Marine Submicron Aerosols from the Gulf of Mexico: Polluted and Acidic with Rapid Production of Sulfate and Organosulfates.

We measured submicron aerosols (PM1) at a beachfront site in Texas in Spring 2021 to characterize the "background" aerosol chemical composition advecting into Texas and the factors controlling this composition. Observations show that marine "background" aerosols from the Gulf of Mexico were highly processed and acidic; sulfate was the most abundant component (on average 57% of total PM1 mass), followed by organic material (26%). These chemical characteristics are similar to those observed at other marine locations globally. However, Gulf "background" aerosols were much more polluted; the average non-refractory (NR-) PM1 mass concentration was 3-70 times higher than that observed in other clean marine atmospheres. Anthropogenic shipping emissions over the Gulf of Mexico explain 78.3% of the total measured "background" sulfate in the Gulf air. We frequently observed haze pollution in the air mass from the Gulf, with significantly elevated concentrations of sulfate, organosulfates, and secondary organic aerosol associated with sulfuric acid. Analysis suggests that aqueous oxidation of shipping emissions over the Gulf of Mexico by peroxides in the particles might potentially be an important pathway for the rapid production of acidic sulfate and organosulfates during the haze episodes under acidic conditions.

Apportioned primary and secondary organic aerosol during pollution events of DISCOVER-AQ Houston.

Understanding the drivers for high ozone (O3) and atmospheric particulate matter (PM) concentrations is a pressing issue in urban air quality, as this understanding informs decisions for control and mitigation of these key pollutants. The Houston, TX metropolitan area is an ideal location for studying the intersection between O3 and atmospheric secondary organic carbon (SOC) production due to the diversity of source types (urban, industrial, and biogenic) and the on- and off-shore cycling of air masses over Galveston Bay, TX. Detailed characterization of filter-based samples collected during Deriving Information on Surface Conditions from Column and VERtically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) Houston field experiment in September 2013 were used to investigate sources and composition of organic carbon (OC) and potential relationships between daily maximum 8 h average O3 and PM. The current study employed a novel combination of chemical mass balance modeling defining primary (i.e. POC) versus secondary (i.e. SOC) organic carbon and radiocarbon (14C) for apportionment of contemporary and fossil carbon. The apportioned sources include contemporary POC (biomass burning [BB], vegetative detritus), fossil POC (motor vehicle exhaust), biogenic SOC and fossil SOC. The filter-based results were then compared with real-time measurements by aerosol mass spectrometry. With these methods, a consistent urban background of contemporary carbon and motor vehicle exhaust was observed in the Houston metropolitan area. Real-time and filter-based characterization both showed that carbonaceous aerosols in Houston was highly impacted by SOC or oxidized OC, with much higher contributions from biogenic than fossil sources. However, fossil SOC concentration and fractional contribution had a stronger correlation with daily maximum 8 h average O3, peaking during high PM and O3 events. The results indicate that point source emissions processed by on- and off-shore wind cycles likely contribute to peak events for both PM and O3 in the greater Houston metropolitan area.

Spatial and Temporal Distributions of Organophosphate Ester Concentrations from Atmospheric Particulate Matter Samples Collected across Houston, TX.

Atmospheric particulate matter (PM) samples were collected from four ground-based sites located in the Houston, TX (September 21-28, 2013) and were analyzed for 12 organophosphate esters (OPEs; current-use plasticizers and flame retardants). Samples analyzed included daytime, nighttime, and 24 h PM of <2.5 µm aerodynamic diameter (PM2.5) and total suspended particulate (TSP) samples. PM2.5 and TSP atmospheric ΣOPE concentrations varied over an order of magnitude and were statistically significantly different between urban and suburban and industrial sites. Additionally, significant temporal variability was also identified; for example, daytime atmospheric concentrations of 2-ethylhexyl diphenyl phosphate (EHDPP; 610 ± 220 pg m-3) measured in TSP samples were significantly higher than nighttime concentrations (280 ± 180 pg m-3; p = 0.03). Detailed discussions of the spatial and temporal distribution are given for Tris-(1-chloro-2-propyl) phosphate (TCiPP), EHDPP, tri-n-butyl phosphate (TnBP), and triphenyl phosphate (TPhP). Correlations to bulk measurements of carbonaceous PM including organic carbon, elemental carbon, and water-soluble organic carbon were used to understand potential sources and urban atmospheric transport. These results highlight the fundamental complexity associated with assessing OPE atmospheric concentrations across a large urban landscape and specific knowledge gaps at the intersection of consumer products and safety with environmental and human health.

Persistent Organic Pollutant and Hormone Levels in Harbor Porpoise with B Cell Lymphoma.

B-cell lymphoma, a common morphologic variant of non-Hodgkin lymphoma, has been associated with persistent pollutants in humans, but this association is not well-characterized in top-level predators sharing marine resources with humans. We characterized and compared blubber contaminants and hormones of a pregnant harbor porpoise (Phocoena phocoena) with B-cell lymphoma, with those in two presumed healthy fishery by-caught porpoises with no lymphoma: a pregnant adult and female juvenile. Common historic use compounds, including polychlorinated biphenyls, polybrominated diphenyl ethers, and pesticides, were evaluated in blubber samples from three porpoises. In addition, blubber cortisol and progesterone levels (ng/g) were determined in all three animals. Total pollutant concentrations were highest in the juvenile porpoise, followed by the lymphoma porpoise and the nonlymphoma adult. Blubber cortisol concentrations were 191% greater in the pregnant with lymphoma porpoise compared with the pregnant no lymphoma porpoise, and 89% greater in the juvenile female compared with the pregnant no lymphoma porpoise. Although both adults were pregnant, progesterone levels were substantially greater (90%) in the healthy compared with the lymphoma adult. Health monitoring of top-level marine predators, such as porpoise, provides a sentinel measure of contaminants that serve as indicators of potential environmental exposure to humans.

Blue whale earplug reveals lifetime contaminant exposure and hormone profiles.

Lifetime contaminant and hormonal profiles have been reconstructed for an individual male blue whale (Balaenoptera musculus, Linnaeus 1758) using the earplug as a natural aging matrix that is also capable of archiving and preserving lipophilic compounds. These unprecedented lifetime profiles (i.e., birth to death) were reconstructed with a 6-mo resolution for a wide range of analytes including cortisol (stress hormone), testosterone (developmental hormone), organic contaminants (e.g., pesticides and flame retardants), and mercury. Cortisol lifetime profiles revealed a doubling of cortisol levels over baseline. Testosterone profiles suggest this male blue whale reached sexual maturity at approximately 10 y of age, which corresponds well with and improves on previous estimates. Early periods of the reconstructed contaminant profiles for pesticides (such as dichlorodiphenyltrichloroethanes and chlordanes), polychlorinated biphenyls, and polybrominated diphenyl ethers demonstrate significant maternal transfer occurred at 0-12 mo. The total lifetime organic contaminant burden measured between the earplug (sum of contaminants in laminae layers) and blubber samples from the same organism were similar. Total mercury profiles revealed reduced maternal transfer and two distinct pulse events compared with organic contaminants. The use of a whale earplug to reconstruct lifetime chemical profiles will allow for a more comprehensive examination of stress, development, and contaminant exposure, as well as improve the assessment of contaminant use/emission, environmental noise, ship traffic, and climate change on these important marine sentinels.

Spatial and Temporal Distribution of Current-Use Pesticides in Atmospheric Particulate Matter in Houston, Texas.

The atmospheric concentrations of seven current-use pesticides in particulate matter were determined at four locations throughout the Houston metropolitan area in TSP and PM2.5 samples from September 2013. Atmospheric concentrations in both TSP and PM2.5 ranged from below method detection limits (MDLs) to nearly 1100 pg m-3. The three compounds most frequently detected above MDLs were chlorothalonil, bifenthrin, and λ-cyhalothrin. Atmospheric chlorothalonil concentrations were above 800 pg m-3 in several TSP samples, but

Selective pressurized liquid extraction technique capable of analyzing dioxins, furans, and PCBs in clams and crab tissue.

A selective pressurized liquid extraction technique (SPLE) was developed for the analysis of polychlorodibenzo-p-dioxins, polychlorodibenzofurans (PCDD/Fs) and dioxin-like polychlorobiphenyls (dl-PCBs) in clam and crab tissue. The SPLE incorporated multiple cleanup adsorbents (alumina, florisil, silica gel, celite, and carbopack) within the extraction cell. Tissue extracts were analyzed by high resolution gas chromatography coupled with electron capture negative ionization mass spectrometry. Mean recovery (n = 3) and percent relative standard deviation for PCDD/Fs and dl-PCBs in clam and crabs was 89 ± 2.3 and 85 ± 4.0, respectively. The SPLE method was applied to clams and crabs collected from the San Jacinto River Waste Pits, a Superfund site in Houston, TX. The dl-PCBs concentrations in clams and crabs ranged from 50 to 2,450 and 5 to 800 ng/g ww, respectively. Sample preparation time and solvents were reduced by 92 % and 65 %, respectively, as compared to USEPA method 1613.

Impacts of anthropogenic emissions and meteorology on spring ozone differences in San Antonio, Texas between 2017 and 2021.

San Antonio has been designated as ozone nonattainment under the current National Ambient Air Quality Standards (NAAQS). Ozone events in the city typically occur in two peaks, characterized by a pronounced spring peak followed by a late summer peak. Despite higher ozone levels, the spring peak has received less attention than the summer peak. To address this research gap, we used the Weather Research and Forecasting (WRF)-driven GEOS-Chem (WRF-GC) model to simulate San Antonio's ozone changes in the spring month of May from 2017 to 2021 and quantified the respective contributions from changes in anthropogenic emissions and meteorology. In addition to modeling, observations from the San Antonio Field Studies (SAFS), the Texas Commission on Environmental Quality (TCEQ) Continuous Ambient Monitoring Stations (CAMS), and the spaceborne TROPOspheric Monitoring Instrument (TROPOMI) are used to examine and validate changes in ozone and precursors. Results show that the simulated daytime mean surface ozone in May 2021 is 3.8 ± 0.6 ppbv lower than in May 2017, which is slightly less than the observed average differences of -5.3 ppbv at CAMS sites. The model predicted that the anthropogenic emission-induced changes contribute to a 1.4 ± 0.5 ppbv reduction in daytime ozone levels, while the meteorology-induced changes account for a 2.4 ± 0.6 ppbv reduction over 2017-2021. This suggests that meteorology plays a relatively more important role than anthropogenic emissions in explaining the spring ozone differences between the two years. We additionally identified (1) reduced NO2 and HCHO concentrations as chemical reasons, and (2) lower temperature, higher humidity, increased wind speed, and a stronger Bermuda High as meteorological reasons for lower ozone levels in 2021 compared to 2017. The quantification of the different roles of meteorology and ozone precursor concentrations helps understand the cause and variation of ozone changes in San Antonio over recent years.

Relative importance of the humic and fulvic fractions of natural organic matter in the aggregation and deposition of silver nanoparticles.

As engineered nanoparticles (NPs) are increasingly used, their entry into the environment has become an important topic for water sustainability. Recent investigations point to the critical role of natural organic matter (NOM) in altering the persistence of NPs by complexing with their surfaces. The NP-NOM complex, in turn, is the new entity that may potentially influence subsequent fate of NPs. To understand the relative impact of humic (HA) and fulvic fraction of NOM on the stability and mobility of silver nanoparticles (AgNPs), a combination of dynamic light scattering and quartz crystal microgravimetry with dissipation monitoring was used. In the absence of unbound NOM, (1) surface modification on either AgNP or silica substrate by different NOM fractions could lead to substantial changes in the extent and kinetics of AgNP aggregation and deposition, and (2) HA has a greater capability to enhance the transport of AgNPs by reducing their aggregation and deposition. With unbound NOM, HA seems to compete more successfully for binding sites on the substrate under electrostatically favorable conditions and formed a steric layer to prevent subsequent deposition of AgNPs. These findings highlighted the importance of NOM fraction in the overall environmental partitioning of AgNPs.

Occurrence of pharmaceuticals and personal care products in German fish tissue: a national study.

German Environment Specimen Bank (GESB) fish tissue samples, collected from 14 different GESB locations, were analyzed for 15 pharmaceuticals, 2 pharmaceutical metabolites, and 12 personal care products. Only 2 pharmaceuticals, diphenhydramine and desmethylsertraline, were measured above MDL. Diphenhydramine (0.04-0.07 ng g(-1) ww) and desmethylsertraline (1.65-3.28 ng g(-1) ww) were measured at 4 and 2 locations, respectively. The maximum concentrations of galaxolide (HHCB) (447 ng g(-1) ww) and tonalide (AHTN) (15 ng g(-1) ww) were measured at the Rehlingen sampling site in the Saar River. A significant decrease in HHCB and AHTN fish tissue concentrations was observed from 1995 to 2008 at select GESB sampling sites (r(2) = 0.69-0.89 for galaxolide and 0.89-0.97 for tonalide with p < 0.003). Galaxolide and tonalide fish tissue concentrations in Germany were ∼19× and ∼28× lower, respectively, as compared to fish tissue concentrations measured in a United States nationwide PPCP study conducted in 2006. Proximity of the sampling locations to the upstream wastewater treatment plant discharging point and mean annual flow at the sampling location were found to significantly predict galaxolide and tonalide fish tissue concentrations (HHCB: r(2) = 0.79, p = 0.021 and AHTN: r(2) = 0.81, p = 0.037) in Germany.

Traffic, transport, and vegetation drive VOC concentrations in a major urban area in Texas.

The population of Texas has increased rapidly in the past decade. The San Antonio Field Study (SAFS) was designed to investigate ozone (O3) production and precursors in this rapidly changing, sprawling metropolitan area. There are still many questions regarding the sources and chemistry of volatile organic compounds (VOCs) in urban areas like San Antonio which are affected by a complex mixture of industry, traffic, biogenic sources and transported pollutants. The goal of the SAFS campaign in May 2017 was to measure inorganic trace gases, VOCs, methane (CH4), and ethane (C2H6). The SAFS field design included two sites to better assess air quality across the metro area: an urban site (Traveler's World; TW) and a downwind/suburban site (University of Texas at San Antonio; UTSA). The results indicated that acetone (2.52 ± 1.17 and 2.39 ± 1.27 ppbv), acetaldehyde (1.45 ± 1.02 and 0.93 ± 0.45 ppbv) and isoprene (0.64 ± 0.49 and 1.21 ± 0.85 ppbv; TW and UTSA, respectively) were the VOCs with the highest concentrations. Additionally, positive matrix factorization showed three dominant factors of VOC emissions: biogenic, aged urban mixed source, and acetone. Methyl vinyl ketone and methacrolein (MVK + MACR) exhibited contributions from both secondary photooxidation of isoprene and direct emissions from traffic. The C2H6:CH4 demonstrated potential influence of oil and gas activities in San Antonio. Moreover, the high O3 days during the campaign were in the NOx-limited O3 formation regime and were preceded by evening peaks in select VOCs, NOx and CO. Overall, quantification of the concentration and trends of VOCs and trace gases in a major city in Texas offers vital information for general air quality management and supports strategies for reducing O3 pollution. The SAFS campaign VOC results will also add to the growing body of literature on urban sources and concentrations of VOCs in major urban areas.

Assessing the atmospheric fate of pesticides used to control mosquito populations in Houston, TX.

During the summer months, urban areas are literal hot spots of mosquito-borne disease transmission and air pollution. Public health authorities release aerosolized pesticides directly into the atmosphere to help control adult mosquito populations and thereby reduce the threat of diseases, such as Zika Virus. The primary adulticides (i.e. pesticides used to control adult mosquito populations) in Houston, TX are permethrin and malathion. These adulticides are typically sprayed at night using ultra-low volume sprayers. Particulate matter (PM) samples including total suspended and fine PM (PM < 2.5 µm in aerodynamic diameter) were collected at four ground-based sites across Houston in 2013 and include daytime, nighttime, and 24 h samples. Malathion is initially sprayed as coarse aerosol (5-25 µm), but is measured in fine aerosol (<2.5 µm) and coarse aerosol in the urban atmosphere. Particle size is relevant both for deposition velocities and for human exposure. Atmospheric permethrin concentrations measured in nighttime samples peak at 60 ng m-3, while malathion nighttime concentrations peak near 40 ng m-3. Malaoxon, an oxidation product of malathion, was also frequently detected at concentrations >10 ng m-3, indicating significant nighttime oxidation. Based on the loss of malathion and the increase in malaoxon, the atmospheric half-life of malathion in Houston was estimated at <12 h, which was significantly shorter than previous half-life estimates (∼days). Importantly, malaoxon is estimated to be 22-33 times more toxic to humans than malathion. Both the aerosol size and the half-life are critical for mosquito control, human exposure, and risk assessment of these routine pesticides.

Evidence of multi-decadal behavior and ecosystem-level changes revealed by reconstructed lifetime stable isotope profiles of baleen whale earplugs.

Biological time series datasets provide an unparalleled opportunity to investigate regional and global changes in the marine environment. Baleen whales are long-lived sentinel species and an integral part of the marine ecosystem. Increasing anthropogenic terrestrial and marine activities alter ocean systems, and such alterations could change foraging and feeding behavior of baleen whales. In this study, we analyzed δ13C and δ15N of baleen whale earplugs from three different species (N = 6 earplugs, n = 337 laminae) to reconstruct the first continuous stable isotope profiles with a six-month resolution. Results of our study provide an unprecedented opportunity to assess behavioral as well as ecological changes. Abrupt shifts and temporal variability observed in δ13C and δ15N profiles could be indicative of behavior change such as shift in foraging location and/or trophic level in response to natural or anthropogenic disturbances. Additionally, five out of six individuals demonstrated long-term declining trends in δ13C profiles, which could suggest influence of emission of depleted 13CO2 from fossil fuel combustion referred to as the Suess effect. After adjusting the δ13C values of earplugs for the estimated Suess effect and re-evaluating δ13C profiles, significant decline in δ13C values as well as different rate of depletion suggest contribution of other sources that could impact δ13C values at the base of the food web.

Eighty years of chemical exposure profiles of persistent organic pollutants reconstructed through baleen whale earplugs.

Despite decades of effort, significant knowledge gaps still exist regarding the global transport and distribution of persistent organic pollutants (POPs) in marine ecosystems, especially for periods prior to the 1970s. Furthermore, for long-lived marine mammals such as baleen whales, POPs impacts on early developmental (first years of life), as well as lifetime exposure profiles for periods of use and phase-out, are not well characterized. Recently, analytical techniques capable of reconstructing lifetime (i.e., birth to death; ~6 mos. resolution) chemical exposure profiles in baleen whale earplugs have been developed. Earplugs represent a unique opportunity to examine the spatiotemporal trends of POPs in the marine ecosystem. Baleen whale earplugs were collected from six whales (one blue whale (Balaenoptera musculus) and five fin whales (Balaenoptera physalus)), including four from archived collections and two from recent strandings. Lifespans for some of these individuals date back to the 1930s and provide insight into early periods of POP use. POP concentrations (reported in ng g-1 dry wt.) were determined in laminae (n = 35) and were combined with age estimates and calendar year to reconstruct lifetime POP exposure profiles and lifetime bioaccumulation rates. Dichlorodiphenyltrichloroethane (DDT) and polychlorinated biphenyls (PCBs) were found to be the most dominant POPs (spanning the past 80 y), were detected as early as the 1930s and were ubiquitous in the North Pacific and Atlantic Oceans. Lifetime bioaccumulation rates determined using baleen whale earplugs were 56 times higher in the North Pacific as compared to the North Atlantic. This suggest baleen whales from the North Pacific may be to be exposed to increased levels of POPs.

Hormone comparison between right and left baleen whale earplugs.

Marine animals experience additional stressors as humans continue to industrialize the oceans and as the climate continues to rapidly change. To examine how the environment or humans impact animal stress, many researchers analyse hormones from biological matrices. Scientists have begun to examine hormones in continuously growing biological matrices, such as baleen whale earwax plugs, baleen and pinniped vibrissae. Few of these studies have determined if the hormones in these tissues across the body of the organism are interchangeable. Here, hormone values in the right and left earplugs from the same individual were compared for two reasons: (i) to determine whether right and left earplug hormone values can be used interchangeably and (ii) to assess methods of standardizing hormones in right and left earplugs to control for individuals' naturally varying hormone expressions. We analysed how absolute, baseline-corrected and Z-score normalized hormones performed in reaching these goals. Absolute hormones in the right and left earplugs displayed a positive relationship, while using Z-score normalization was necessary to standardize the variance in hormone expression. After Z-score normalization, it was possible to show that the 95% confidence intervals of the differences in corresponding lamina of the right and left earplugs include zero for both cortisol and progesterone. This indicates that the hormones in corresponding lamina of right and left earplugs are no different from zero. The results of this study reveal that both right and left earplugs from the same baleen whale can be used in hormone analyses after Z-score normalization. This study also shows the importance of Z-score normalization to interpretation of results and methodologies associated with analysing long-term trends using whale earplugs.

Gas chromatography-mass spectrometry screening methods for select UV filters, synthetic musks, alkylphenols, an antimicrobial agent, and an insect repellent in fish.

Two screening methods have been developed for simultaneous determination of ten extensively used personal care products (PCPs) and two alkylphenol surfactants in fish. The methods consisted of extraction, clean-up, derivatization and analysis by gas chromatography-mass spectrometry with selected ion monitoring (GC-SIM-MS) or gas chromatography-tandem mass spectrometry (GC-MS/MS) techniques. Among solvents tested to assess recovery of target compounds from 1-g tissue homogenates, acetone was selected as optimal for extracting compounds with dissimilar physicochemical properties from fish tissue. Initial experiments confirmed that GC-SIM-MS could be applied for analysis of lean fillet tissue (<1% lipid) without gel-permeation chromatography (GPC), and this approach was applied to assess the presence of target analytes in fish fillets collected from a regional effluent-dominated stream in Texas, USA. Benzophenone, galaxolide, tonalide, and triclosan were detected in 11 of 11 environmental samples at concentrations ranging from; 37 to 90, 234 to 970, 26 to 97, and 17 to 31 ng/g, respectively. However, performance of this analytical approach declined appreciably with increasing lipid content of analyzed tissues. Successful analysis of samples with increased lipid content was enabled by adding GPC to the sample preparation protocol and monitoring analytes with tandem mass spectrometry. Both analytical approaches were validated using fortified fillet tissue collected from locations expected to be minimally impacted by anthropogenic influences. Average analyte recoveries ranged from 87% to 114% with RSDs <11% and from 54% to 107% with RSDs <20% for fish tissue containing <1% and 4.9% lipid, respectively. Statistically derived method detection limits (MDLs) for GC-SIM-MS and GC-MS/MS methodologies ranged from 2.4 to 16 ng/g, and 5.1 to 397 ng/g, respectively.

Probabilistic ecological hazard assessment of parabens using Daphnia magna and Pimephales promelas.

Parabens are common antimicrobial agents found in thousands of pharmaceuticals and personal care products. Parabens are introduced into aquatic ecosystems from wastewater treatment plant effluents and have been detected in surface waters in the low microgram per liter range. Although these compounds display low toxicity in mammals, paraben toxicity to aquatic organisms has not been investigated. Standardized acute and subchronic endpoints in larval fish (Pimephales promelas) and cladoceran (Daphnia magna) models were examined for seven different parabens (methyl-, ethyl-, isopropyl-, propyl-, isobutyl-, butyl-, benzylparaben), which encompassed a range of log P values. Paraben 48 h median lethal concentration values (LC50) ranged from 4.0 to 24.6 mg/L in D. magna and 3.3 to >160.0 mg/L in fathead minnow. Growth and reproduction in D. magna had lowest-observed-effect concentrations (LOECs) ranging from 0.12 to 9.0 mg/L and 1.5 to 6.0 mg/L, respectively. Fathead minnow growth was adversely affected at levels ranging from 1.0 to 25.0 mg/L. Aquatic toxicity of the parabens was inversely related to lipophilicity, suggesting that responses using standardized endpoints resulted from narcosis. Utilizing toxicity benchmark concentrations (e.g., LC50s, LOECs) for each compound, chemical toxicity distributions, a probabilistic hazard assessment technique, were developed to assess the probabilities of detecting parabens that elicit a response at or below a given concentration. For the responses assessed in the present study, the 5th centile values (the concentration at which 5% of parabens elicit a response) ranged from 15 microg/L to 2.43 mg/L, with D. magna growth eliciting the lowest 5th centile value and acute D. magna mortality eliciting the highest. The distributions demonstrated that at environmentally relevant concentrations in developed countries there is limited acute or subchronic aquatic hazard of parabens to the organisms and responses examined.

Influence of nitrogen and phosphorus concentrations and ratios on Lemna gibba growth responses to triclosan in laboratory and stream mesocosm experiments.

The effects of co-occurring nutrient and contaminant stressors are very likely to interact in aquatic systems, particularly at the level of primary producers. Site-specific nitrogen (N) and phosphorus (P) concentrations are often much lower and differ in relative availability than those used in nutrient-saturated laboratory assays for aquatic plants, which can introduce uncertainty in prospective ecological hazard and risk assessments. Because triclosan, an antimicrobial agent included in personal care products, potentially presents high relative risk among antimicrobial agents to aquatic plants and algae, we performed laboratory experiments with the model aquatic macrophyte Lemna gibba across a gradient of environmentally relevant N:P levels with and without triclosan co-exposure. Frond numbers (7 d) were significantly higher in N:P treatments of 16 and 23 but were lower in N:P of 937 and 2,500 treatments relative to standardized control media (N:P=3). When triclosan co-exposure occurred at high nutrient concentrations, frond number median effective concentration values at N:P 0.75, 3, and 16 were more than twofold lower than triclosan median effective concentration values in low nutrient media N:P ratios. However, a triclosan median effective concentration for frond number was twofold lower at N:P of 2,500 than at other N:P ratios in low concentration media. Influences of P enrichment on triclosan toxicity to L. gibba were further explored during a 14-d outdoor experimental stream mesocosm study. Effects of 2.6 and 20.8 microg L(-1) triclosan on L. gibba growth rates were more pronounced with increasing P treatment levels, which was generally consistent with our laboratory observations. Findings from these laboratory and field studies indicate that site-specific nutrient concentrations and ratios should be considered during assessments of primary producer responses to chemical stressors.

Occurrence of pharmaceuticals and personal care products in fish: results of a national pilot study in the United States.

Pharmaceuticals and personal care products are being increasingly reported in a variety of biological matrices, including fish tissue; however, screening studies have presently not encompassed broad geographical areas. A national pilot study was initiated in the United States to assess the accumulation of pharmaceuticals and personal care products in fish sampled from five effluent-dominated rivers that receive direct discharge from wastewater treatment facilities in Chicago, Illinois; Dallas, Texas; Orlando, Florida; Phoenix, Arizona; and West Chester, Pennsylvania, USA. Fish were also collected from the Gila River, New Mexico, USA, as a reference condition expected to be minimally impacted by anthropogenic influence. High performance liquid chromatography-tandem mass spectrometry analysis of pharmaceuticals revealed the presence of norfluoxetine, sertraline, diphenhydramine, diltiazem, and carbamazepine at nanogram-per-gram concentrations in fillet composites from effluent-dominated sampling locations; the additional presence of fluoxetine and gemfibrozil was confirmed in liver tissue. Sertraline was detected at concentrations as high as 19 and 545 ng/g in fillet and liver tissue, respectively. Gas chromatography-tandem mass spectrometry analysis of personal care products in fillet composites revealed the presence of galaxolide and tonalide at maximum concentrations of 2,100 and 290 ng/g, respectively, and trace levels of triclosan. In general, more pharmaceuticals were detected at higher concentrations and with greater frequency in liver than in fillet tissues. Higher lipid content in liver tissue could not account for this discrepancy as no significant positive correlations were found between accumulated pharmaceutical concentrations and lipid content for either tissue type from any sampling site. In contrast, accumulation of the personal care products galaxolide and tonalide was significantly related to lipid content. Results suggest that the detection of pharmaceuticals and personal care products was dependent on the degree of wastewater treatment employed.

Polychlorinated biphenyl (PCB) contamination in Galveston Bay, Texas: Comparing concentrations and profiles in sediments, passive samplers, and fish.

The industrialized portion of the Houston Ship Channel (HSC) is heavily contaminated with anthropogenic contaminants, most prominent of which are the polychlorinated biphenyls (PCBs). This contamination has driven adaptive evolution in a keystone species for Galveston Bay, the Gulf killifish (Fundulus grandis). We investigated the geographical extent of PCB impacts by sampling 12 sites, ranging from the heavily industrialized upper portion of the HSC to Galveston Island. At each site, PCB concentrations and profiles were determined in three environmental compartments: sediment, water (polyethylene passive samplers), and fish tissue (resident Gulf killifish). We observed a steep gradient of PCB contamination, ranging from 4.00 to 100,000 ng/g organic carbon in sediment, 290-110,000 ng/g lipid in fish, and 4.5-2300 ng/g polyethylene in passive samplers. The PCB congener profiles in Gulf killifish at the most heavily contaminated sites were shifted toward the higher chlorinated PCBs and were highly similar to the sediment contamination profiles. In addition, while magnitude of total PCB concentrations in sediment and total fish contamination levels were highly correlated between sites, the relative PCB congener profiles in fish and passive samplers were more alike. This strong correlation, along with a lack of dependency of biota-sediment accumulation factors with total contamination rates, confirm the likely non-migratory nature of Gulf killifish and suggest their contamination levels are a good site-specific indicator of contamination in the Galveston Bay area. The spatial gradient of PCB contamination in Galveston Bay was evident in all three matrices studied and was observed effectively using Gulf killifish contamination as an environmentally relevant bioindicator of localized contamination in this environment.