was positively correlated with targeted PP-PAH concentration (r2 = 0.74). However, comparison of bioassay- and analytically-derived toxicity equivalents revealed targeted PP-PAHs were responsible for less than 0.06% of the total EROD-inducing potential. CONCLUSIONS AND OUTLOOK: The combination of SPMD-based sampling with appropriate bioassays and chemical analysis provided an effective tool for the identification of environmentally relevant waterborne pollutants in Lake Shkodra/Skadar. Our results show that toxicologically relevant HOPs including EROD-inducing and potentially estrogenic compounds are widely distributed in the lake and readily available for uptake by aquatic biota. Our results also suggest that alkylated PAHs rather than parent compounds may be of greater toxicological relevance in the lake. As anthropogenic influences continue to increase, SPMD-based sampling is expected to play a central role in future research concerned with the identification, monitoring and assessment of the risk posed by HOPs to Lake Shkodra/Skadar's aquatic biota.
Article
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An estrogen-inducible bacterial lux-based bioluminescent reporter was developed in Saccharomyces cerevisiae for applications in chemical sensing and environmental assessment of estrogen disruptor activity. The strain, designated S. cerevisiae BLYES, was constructed by inserting tandem estrogen response elements between divergent yeast promoters GPD and ADH1 on pUTK401 (formerly pUA12B7) that constitutively express luxA and luxB to create pUTK407. Cotransformation of this plasmid with a second plasmid (pUTK404) containing the genes required for aldehyde synthesis (luxCDE) and FMN reduction (frp) yielded a bioluminescent bioreporter responsive to estrogen-disrupting compounds. For validation purposes, results with strain BLYES were compared to the colorimetric-based estrogenic assay that uses the yeast lacZ reporter strain (YES). Strains BLYES and YES were exposed to 17beta-estradiol over the concentration range of 1.2 x 10(-8) through 5.6 x 10(-12) M. Calculated 50% effective concentration values from the colorimetric and bioluminescence assays (n = 7) were similar at (4.4 +/- 1.1) x 10(-10) and (2.4 +/- 1.0) x 10(-10) M, respectively. The lower and upper limits of detection for each assay were also similar and were approximately 4.5 x 10(-11) to 2.8 x 10(-9) M. Bioluminescence was observed in as little as 1 h and reached its maximum in 6 h. In comparison, the YES assay required a minimum of 3 days for results. Strain BLYES fills the niche for rapid, high-throughput screening of estrogenic compounds and has the ability to be used for remote, near-real-time monitoring of estrogen-disrupting chemicals in the environment.
Article
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Intersex, or the presence of characteristics of both sexes, in fishes that are normally gonochoristic has been used as an indicator of exposure to estrogenic compounds. In 2003, during health assessments conducted in response to kills and a high prevalence of skin lesions observed in smallmouth bass Micropterus dolomieu in the South Branch of the Potomac River, the presence of immature oocytes within testes was noted. To evaluate this condition, a severity index (0-4) was developed based on the distribution of oocytes within the testes. Using gonad samples collected from 2003 to 2005, the number of histologic sections needed to accurately detect the condition in mature smallmouth bass was statistically evaluated. The reliability of detection depended on the severity index and the number of sections examined. Examining five transverse sections taken along the length of the gonad resulted in a greater than 90% probability of detecting testicular oocytes when the severity index exceeded 0.5. Using the severity index we compared smallmouth bass collected at selected sites within the South Branch during three seasons in 2004. Seasonal differences in severity and prevalence were observed. The highest prevalence and severity were consistently noted during the prespawn-spawning season, when compared with the postspawn season. In 2005, smallmouth bass were collected at selected out-of-basin sites in West Virginia where fish kills and external skin lesions have not been reported, as well as at sites in the Shenandoah River, Virginia (part of the Potomac drainage), where kills and lesions occurred in 2004-2005. The prevalence of testicular oocytes is discussed in terms of human population and agricultural intensity.
Article
Preemergent herbicides and their metabolites, particularly atrazine, deethylatrazine, and metolachlor, persisted from 1989 to 1990 in the majority of rivers and streams in the midwestern United States. In spring, after the application of herbicides, the concentrations of atrazine, alachlor, and simazine were frequently 3-10 times greater than the U.S. Environmental Protection Agency maximum contaminant level (MCL). The concentration of herbicides exceeded the MCLs both singly and in combination. Two major degradation products of atrazine (deisopropylatrazine and deethylatrazine) also were found in many of the streams. The order of persistence of the herbicides and their metabolites in surface water was atrazine > deethylatrazine > metolachlor > alachlor > deisopropylatrazine > cyanazine. Storm runoff collected at several sites exceeded the MCL multiple times during the summer months as a function of stream discharge, with increased concentrations during times of increased streamflow. It is proposed that metabolites of atrazine may be used as indicators of surface-water movement into adjacent alluvial aquifers.
Book
This book summarizes the work of 15 years of research as reported in almost 200 refereed papers, and offers critical discussion of their implications. The authors are pioneers of the passive, integrative sampling approach and developers of globally applied semipermeable membrane devices (SPMDs). The information contained in this book will boost understanding of how passive samplers such as SPMD function by examining basic exchange processes that mediate the concentration of SVOCs in a sampling matrix. The book delineates both the fundamental theory and the modeling techniques needed for full development of new technology, while providing a practical guide for its proper application. Monitors of Organic Chemicals in the Environment:SPMDs will be of interest to all scientists involved in research concerning environmental contaminants. In addition, natural resource managers and regulatory agencies will benefit from an awareness of this technology and its application to monitoring, exposure assessment and mitigation/remediation of environmental pollution. As the passive, integrative sampling approach gains use in the environmental sciences this book has po. © 2006 Springer Science+Business Media, LLC. All rights reserved.
Article
The development of the polar organic chemical integrative sampler (POCIS) provides environmental scientists and policy makers a tool for assessing the presence and potential impacts of the hydrophilic component of these organic contaminants. The POCIS provides a means for determining the time-weighted average (TWA) concentrations of targeted chemicals that can be used in risk assessments to determine the biological impact of hydrophilic organic compounds (HpOCs) on the health of the impacted ecosystem. Field studies have shown that the POCIS has advantages over traditional sampling methods in sequestering and concentrating ultra-trace to trace levels of chemicals over time resulting in increased method sensitivity, ability to detect chemicals with a relatively short residence time or variable concentrations in the water, and simplicity in use. POCIS extracts can be tested using bioassays and can be used in organism dosing experiments for determining toxicological significance of the complex mixture of chemicals sampled. The POCIS has been successfully used worldwide under various field conditions ranging from stagnant ponds to shallow creeks to major river systems in both fresh and brackish water.
Article
Atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) and two degradation products were monitored at seven depths in the soil and vadose zone throughout the growing season in two experimental plots in which corn (Zea mays L.) was grown. The soils in these plots were a Kimo silty clay loam (clayey over loamy, montmorillonitic, mesic, Fluvaquentic Hapludoll) and a Eudora silt loam (coarse, silty, mixed, mesic, Fluventic Hapludoll). The purpose of this field study was to identify and quantify the mobile and persistent degradation products of atrazine that comprise the input, or ''source term,'' to groundwater resulting from the application of atrazine to the soils. The formation of deethylatrazine (2-amino-4-chloro-6-is-opropylamino-s-triazine) and deisopropylatrazine (2-amino-4-chloro-6-ethylamino-s-triazine) was monitored at various depths using suction lysimeters to determine the relative proportions at which these compounds enter the aquifer. Deethylatrazine was the major degradation product of atrazine identified in the soil water and appeared to enter the underlying aquifer at a concentration of 5.0 μg/L, which was greater than the concentration of atrazine entering the aquifer. Deisopropylatrazine also was detected in the soil water, but only in minor concentrations relative to atrazine and deethylatrazine. Because deethylatrazine was the major degradation product in the unsaturated zone, the deethylatrazine-to-atrazine ratio (DAR) may be a good indicator of transport of atrazine through the soil. The hypothesis is proposed that the DAR may be used to distinguish point-source from nonpoint-source contamination of an aquifer.
Article
Preemergent herbicides and their metabolites, particularly atrazine, deethylatrazine, and metolachlor, persisted from 1989 to 1990 in the majority of rivers and streams in the midwestern United States. In spring, after the application of herbicides, the concentrations of atrazine, alachlor, and simazine were frequently 3-10 times greater than the U.S. Environmental Protection Agency maximum contaminant level (MCL). The concentration of herbicides exceeded the MCLs both singly and in combination. Two major degradation products of atrazine (deisopropylatrazine and deethylatrazine) also were found in many of the streams. The order of persistence of the herbicides and their metabolites in surface water was atrazine > deethylatrazine > metolachlor > alachlor > deisopropylatrazine > cyanazine. Storm runoff collected at several sites exceeded the MCL multiple times during the summer months as a function of stream discharge, with increased concentrations during times of increased streamflow. It is proposed that metabolites of atrazine may be used as indicators of surface-water movement into adjacent alluvial aquifers.
Article
Intersex (specifically, testicular oocytes) has been observed in male smallmouth bass (SMB; Micropterus dolomieu) and other centrarchids in the South Branch of the Potomac River, U.S.A., and forks of the Shenandoah River, U.S.A., during the past five years. This condition often is associated with exposure to estrogenic endocrine-disrupting chemicals in some fish species, but such chemicals and their sources have yet to be identified in the Potomac. In an attempt to better understand the plausible causes of this condition, we investigated the reproductive health of bass sampled up- and downstream of wastewater treatment plant (WWTP) effluent point sources on the Potomac River in Maryland, U.S.A. Smallmouth bass were sampled from the Conococheague Creek and the Monocacy River, and largemouth bass (LMB; Micropterus salmoides) were collected near the Blue Plains WWTP on the mainstem of the Potomac River. Chemical analyses of compounds captured in passive samplers at these locations also were conducted. A high prevalence of intersex (82-100%) was identified in male SMB at all sites regardless of collection area. A lower prevalence of intersex (23%) was identified in male LMB collected at the Blue Plains site. When up- and downstream fish were compared, significant differences were noted only in fish from the Conococheague. Differences included condition factor, gonadosomatic index, plasma vitellogenin concentration, and estrogen to testosterone ratio. In general, chemicals associated with wastewater effluent, storm-water runoff, and agriculture were more prevalent at the downstream sampling sites. An exception was atrazine and its associated metabolites, which were present in greater concentrations at the upstream sites. It appears that proximity to effluent from WWTPs may influence the reproductive health of bass in the Potomac watershed, but inputs from other sources likely contribute to the widespread, high incidence of testicular oocytes.
Article
Semipermeable membrane devices (SPMDs) are used with increasing frequency, and throughout the world as samplers of organic contaminants. The devices can be used to detect a variety of lipophilic chemicals in water, sediment/soil, and air. SPMDs are designed to sample nonpolar, hydrophobic chemicals. The maximum concentration factor achievable for a particular chemical is proportional to its octanol-water partition coefficient. Techniques used for cleanup of SPMD extracts for targeted analytes and for general screening by full-scan mass spectrometry do not differ greatly from techniques used for extracts of other matrices. However, SPMD extracts contain potential interferences that are specific to the membrane-lipid matrix. Procedures have been developed or modified to alleviate these potential interferences. The SPMD approach has been demonstrated to be applicable to sequestering and analyzing a wide array of environmental contaminants including organochlorine pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polychlorinated dioxins and dibenzofurans, selected organophosphate pesticides and pyrethroid insecticides, and other nonpolar organic chemicals. We present herein an overview of effective procedural steps for analyzing exposed SPMDs for trace to ultra-trace levels of contaminants sequestered from environmental matrices.
Article
The purpose of this study was to test the hypothesis that acetaminophen would alter an estrogen-regulated process in human cells that express endogenous estrogen receptor alpha and beta (ERalpha and ERbeta). Specifically, the extent to which acetaminophen altered the expression of estrogen-inducible alkaline phosphatase in endometrial adenocarcinoma (Ishikawa) cells and directly interacted with ERbeta and ERalpha was determined. Ishikawa cells were exposed to estradiol and/or to a range of concentrations of acetaminophen for four days, and alkaline phosphatase activity was measured spectrophotometrically. Acetaminophen inhibited both basal and estradiol-induced alkaline phosphatase activity in Ishikawa cells in a concentration-dependent manner. The reduction of Ishikawa cell alkaline phosphatase was not due to direct inhibition of enzyme activity by acetaminophen. Toxic effects of acetaminophen on Ishikawa cells were determined by measuring loss of cellular lactate dehydrogenase to culture medium. High concentrations of acetaminophen (>/=0.5 mM) induced lactate dehydrogenase release from cells and reduced the amount of cellular protein in culture dishes, indicating some acetaminophen-induced reduction of alkaline phosphatase activity might be attributed to toxic effects. However, lower concentrations of acetaminophen significantly reduced alkaline phosphatase activity in the absence of detectable toxicity. Acetaminophen also augmented 4-hydroxy-tamoxifen reduction of alkaline phosphatase activity. Competition binding assays with human ERalpha and ERbeta demonstrated 10(6)-fold molar excess acetaminophen did not directly interact significantly with the ligand-binding domain of either receptor. These studies indicate acetaminophen exerts weak antiestrogenic activity in Ishikawa cells without directly binding ERalpha or ERbeta.
Article
Analyses of triolein-containing semipermeable membrane devices (SPMDs) have sometimes been impeded by interferences caused by impurities endemic to triolein that codialyze with the analytes. Oleic acid and methyl oleate have been the most troublesome of these impurities because of their relatively high concentrations in triolein and because significant residues of both can persist even after size exclusion chromatographic (SEC) fractionation. These residues have also been blamed for false-positive signals during bioindicator testing of SPMD dialysates. To prevent these problems, a simple, cost-effective procedure was developed for purifying triolein destined for use in SPMDs: the bulk triolein is repeatedly (6x) partitioned against methanol. Tests of the procedure show that 14C-oleic acid is completely removed from the triolein. After SEC fractionation, dialysates of standard-size SPMDs made with the purified triolein contain less than 5 microg of methyl oleate as compared to sometimes more than 500 microg for dialysates (also after SEC) of SPMDs made with unpurified triolein. Gas chromatographic analyses with flame ionization and electron capture detection show that the purification treatment also greatly reduces the number and size of peaks caused by unidentified contaminants in the triolein. Microtox basic assay of dialysates of SPMDs shows that those made with the purified triolein have lower acute toxicities than dialysates of SPMDs made with unpurified triolein. Yeast estrogen screen (YES) testing of SPMDs fabricated with unpurified and purified triolein demonstrates that the purification process removes all background estrogenic activity.
Article
During 2001, 76 water samples were collected upstream and downstream of select towns and cities in Iowa during high-, normal- and low-flow conditions to determine the contribution of urban centers to concentrations of pharmaceuticals and other organic wastewater contaminants (OWCs) in streams under varying flow conditions. The towns ranged in population from approximately 2000 to 200,000. Overall, one or more OWCs were detected in 98.7% of the samples collected, with 62 of the 105 compounds being found. The most frequently detected compounds were metolachlor (pesticide), cholesterol (plant and animal sterol), caffeine (stimulant), beta-sitosterol (plant sterol) and 1,7-dimethylxanthine (caffeine degradate). The number of OWCs detected decreased as streamflow increased from low- (51 compounds detected) to normal- (28) to high-flow (24) conditions. Antibiotics and other prescription drugs were only frequently detected during low-flow conditions. During low-flow conditions, 15 compounds (out of the 23) and ten compound groups (out of 11) detected in more than 10% of the streams sampled had significantly greater concentrations in samples collected downstream than in those collected upstream of the urban centers. Conversely, no significant differences in the concentrations were found during high-flow conditions. Thus, the urban contribution of OWCs to streams became progressively muted as streamflow increased.
Article
An integrated approach combining chemistry and biological methods was conducted to assess the toxicity of seven sewage treatment plant effluents. Solid phase concentration procedures were applied to facilitate the study of organic micro pollutants. A chemical analysis was performed by GC/MS. Organic fraction toxicity was determined by using bioassays such as Daphnia magna and Chlorella vulgaris tests and sub-lethal effects were also evaluated by using Salmonella typhimurium Test (mutagenicity), recombinant yeast screen (estrogenicity), and Oryzias latipes embryo-larval test. More than 49 compounds were detected in the organic fraction due to the various inputs of each effluents. The most frequently detected compounds in the effluents were bisphenol A (BPA), octylphenol (OP), 1,2-benzenedicarboxylic acid, bis(2-ethylhexyl) ester (DEHP) and 1,2-benzenedicarboxylic acid, bis(methylpropyl) ester (DBP). Biological assays showed toxicity effects on D. magna tests in all samples, whereas toxicity on C. vulgaris or S. typhimurium tests were not observed. Estrogenicity and teratogenicity were observed in several samples. The cause-effect relationship could not be established given the high chemical complexity of the effluents and the lack of information available on 70% of the detected compounds subsequent to reviewing various data bases. Nevertheless, due to the high chemical variability revealed by STP effluents, bioassay sets may provide a very useful amount of information for detecting potential toxicity risks.
Article
Increasingly it is being realized that a holistic hazard assessment of complex environmental contaminant mixtures requires data on the concentrations of hydrophilic organic contaminants including new generation pesticides, pharmaceuticals, personal care products, and many chemicals associated with household, industrial, and agricultural wastes. To address this issue, we developed a passive in situ sampling device (the polar organic chemical integrative sampler [POCIS]) that integratively concentrates trace levels of complex mixtures of hydrophilic environmental contaminants, enables the determination of their time-weighted average water concentrations, and provides a method of estimating the potential exposure of aquatic organisms to the complex mixture of waterborne contaminants. Using a prototype sampler, linear uptake of selected herbicides and pharmaceuticals with log K(ow)s < 4.0 was observed for up to 56 d. Estimation of the ambient water concentrations of chemicals of interest is achieved by using appropriate uptake models and determination of POCIS sampling rates for appropriate exposure conditions. Use of POCIS in field validation studies targeting the herbicide diuron in the United Kingdom resulted in the detection of the chemical at estimated concentrations of 190 to 600 ng/L. These values are in agreement with reported levels found in traditional grab samples taken concurrently.
Article
Phytoremediation in a simulated crude oil spill was studied with a "minimalistic" approach. The SPMD-TOX paradigm-a miniature passive sorptive device to collect and concentrate chemicals and microscale tests to detect toxicity-was used to monitor over time the bioavailability and potential toxicity of an oil spill. A simulated crude oil spill was initiated on an intertidal freshwater grass-wetland along the St. Lawrence River southwest of Quebec City, Quebec, Canada. Several phytoremediation treatments were investigated; to dissipate and ameliorate the spill, treatments included nutrient amendments with inorganic nitrogen sources (ammonium nitrate and sodium nitrate) and phosphate (super triple phosphate) with and without cut plants, with natural attenuation (no phytoremedial treatment) as a control. Sequestered oil residues were bioavailable in all oil-treated plots in Weeks 1 and 2. Interestingly, the samples were colored and fluoresced under ultraviolet light. In addition, microscale tests showed that sequestered residues were acutely toxic and genotoxic, as well as that they induced hepatic P(450) enzymes. Analysis of these data suggested that polycyclic aromatic hydrocarbons were among the bioavailable residues sequestered. In addition, these findings suggested that the toxic bioavailable fractions of the oil spill and degradation products dissipated rapidly over time because after the second week the water column contained no oil or detectable degradation products in this riverine intertidal wetland. SPMD-TOX revealed no evidence of bioavailable oil products in Weeks 4, 6, 8, and 12. All phytoremediation efforts appeared to be ineffective in changing either the dissipation rate or the ability to ameliorate the oil toxicity. SPMD-TOX analysis of the water columns from these riverine experimental plots profiled the occurrence, dissipation, and influence of phytoremediation on the bioavailability and toxicity of oil products (parent or degradation products).
Article
In order to identify the dominant contributors to estrogenic activity in environmental waters, a comprehensive fractionation method using silica gel column chromatography, combined with recombinant yeast assay for detecting estrogenic activity and with gas chromatography-mass spectrometry for quantifying endocrine disruptors and natural estrogens, was developed. The method was applied to the municipal sewage treatment plant (STP) secondary effluent discharged to the Tamagawa River in Tokyo, Japan, where endocrine disruption was observed in wild carp. The instrumental analysis demonstrated that averaged concentrations of nonylphenol, bisphenol A, estrone (E1), and 17beta-estradiol (E2) were 564 +/- 127, 27 +/- 19, 33 +/- 11, and 4.6 +/- 3.0 ng/L, respectively. Based on the concentration and relative potency of these compounds, the natural estrogens E1 and E2 represented more than 98% of the total estrogen equivalent concentration (EEQ) in the STP effluent, while the contribution of phenolic compounds to total EEQ was less than 2%. Estrogenic activities associated with the dissolved phase of the effluent samples were detected by a recombinant yeast assay. By using silica gel column chromatography, the dissolved phase was separated into several fractions that were subjected to the bioassay. The polar fractions exhibited estrogenic activity. The greatest estrogenic activity was found in a polar fraction containing E1 and E2 and represented 66 to 88% of the total estrogenic activities estimated from the bioassay data. These results lead to the conclusion that E1 and E2 were the dominant environmental estrogens in the STP effluent, but a significant contribution to estrogenic activities stems from unidentified components in the effluents.
Article
Common carp (Cyprinus carpio) were treated in aquatic mesocosms with a single pulse of the herbicides atrazine or alachlor to study the bioavailability and biological activity of these herbicides using molecular indicators: Liver vitellogenin gene expression in male fish for estrogenic activity, liver cytochrome P4501A1 gene expression, and DNA damage in blood cells using the single-cell gel electrophoresis method. Both alachlor and atrazine showed dose-related increases in DNA strand breaks at environmentally relevant concentrations (<100 ppb). Gene expression indicators showed that neither herbicide had estrogenic activity in the carp, whereas atrazine at concentrations as low as 7 ppb induced cytochrome P4501A1. These results support the study of molecular indicators for exposure in surrogate ecosystems to gauge relevant environmental changes following herbicide treatments.
Article
In this paper we describe the construction and use of a set of bioluminescent yeast strains for the detection of compounds that can affect androgen or estrogen receptor mediated hormonal signalling. The set includes Saccharomyces cerevisiae strains expressing human androgen receptor (AR), estrogen receptor alpha (ERalpha) or estrogen receptor beta (ERbeta), along with firefly luciferase controlled by a respective hormone responsive promoter. A constitutively luminescent strain was included in the set for determining the cytotoxicity of the sample. Yeast cells were incubated with pure chemicals or complex samples for 2.5 h, after which the signal could be detected from the cell-sample mixture after simply adding the D-luciferin substrate. The assays could be completed in one day and they required no cell lysis or centrifugation steps, which makes them suitable for high-throughput analysis of samples. Due to a short incubation time the assays are directly applicable to different sample matrices, requiring no pretreatment of the samples. The assays were used to assess the hormonal activity in moisturizing lotions as an example of a complex sample matrix known to contain endocrine disrupting chemicals. Six out of eight tested moisturisers showed high estrogenic activity, whereas no androgenic activity was observed in the samples.
Article
Four water samples collected using standard depth and width water-column sampling methodology were compared to an innovative passive, in situ, sampler (the polar organic chemical integrative sampler or POCIS) for the detection of 96 organic wastewater-related contaminants (OWCs) in a stream that receives agricultural, municipal, and industrial wastewaters. Thirty-two OWCs were identified in POCIS extracts whereas 9-24 were identified in individual water-column samples demonstrating the utility of POCIS for identifying contaminants whose occurrence are transient or whose concentrations are below routine analytical detection limits. Overall, 10 OWCs were identified exclusively in the POCIS extracts and only six solely identified in the water-column samples, however, repetitive water samples taken using the standard method during the POCIS deployment period required multiple trips to the sampling site and an increased number of samples to store, process, and analyze. Due to the greater number of OWCs detected in the POCIS extracts as compared to individual water-column samples, the ease of performing a single deployment as compared to collecting and processing multiple water samples, the greater mass of chemical residues sequestered, and the ability to detect chemicals which dissipate quickly, the passive sampling technique offers an efficient and effective alternative for detecting OWCs in our waterways for wastewater contaminants.
Article
Passive sampling methodologies were used to conduct a chemical and toxicologic assessment of organic contaminants in the surface waters of three geographically distinct agricultural watersheds. A selection of current-use agrochemicals and persistent organic pollutants, including polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and organochlorine pesticides, were targeted using the polar organic chemical integrative sampler (POCIS) and the semipermeable membrane device passive samplers. In addition to the chemical analysis, the Microtox assay for acute toxicity and the yeast estrogen screen (YES) were conducted as potential assessment tools in combination with the passive samplers. During the spring of 2004, the passive samplers were deployed for 29 to 65 d at Leary Weber Ditch, IN; Morgan Creek, MD; and DR2 Drain, WA. Chemical analysis of the sampler extracts identified the agrochemicals predominantly used in those areas, including atrazine, simazine, acetochlor, and metolachlor. Other chemicals identified included deethylatrazine and deisopropylatrazine, trifluralin, fluoranthene, pyrene, cis- and trans-nonachlor, and pentachloroanisole. Screening using Microtox resulted in no acutely toxic samples. POCIS samples screened by the YES assay failed to elicit a positive estrogenic response.
Atrazine effects on biomarker of reproduc-tive function in fathead minnow (Pimephales promelas) and Jap-anese medaka (Oryzias latipes). Abstracts, 27th Annual Meeting of SETAC North America
  • Pappoulias Dm Jj Whyte
  • Villeneuve Dl
  • Ankley Gt
  • Tillitt
  • De
Richter CA, Pappoulias DM, Whyte JJ, Villeneuve DL, Ankley GT, Tillitt DE. 2006. Atrazine effects on biomarker of reproduc-tive function in fathead minnow (Pimephales promelas) and Jap-anese medaka (Oryzias latipes). Abstracts, 27th Annual Meeting of SETAC North America, Montreal, PQ, Canada, November 5–9, p 167.
Endocrine disruption in fish: Assess-ment of recent research and results. NOAA Technical Memoran-dum NOS NCCOS CCMA 149. National Oceanic and Atmo-spheric Administration, National Ocean Service, Center for Coastal Monitoring and Assessment
  • Pait
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  • Nelson
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Pait AS, Nelson JO. 2002. Endocrine disruption in fish: Assess-ment of recent research and results. NOAA Technical Memoran-dum NOS NCCOS CCMA 149. National Oceanic and Atmo-spheric Administration, National Ocean Service, Center for Coastal Monitoring and Assessment, Silver Spring, MD, USA.
Investigation of organic chemicals potentially responsible for mortality and intersex in fish of the North Fork of the Shenandoah River, Virginia, during spring of 2007. Open-File
  • Alvarez Da
  • Wl Cranor
  • Perkins
  • Sd
  • Schroeder
  • Vl
  • S Werner
  • Et Furlong
  • Holmes
Alvarez DA, Cranor WL, Perkins SD, Schroeder VL, Werner S, Furlong ET, Holmes J. 2008. Investigation of organic chemicals potentially responsible for mortality and intersex in fish of the North Fork of the Shenandoah River, Virginia, during spring of 2007. Open-File Report 2008-1093. U.S. Geological Survey, Res-ton, VA.
Investigation of organic chemicals potentially responsible for mortality and intersex in fish of the North Fork of the Shenandoah River, Virginia, during spring of
  • Da Alvarez
  • Wl Cranor
  • Sd Perkins
  • Vl Schroeder
  • S Werner
  • Et Furlong
  • J Holmes
Alvarez DA, Cranor WL, Perkins SD, Schroeder VL, Werner S, Furlong ET, Holmes J. 2008. Investigation of organic chemicals potentially responsible for mortality and intersex in fish of the North Fork of the Shenandoah River, Virginia, during spring of 2007. Open-File Report 2008-1093. U.S. Geological Survey, Reston, VA.
Atrazine effects on biomarker of reproductive function in fathead minnow (Pimephales promelas) and Japanese medaka (Oryzias latipes). Abstracts
  • Ca Richter
  • Dm Pappoulias
  • Jj Whyte
  • Dl Villeneuve
  • Gt Ankley
  • De Tillitt
Richter CA, Pappoulias DM, Whyte JJ, Villeneuve DL, Ankley GT, Tillitt DE. 2006. Atrazine effects on biomarker of reproductive function in fathead minnow (Pimephales promelas) and Japanese medaka (Oryzias latipes). Abstracts, 27th Annual Meeting of SETAC North America, Montreal, PQ, Canada, November 5–9, p 167.