Geology topics

David A. Alvarez

Publications and source records attributed to David A. Alvarez.

At least 37 records · Page 2Linked to original sources

USGS2020

Factors affecting sampling strategies for design of an effects‐directed analysis for endocrine‐active chemicals

Effects‐directed analysis (EDA) is an important tool for identifying unknown bioactive components in a complex mixture. Such an analysis of endocrine‐active chemicals (EACs) from water sources has promising regulatory implications but also unique logistical challenges. We propose a conceptual EDA (framework) based on a critical review of EDA literature and concentrations of common EACs in waste and surface waters. Required water volumes for identification of EACs under this EDA framework were estimated based on bioassay performance (in vitro and in vivo bioassays), limits of quantification by mass spectrometry (MS), and EAC water concentrations. Sample volumes for EDA across the EACs showed high variation in the bioassay detectors, with genistein, bisphenol A, and androstenedione requiring very high sample volumes and ethinylestradiol and 17β‐trenbolone requiring low sample volumes. Sample volume based on the MS detector was far less variable across the EACs. The EDA framework equation was rearranged to calculate detector “thresholds,” and these thresholds were compared with the literature EAC water concentrations to evaluate the feasibility of the EDA framework. In the majority of instances, feasibility of the EDA was limited by the bioassay, not MS detection. Mixed model analysis showed that the volumes required for a successful EDA were affected by the potentially responsible EAC, detection methods, and the water source type, with detection method having the greatest effect on the EDA of estrogens and androgens. The EDA framework, equation, and model we present provide a valuable tool for designing a successful EDA.

Environmental Toxicology and Chemistry↗

USGS2020

Urban stream syndrome and contaminant uptake in salamanders of Central Texas

We studied the ecological health of springs experiencing varying levels of urban development to assess impacts to rare endemic salamanders ( Eurycea spp.) of Central Texas. We evaluated measures of invertebrate species richness, water quality, and contaminant uptake by salamanders to determine how springs and their inhabitants were being affected by urban growth and changing land-use patterns. The number of environmental contaminants present and concentrations of contaminants increased in both water and salamander tissues with increasing age of the developments (i.e., years postconstruction) and increasing levels of impervious cover (e.g., roads) in urban watersheds compared with nondeveloped sites. We conclude that urbanization and associated increases in pollutant loading in watersheds can result in a loss of spring biodiversity and the accumulation of persistent and potentially toxic pollutants in salamanders. Although we detected generally low levels of pollutants, the altered water quality and invertebrate composition observed at springs, coupled with the changing hydrology and chronic contaminant exposure inherent in urban landscapes, is cause for concern, with potential implications for the long-term health, survival, and recovery of salamanders.

Texas↗

USGS2020

Evaluation of legacy and emerging organic chemicals using passive sampling devices on the North Branch Au Sable River near Lovells, Michigan, June 2018

The North Branch Au Sable River, located in the northern lower peninsula of Michigan near Lovells, Michigan, has historically been known for its brook trout ( Salvelinus fontinalis ) and its status as a blue ribbon trout stream; however, within the past few decades, there has been a decline in fish population. The objectives of this study were to assess if concentrations of organic chemicals were present in quantities in the North Branch Au Sable River that may potentially harm aquatic species and to establish current baseline concentrations of organic chemicals against which future data can be compared. Passive sampling technology was used to collect information on the concentration, occurrence, transport, and fate of organic chemicals; these samplers absorb dissolved organic chemicals in the river over several weeks, as the timing and intensity of pesticide applications and the frequency of storm events and irrigation can cause fluctuations in organic chemical loading to surface waters. The chemical classes investigated as part of this study included pesticides (both legacy [organochlorine] and current use), polychlorinated biphenyls, polybrominated diphenyl ethers (PBDEs), and polycyclic aromatic hydrocarbons (PAHs). Passive samplers, including semipermeable membrane devices and polar organic chemical integrative samplers, were deployed at four locations along the North Branch Au Sable River, near Lovells, Mich., in June 2018 for a total of 28 days. Several organic chemicals were detected in the North Branch Au Sable River at low concentrations. Organic chemicals were detected at every sampling location on the North Branch Au Sable River; however, not all chemicals were detected at every location. The highest number of organic chemicals were detected at the most downstream sampling site (North Branch Au Sable River at Kellogg's Bridge), and the lowest number of organic chemicals were detected at the next site upstream (North Branch Au Sable River at Twin Bridge Road). The organic contaminants most frequently detected at all sampling locations include the legacy pesticides pentachloroanisole, trans -chlordane, p,p'-dichlorodiphenyldichloroethylene, and p,p'-dichlorodiphenyltrichloroethane; the PBDE PBDE-28; and the PAHs 2-methylphenanthrene and perylene. Organic chemical concentrations detected on the North Branch Au Sable River were below almost all water-quality benchmarks included in this report. However, low concentrations of organic chemicals may still pose a risk to aquatic organisms and throughout the trophic hierarchy because of low-dose additive and synergistic mixture effects, transgenerational effects, and a lack of established water-quality benchmarks for many organic chemicals. This report provides data on the current (2018) state of the North Branch Au Sable River and provided a baseline of organic contaminant data against which future data on the North Branch Au Sable River can be evaluated.

Michigan↗

USGS2020

Petroleum hydrocarbons in semipermeable membrane devices deployed in the Northern Gulf of Mexico and Florida keys following the Deepwater Horizon incident

The Deepwater Horizon (DWH) oil spill from April to July of 2010 contaminated Gulf of Mexico waters through release of an estimated 4.1 × 10 6 barrels of oil. Beginning in June of 2010, semipermeable membrane devices (SPMDs) were deployed near areas with sensitive marine habitats (Alabama Alps and Western Shelf) potentially exposed to that oil. Elevated TPAH50 concentrations, flux rates and similarity of histograms and diagnostic ratios for polycyclic aromatic hydrocarbons (PAH) from SPMDs to weathered floating oil collected during the DWH spill indicates the Alabama Alps habitats were affected. While not affected by oil from the DWH spill, the temporal pattern of PAH contamination of SPMDs deployed near the Western Shelf between July 2010 and March 2011 could indicate prevailing currents affected contaminant transport to the Western Shelf Area (East and West Flower Garden, Sonnier, and Stetson Banks) from non-DWH sources, including oil and gas exploration, shipping, and Mississippi River effluent.

Florida↗

USGS2020

Wastewater-based epidemiology pilot study to examine drug use in the Western United States

The extent of prescription and illicit drug abuse in geographically isolated rural and micropolitan communities in the intermountain western United States (US) has not been well tracked. The goal of this pilot study was to accurately measure drug dose consumption rates (DCR) between two select populations, normalize the data and compare the DCRs to similar communities. To learn about patterns of drug abuse between the two disparate communities, we used the emergent field of wastewater-based epidemiology (WBE). A rapid, quantitative and systematic process for the determination of multiple classes of prescribed and illicit drugs was applied to influent wastewater samples. Influent samples were collected over the course of three months (April to June 2019) at two wastewater treatment plants representing a small urban and a rural community. Collection of sewage influent included 24-h composite samples and the use of polar organic chemical integrative samplers (POCIS), time-weighted samplers. Using the results from the composite sampling data, DCRs per 1000 population could be calculated from the concentration data and the use of excretion correction factors. The following 18 compounds: amphetamine, methamphetamine, MDA, MDMA, morphine, 6-acetylmorphine, methadone, EDDP, codeine, benzoylecgonine, hydrocodone, hydromorphone, oxycodone, noroxycodone, ketamine, fluoxetine, tramadol, and ritalinic acid; represent a subset of the targeted analytes that were consistently measured at detectable concentration levels, and present at both sites. Following normalization of the drug measurements to influent flow rates and per capita, the small urban community demonstrated greater collective excretion rates (CER) than the rural community, with the exceptions of amphetamine and methamphetamine.

Science of the Total Environment↗

USGS2019

Assessment of polycyclic aromatic hydrocarbon concentrations in southern Lake Powell, Glen Canyon National Recreation Area, Arizona and Utah, 2016–17

Polycyclic aromatic hydrocarbon contamination related to boat use is one of the most important water-quality issues affecting Lake Powell. High concentrations of polycyclic aromatic hydrocarbons in water are common around marinas and other areas with extensive motorboat activity because of releases of uncombusted or partially combusted oil and gasoline from boat engines. The fate of these compounds in Lake Powell is of serious environmental concern because of their toxicity and carcinogenicity and their moderate persistence once they enter the aquatic ecosystem. In 2016–17, the U.S. Geological Survey (USGS) assessed the presence and concentrations of polycyclic aromatic hydrocarbons in Lake Powell at seven sites where concentrations have historically been elevated and one site where concentrations have historically been relatively low. Semipermeable membrane devices were used to collect samples that represent time-weighted averages of polycyclic aromatic hydrocarbon concentrations in water over one-month deployment periods. Samples were collected from the epilimnion of the lake at each of the eight sampling sites during two periods of relatively high boat use (summer), and one period of relatively low boat use (spring). Twenty-eight out of 33 polycyclic aromatic hydrocarbons analyzed were detected in Lake Powell during the three sampling events. During the two summer sampling events, concentrations were generally higher, and more compounds were detected, than during the spring sampling event. Twenty-two of the polycyclic aromatic hydrocarbons analyzed in 2016–17 had previously been analyzed by the USGS in the summer of 2010 at the same 8 sites using the same collection method. Eleven of 22 compounds were detected in the summer 2010, summer 2016, and summer 2017 sampling events, and 1 was detected in the summer 2010 and summer 2017 samplings, but not in the summer 2016 sampling event. During both the current and previous sampling events, concentrations were generally higher, and more compounds were detected, at the high-use marina sites located most downstream on the lake. The consistent presence of a wide range of polycyclic aromatic hydrocarbons in the water of Lake Powell indicates chronic and (or) recent anthropogenic sources of contamination. The results from this study will provide the National Park Service with information necessary to determine if the current regulations on emission standards for personal watercraft used on Lake Powell are effective in lowering polycyclic aromatic hydrocarbon concentrations in the lake.

Arizona, Utah↗

USGS2019

Multiple approaches to surface water quality assessment provide insight for small streams experiencing oil and natural gas development

Historic, current, and future oil and natural gas development can affect water quality in streams flowing through developed areas. We compared small stream drainages in a semi-arid landscape with varying amounts of disturbance from oil and natural gas development to examine potential effects of this development on surface water quality. We used physical, chemical, and biological approaches to assess water quality and found several potential avenues of degradation. Surface disturbance likely contributed to elevated suspended sediment concentrations and spill history likely led to elevated stream polycyclic aromatic hydrocarbon concentrations. In combination, these environmental stressors could explain the loss of sensitive aquatic macroinvertebrate groups at sites highly affected by oil and natural gas development. Our results provide insight into advantages and disadvantages of approaches for assessing surface water quality in areas affected by oil and natural gas development.

Wyoming↗

USGS2018

Chronic toxicity of 4-nonylphenol to two unionid mussels in water-only exposures

Limited studies indicate that mussels are generally insensitive to organic chemicals; however, these studies were conducted in acute or short-term exposures, and little is known about the chronic sensitivity of mussels to organic chemicals. We evaluated the chronic (28 days) toxicity of 4-nonylphenol (4-NP) to two commonly tested species of mussels: fatmucket ( Lampsilis siliquoidea ) and rainbow mussel (Villosa iris). By the end of the 28 days chronic exposures, mean survival was ≥93% in all treatments, but the mean dry weight and biomass of mussels at the highest exposure concentrations were significantly reduced relative to the control. The 20% effect concentrations were similar between the two species. When compared to all other tested species, fatmucket and rainbow mussels are among the top four most sensitive species to 4-NP. However, U.S. Environmental Protection Agency chronic water quality criterion of 6.6 μg 4-NP/L should protect the two mussel species.

Bulletin of Environmental Contamination and Toxico↗

USGS2018

Risk factors associated with mortality of age-0 Smallmouth Bass in the Susquehanna River basin, Pennsylvania

Evidence of disease and mortalities of young of the year (age‐0) Smallmouth Bass Micropterus dolomieu has occurred during the late spring and summer in many parts of the Susquehanna River watershed since 2005. To better understand contributing factors, fish collected from multiple areas throughout the watershed as well as out‐of‐basin reference populations (Allegheny and Delaware River basins; experimental ponds, Kearneysville, West Virginia) were examined grossly and histologically for abnormalities. Tissue contaminant concentrations were determined from whole‐body homogenates, and water contaminant concentrations were estimated using time‐integrated passive samplers at selected sites. Observed or isolated pathogens included bacteria, predominantly motile Aeromonas spp. and Flavobacterium columnare ; largemouth bass virus, and parasites, including trematode metacercariae, cestodes, and the myxozoan Myxobolus inornatus . Although these pathogens were found in age‐0 Smallmouth Bass from multiple sites, no one pathogen was consistently associated with mortality. Chemicals detected in tissue included polychlorinated biphenyl (PCB) congeners, organochlorine, and current‐use pesticides. Pyraclostrobin, PCB congeners 170 and 187, cis ‐chlordane and trans ‐nonachlor were detected in all Susquehanna watershed samples but rarely in samples from the reference site. The findings support the idea that there is no single cause for disease of age‐0 Smallmouth Bass; rather the cumulative effects of co‐infections and potential immunomodulation by environmental stressors during a sensitive developmental life stage may lead to mortality. Identifying the most important risk factors will be necessary for more in‐depth analyses of individual stressors and better management of the habitat and fish populations.

Pennsylvania↗

USGS2018

Contaminants of emerging concern presence and adverse effects in fish: A case study in the Laurentian Great Lakes

The Laurentian Great Lakes are a valuable natural resource that is affected by contaminants of emerging concern (CECs), including sex steroid hormones, personal care products, pharmaceuticals, industrial chemicals, and new generation pesticides. However, little is known about the fate and biological effects of CECs in tributaries to the Great Lakes. In the current study, 16 sites on three rivers in the Great Lakes basin (Fox, Cuyahoga, and Raquette Rivers) were assessed for CEC presence using polar organic chemical integrative samplers (POCIS) and grab water samplers. Biological activity was assessed through a combination of in vitro bioassays (focused on estrogenic activity) and in vivo assays with larval fathead minnows. In addition, resident sunfish, largemouth bass, and white suckers were assessed for changes in biological endpoints associated with CEC exposure. CECs were present in all water samples and POCIS extracts. A total of 111 and 97 chemicals were detected in at least one water sample and POCIS extract, respectively. Known estrogenic chemicals were detected in water samples at all 16 sites and in POCIS extracts at 13 sites. Most sites elicited estrogenic activity in bioassays. Ranking sites and rivers based on water chemistry, POCIS chemistry, or total in vitro estrogenicity produced comparable patterns with the Cuyahoga River ranking as most and the Raquette River as least affected by CECs. Changes in biological responses grouped according to physiological processes, and differed between species but not sex. The Fox and Cuyahoga Rivers often had significantly different patterns in biological response Our study supports the need for multiple lines of evidence and provides a framework to assess CEC presence and effects in fish in the Laurentian Great Lakes basin.

Environmental Pollution↗

USGS2018

Temporal evaluation of estrogenic endocrine disruption markers in smallmouth bass (Micropterus dolomieu) reveals seasonal variability in intersex

A reconnaissance project completed in 2009 identified intersex and elevated plasma vitellogenin in male smallmouth bass inhabiting the Missisquoi River, VT. In an attempt to identify the presence and seasonality of putative endocrine disrupting chemicals or other factors associated with these observations, a comprehensive reevaluation was conducted between September 2012 and June 2014. Here, we collected smallmouth bass from three physically partitioned reaches along the river to measure biomarkers of estrogenic endocrine disruption in smallmouth bass. In addition, polar organic chemical integrative samples (POCIS) were deployed to identify specific chemicals associated with biological observations. We did not observe biological differences across reaches indicating the absence of clear point source contributions to the observation of intersex. Interestingly, intersex prevalence and severity decreased in a stepwise manner over the timespan of the project. Intersex decreased from 92.8% to 28.1%. The only significant predictor of intersex prevalence was year of capture, based on logistic regression analysis. The mixed model of fish length and year-of-capture best predicted intersex severity. Intersex severity was also significantly different across late summer and early spring collections indicating seasonal changes in this metric. Plasma vitellogenin and liver vitellogenin Aa transcript abundance in males did not indicate exposure to estrogenic endocrine disrupting chemicals at any of the four sample collections. Analysis of chemicals captured by the POCIS as well as results of screening discrete water samples or POCIS extracts did not indicate the contribution of appreciable estrogenic chemicals. It is possible that unreported changes in land-use activity have ameliorated the problem, and our observations indicate recovery. Regardless, this work clearly emphasizes that single, snap shot sampling for intersex may not yield representative data given that the manifestation of this condition within a population can change dramatically over time.

Vermont↗

USGS2017

Complex mixtures of Pesticides in Midwest U.S. streams indicated by POCIS time-integrating samplers

The Midwest United States is an intensely agricultural region where pesticides in streams pose risks to aquatic biota, but temporal variability in pesticide concentrations makes characterization of their exposure to organisms challenging. To compensate for the effects of temporal variability, we deployed polar organic chemical integrative samplers (POCIS) in 100 small streams across the Midwest for about 5 weeks during summer 2013 and analyzed the extracts for 227 pesticide compounds. Analysis of water samples collected weekly for pesticides during POCIS deployment allowed for comparison of POCIS results with periodic water-sampling results. The median number of pesticides detected in POCIS extracts was 62, and 141 compounds were detected at least once, indicating a high level of pesticide contamination of streams in the region. Sixty-five of the 141 compounds detected were pesticide degradates. Mean water concentrations estimated using published POCIS sampling rates strongly correlated with means of weekly water samples collected concurrently, however, the POCIS-estimated concentrations generally were lower than the measured water concentrations. Summed herbicide concentrations (units of ng/POCIS) were greater at agricultural sites than at urban sites but summed concentrations of insecticides and fungicides were greater at urban sites. Consistent with these differences, summed concentrations of herbicides correlate to percent cultivated crops in the watersheds and summed concentrations of insecticides and fungicides correlate to percent urban land use. With the exception of malathion concentrations at nine sites, POCIS-estimated water concentrations of pesticides were lower than aquatic-life benchmarks. The POCIS provide an alternative approach to traditional water sampling for characterizing chronic exposure to pesticides in streams across the Midwest region.

Environmental Pollution↗

USGS2017

Baseline aquatic contamination and endocrine status in a resident fish of Biscayne National Park

Surface water, sediment, and fish from Biscayne Bay, coastal wetlands adjacent to the Bay, and canals discharging into the Bay were sampled for determination of baseline contamination in Biscayne National Park. While the number of contaminants detected in canal waters was greater during the wet season than the dry season, no seasonal difference was evident for Biscayne Bay or coastal wetland waters. Estrogen equivalency (as 17β-estradiol equivalents), as predicted by the Yeast Estrogen Screen, for extracts of passive water samplers deployed in canals and wetlands was elevated during the wet relative to the dry season. Generally, contamination in water, sediments, and fish was greater in the canals than in Biscayne Bay and the wetlands. Guideline levels for sediment contaminant were exceeded most frequently in canals relative to the coastal wetlands and the Bay. Further investigation is necessary to better understand the impact of contaminants in Biscayne National Park.

Florida↗

USGS2016

Acute sensitivity of a broad range of freshwater mussels to chemicals with different modes of toxic action

Freshwater mussels, one of the most imperiled groups of animals in the world, are generally underrepresented in toxicity databases used for the development of ambient water quality criteria and other environmental guidance values. Acute 96-h toxicity tests were conducted to evaluate the sensitivity of 5 species of juvenile mussels from 2 families and 4 tribes to 10 chemicals (ammonia, metals, major ions, and organic compounds) and to screen 10 additional chemicals (mainly organic compounds) with a commonly tested mussel species, fatmucket ( Lampsilis siliquoidea ). In the multi-species study, median effect concentrations (EC50s) among the 5 species differed by a factor of ≤2 for chloride, potassium, sulfate, and zinc; a factor of ≤5 for ammonia, chromium, copper, and nickel; and factors of 6 and 12 for metolachlor and alachlor, respectively, indicating that mussels representing different families or tribes had similar sensitivity to most of the tested chemicals, regardless of modes of action. There was a strong linear relationship between EC50s for fatmucket and the other 4 mussel species across the 10 chemicals ( r 2 = 0.97, slope close to 1.0), indicating that fatmucket was similar to other mussel species; thus, this commonly tested species can be a good surrogate for protecting other mussels in acute exposures. The sensitivity of juvenile fatmucket among different populations or cultured from larvae of wild adults and captive-cultured adults was also similar in acute exposures to copper or chloride, indicating captive-cultured adult mussels can reliably be used to reproduce juveniles for toxicity testing. In compiled databases for all freshwater species, 1 or more mussel species were among the 4 most sensitive species for alachlor, ammonia, chloride, potassium, sulfate, copper, nickel, and zinc; therefore, the development of water quality criteria and other environmental guidance values for these chemicals should reflect the sensitivity of mussels. In contrast, the EC50s of fatmucket tested in the single-species study were in the high percentiles (>75th) of species sensitivity distributions for 6 of 7 organic chemicals, indicating mussels might be relatively insensitive to organic chemicals in acute exposures.

Environmental Toxicology and Chemistry↗

USGS2016

Year-round monitoring of contaminants in Neal and Rogers Creeks, Hood River Basin, Oregon, 2011-12, and assessment of risks to salmonids

Pesticide presence in streams is a potential threat to Endangered Species Act listed salmonids in the Hood River basin, Oregon, a primarily forested and agricultural basin. Two types of passive samplers, polar organic chemical integrative samplers (POCIS) and semipermeable membrane devices (SPMDs), were simultaneously deployed at four sites in the basin during Mar. 2011–Mar. 2012 to measure the presence of pesticides, polybrominated diphenyl ethers (PBDEs), and polychlorinated biphenyls (PCBs). The year-round use of passive samplers is a novel approach and offers several new insights. Currently used pesticides and legacy contaminants, including many chlorinated pesticides and PBDEs, were present throughout the year in the basin’s streams. PCBs were not detected. Time-weighted average water concentrations for the 2-month deployment periods were estimated from concentrations of chemicals measured in the passive samplers. Currently used pesticide concentrations peaked during spring and were detected beyond their seasons of expected use. Summed concentrations of legacy contaminants in Neal Creek were highest during July–Sept., the period with the lowest streamflows. Endosulfan was the only pesticide detected in passive samplers at concentrations exceeding Oregon or U.S. Environmental Protection Agency water-quality thresholds. A Sensitive Pesticide Toxicity Index (SPTI) was used to estimate the relative acute potential toxicity among sample mixtures. The acute potential toxicity of the detected mixtures was likely greater for invertebrates than for fish and for all samples in Neal Creek compared to Rogers Creek, but the indices appear to be low overall (<0.1). Endosulfans and pyrethroid insecticides were the largest contributors to the SPTIs for both sites. SPTIs of some discrete (grab) samples from the basin that were used for comparison exceeded 0.1 when some insecticides (azinphos methyl, chlorpyrifos, malathion) were detected at concentrations near or exceeding acute water-quality thresholds. Early life stages and adults of several sensitive fish species, including salmonids, are present in surface waters of the basin throughout the year, including during periods of peak estimated potential toxicity. Based on these data, direct toxicity to salmonids from in-stream pesticide exposure is unlikely, but indirect impacts (reduced fitness due to cumulative exposures or negative impacts to invertebrate prey populations) are unknown.

Oregon↗

USGS2016

Exposure to the contraceptive progestin, gestodene, alters reproductive behavior, arrests egg deposition, and masculinizes development in the fathead minnow ( Pimephales promelas )

Endogenous progestogens and pharmaceutical progestins enter the environment through wastewater treatment plant effluent and agricultural field runoff. Lab studies demonstrate strong, negative exposure effects of these chemicals on aquatic vertebrate reproduction. Behavior can be a sensitive, early indicator of exposure to environmental contaminants associated with altered reproduction yet is rarely examined in ecotoxicology studies. Gestodene is a human contraceptive progestin and a potent activator of fish androgen receptors. Our objective was to test the effects of gestodene on reproductive behavior and associated egg deposition in the fathead minnow. After only 1 day, males exposed to ng/L of gestodene were more aggressive and less interested in courtship and mating, and exposed females displayed less female courtship behavior. Interestingly, 25% of the gestodene tanks contained a female that drove the male out of the breeding tile and displayed male-typical courtship behaviors toward the other female. Gestodene decreased or arrested egg deposition with no observed gonadal histopathology. Together, these results suggest that effects on egg deposition are primarily due to altered reproductive behavior. The mechanisms by which gestodene disrupts behavior are unknown. Nonetheless, the rapid and profound alterations of the reproductive biology of gestodene-exposed fish suggest that wild populations could be similarly affected.

Environmental Science & Technology↗

USGS2015

Developing analytical approaches to explore the connection between endocrine-active pharmaceuticals in water to effects in fish

The emphasis of this research project was to develop and optimize a solid-phase extraction method and highperformance liquid chromatography-electrospray ionizationmass spectrometry method, such that a linkage between the detection of endocrine-active pharmaceuticals (EAPs) in the aquatic environment and subsequent effects on fish populations could eventually be studied. Four EAPs were studied: tamoxifen (TAM), exemestane (EXE), letrozole (LET), anastrozole (ANA); and three TAM metabolites: 4- hydroxytamoxifen, e/z endoxifen, and n-desmethyl tamoxifen. In aqueous matrices, the use of isotopically labeled standards for the EAPs allowed for the generation of good recoveries, greater than 80 %, and low relative standard deviations (% RSDs) (3 to 27 %). TAM metabolites had lower recoveries in the spiked water matrices: 35 to 93 % in waste/source water compared to 58 to 110 % in DI water. The precision in DI water was acceptable ranging from 8 to 38 % RSD. However, the precision in real environmental wastewaters could be poor, ranging from 15 to 120 % RSD, dependent upon unique matrix effects. In plasma, the overall recoveries of the EAPs were acceptable: 88 to 110 %, with %RSDs of 6 to 18 % (Table 3). The spiked recoveries of the TAM metabolites from plasma were good, ranging from 77 to 120 %, with %RSDs ranging from 27 to 32 %. Two of the TAM metabolites, 4- hydroxytamoxifen and n-desmethyl tamoxifen, were confirmed in most of the environmental aqueous samples. The discovery of TAM metabolites demonstrates that the source of the TAM metabolites, TAM, is constant, introducing a pseudo-persistence of this chemical into the environment.

Analytical and Bioanalytical Chemistry↗

USGS2015

Synthetic ultraviolet light filtering chemical contamination of coastal waters of Virgin Islands National Park, St. John, U.S. Virgin Islands

Contamination of surface waters by synthetic ultraviolet light (UV) filtering chemicals is a concern for the Virgin Islands National Park (VINP). Discrete water samples were collected from VINP bays to determine UV filter chemical presence in the coastal waters. Spatial distribution and the potential for partitioning between subsurface waters and the sea surface microlayer (SML) were also examined. The UV filter chemicals 4-methylbenzylidene camphor, benzophenone-3, octinoxate, homosalate, and octocrylene were detected at concentrations up to 6073 ng/L (benzophenone-3). Concentrations for benzophenone-3 and homosalate declined exponentially (r 2 = 0.86 to 0.98) with distance from the beach. Limited data indicate that some UV filter chemicals may partition to the SML relative to the subsurface waters. Contamination of VINP coastal waters by UV filter chemicals may be a significant issue, but an improved understanding of the temporal and spatial variability of their concentrations would be necessary to better understand the risk they present.

St.John Island, Virgin Island↗