Although bisphenol A (BPA) is commonly recognized as an endocrine disruptor, the metabolic consequences of its exposure are still poorly understood. In this study, we present a non-targeted LC-MS based metabolomic analysis in combination with a full-genome, high-throughput RNA sequencing (RNA-Seq) to reveal the metabolic effects and the subjacent regulatory pathways of exposing zebrafish embryos to BPA during the first 120 hours post-fertilization. We applied multivariate data analysis methods to extract biochemical information from the LC-MS and RNA-Seq complex datasets and to perform testable predictions of the phenotypic adverse effects. Metabolomic and transcriptomic data revealed a similar subset of altered pathways, despite the large difference in the number of identified biomarkers (around 50 metabolites and more than 1000 genes). These results suggest that even a moderate coverage of zebrafish metabolome may be representative of the global metabolic changes. These multi-omic responses indicate a specific metabolic disruption by BPA affecting different signaling pathways, such as retinoid and prostaglandin metabolism. The combination of transcriptomic and metabolomic data allowed a dynamic interpretation of the results that could not be drawn from either single dataset. These results illustrate the utility of -omic integrative analyses for characterizing the physiological effects of toxicants beyond the mere indication of the affected pathways.

Recent work identified the need for site-specific Pb bioaccessibility evaluation and scaled contaminant modeling. Pb heterogeneity has made bioaccessibility characterization difficult, and complicated distribution models. Using field testing, bioaccessibility measurement, Integrated Exposure Uptake and Biokinetic (IEUBK) modeling, and geospatial techniques, we propose a framework for conducting applied risk-based, multiscale assessment. This framework was tested and implemented in Burlington, VT, an area of old housing stock and high Pb burden (up to 15 000 mg kg−1) derived primarily from paint. After analyzing local soil samples for total and bioaccessible Pb, it was determined that bioaccessible and total Pb were well correlated in this area, through which an average bioaccessibility parameter was derived approximating Pb bioaccessibility for this soil type and Pb impact. This parameter was used with the IEUBK to recommend the local limit for residential soil Pb be reduced from 400 to 360 mg kg−1, taking into consideration the lowering of the blood lead level threshold for Pb poisoning from 10 to 5 μg dL−1 by the Centers for Disease Control (CDC). Geospatial investigation incorporated samples collected during this investigation and samples from a high school summer science academy, and relied on three techniques, used at different scales: kriging of total and background Pb alone, kriging of total and background Pb with housing age as a well-sampled, well-correlated secondary variable (cokriging), and inverse distance weighting of total and bioaccessible Pb. Modeling at different scales allowed for characterization of Pb impact at single sites as well as citywide. Model maps show positive correlation between areas of older housing and areas of high Pb burden, as well as potential at different scales for reducing the effects of Pb heterogeneity.

Metals are ubiquitous and normally co-occur as mixtures in soil, but there remains much to do regarding the development of appropriate models which incorporate mixture interactions and bioavailability to estimate their phytotoxicity and phytoaccumulation. Here, we developed a probability-based electrostatic toxicity model (ETM) and a Langmuir-type electrostatic uptake model (EUM) to predict and normalize toxicity and uptake of zinc-copper mixtures in Hordeum vulgare L. in different soils. For model development, the electrical potential (ψ0) and metal ion activities ({M2+}0) at the cell-membrane surface was computed based on plant physiological properties and soil solution chemistry. Single metal toxicity correlated more closely to their corresponding {M2+}0 than to ion activities in soil solution or total soil metal concentrations. The ETM explained up to 89% of the variance in mixture toxicity across different soils. Incorporation of ψ0 into the EUM improved the model's ability for predicting metal uptake. Besides, cell-surface H+ appeared to significantly inhibit copper uptake via competition or other mechanisms, beyond its effect upon ψ0. Our results for the first time demonstrate that electrostatic theory can be used to predict and reconcile mixture toxicity and uptake data in different soils, indicating the potential of electrostatic-based models in risk assessment of multimetal-contaminated soils.

Benzotriazole ultraviolet stabilizers (BUVSs) are prominent chemicals widely used in industrial and consumer products to protect against ultraviolet radiation. They are becoming contaminants of emerging concern since their residues are frequently detected in multiple environmental matrices and their toxicological implications are increasingly reported. We herein investigated the antiandrogenic activities of eight BUVSs prior to and after human CYP3A4-mediated metabolic activation/deactivation by the two-hybrid recombinant human androgen receptor yeast bioassay and the in vitro metabolism assay. More potent antiandrogenic activity was observed for the metabolized UV-328 in comparison with UV-328 at 0.25 μM ((40.73 ± 4.90)% vs. (17.12 ± 3.00)%), showing a significant metabolic activation. In contrast, the metabolized UV-P at 0.25 μM resulted in a decreased antiandrogenic activity rate from (16.08 ± 0.95)% to (6.91 ± 2.64)%, indicating a metabolic deactivation. Three mono-hydroxylated (OH) and three di-OH metabolites of UV-328 were identified by ultra-performance liquid chromatography quadrupole time of flight mass spectrometry (UPLC-Q-TOF-MS/MS), which were not reported previously. We further surmised that the hydroxylation of UV-328 occurs mainly at the alicyclic hydrocarbon atoms based on the in silico prediction of the lowest activation energies of hydrogen abstraction from C-H bond. Our results for the first time relate antiandrogenic activity to human CYP3A4 enzyme-mediated hydroxylated metabolites of BUVSs. The biotransformation through hydroxylation should be fully considered during the health risk assessment of structurally similar analogs of BUVSs and other emerging contaminants.

Trace elements are added to poultry feed to control infection and improve weight gain. However, the fate of these trace elements in poultry litter is poorly understood. Because poultry litter is applied as fertilizer in many agricultural regions, evaluation of the environmental processes that influence the mobility of litter-derived trace elements is critical for predicting if trace elements are retained in soil or released to water. This study examined the effect of dissolved organic carbon (DOC) in poultry litter leachate on the fate and transport of litter-derived elements (As, Cu, P and Zn) using laboratory column experiments with soil collected from the Delmarva Peninsula (Mid-Atlantic, USA), a region of intense poultry production. Results of the experiments showed that DOC enhanced the mobility of all of the studied elements. However, despite the increased mobility, 60–70% of Zn, As and P mass was retained within the soil. In contrast, almost all of the Cu was mobilized in the litter leachate experiments, with very little retention in soil. Overall, our results demonstrate that the mobility of As, Cu, Zn and P in soils which receive poultry litter application is strongly influenced by both litter leachate composition, specifically organic acids, and adsorption to soil. Results have implications for understanding fate and transport of trace elements released from litter application to soil water and groundwater, which can affect both human health and the environment.

Intermittent, fluctuating and pulsed contaminant discharges may result in organisms receiving highly variable contaminant exposures. This study investigated the effects of dissolved copper pulse concentration and exposure duration on the toxicity to two freshwater green algae species. The effects of single copper pulses of between 1 and 48 h duration and continuous exposures (72 h) on growth rate inhibition of Pseudokirchneriella subcapitata and Chlorella sp. were compared on a time-averaged concentration (TAC) basis. Relationships were then derived between the exposure concentration and duration required to elicit different levels of toxicity expressed as inhibition concentration (IC). Continuous exposure IC50's of 3.0 and 1.9 μg/L were measured on a TAC basis for P. subcapitata and Chlorella sp., respectively. Algal growth rates generally recovered to control levels within 24–48 h of the copper pulse removal, with some treatments exhibiting significantly (p < 0.05) higher rates of cell division than controls in this recovery period. For both algae, when exposed to treatments with equivalent TACs, the continuous exposure elicited similar or slightly greater growth rate inhibition than the pulsed exposures. To elicit equivalent inhibition, the exposure concentration increased as the exposure duration decreased, and power models fitted this relationship reasonably well for both species. Water quality guideline values (WQGVs) are predominantly derived using data from continuous exposure toxicity bioassays, despite intermittent contaminant exposures often occurring in aquatic systems. The results indicate the WQGV for copper may be relaxed for pulsed exposures by a factor less than or equivalent to the TAC and still achieve a protection to these sensitive algae species.

Hypoxia is a global problem in aquatic systems and often co-occurs with pollutants. Despite this, little is known about the combined effects of these stressors on aquatic organisms. The objective of this study was to investigate the combined effects of hypoxia and copper, a toxic metal widespread in the aquatic environment. We used the three-spined stickleback (Gasterosteus aculeatus) as a model because of its environmental relevance and amenability for environmental toxicology studies. We focused on embryonic development as this is considered to be a sensitive life stage to environmental pollution. We first investigated the effects of hypoxia alone on stickleback development to generate the information required to design subsequent studies. Our data showed that exposure to low oxygen concentrations (24.7 ± 0.9% air saturation; AS) resulted in strong developmental delays and increased mortalities, whereas a small decrease in oxygen (75.0 ± 0.5%AS) resulted in premature hatching. Stickleback embryos were then exposed to a range of copper concentrations under hypoxia (56.1 ± 0.2%AS) or normoxia (97.6 ± 0.1%AS), continuously, from fertilisation to free swimming larvae. Hypoxia caused significant changes in copper toxicity throughout embryonic development. Prior to hatching, hypoxia suppressed the occurrence of mortalities, but after hatching hypoxia significantly increased copper toxicity. Interestingly, when exposures were conducted only after hatching, the onset of copper-induced mortalities was delayed under hypoxia compared to normoxia, but after 48 h, copper was more toxic to hatched embryos under hypoxia. This is the second species for which the protective effect of hypoxia on copper toxicity prior to hatching, followed by its exacerbating effect after hatching is demonstrated, suggesting the hypothesis that this pattern may be common for teleost species. Our research highlights the importance of considering the interactions between multiple stressors, as understanding these interactions is essential to facilitate the accurate prediction of the consequences of exposure to complex stressors in a rapidly changing environment.

The present study aimed to investigate biodegradation mechanisms of black carbon (BC)-bound contaminants in BC-amended sediment when BC was applied to control organic pollution. The single-point Tenax desorption technique was applied to track the species changes of nonylphenol (NP) during biodegradation process in the rice straw carbon (RC)-amended sediment. And the correlation between the biodegradation and desorption of NP was analyzed. Results showed that microorganisms firstly degraded the rapid-desorbing NP (6 h Tenax desorption) in RC-amended sediment. The biodegradation facilitated the desorption of slow-desorbing NP, which was subsequently degraded as well (192 h Tenax desorption). Notably, the final amount of NP degradation was greater than that of NP desorption, indicating that absorbed NP by RC amendment can be degraded by microorganisms. Finally, the residual NP amount in RC-amended sediment was decided by RC content and its physicochemical property. Moreover, the presence of the biofilm was observed by the confocal laser scanning microscope (CLSM) and scanning electron microscope (SEM) so that microorganisms were able to overcome the mass transfer resistance and directly utilized the absorbed NP. Therefore, single-point Tenax desorption alone may not be an adequate basis for the prediction of the bioaccessibility of contaminants to microorganisms or bioremediation potential in BC-amended sediment.

The arrival and discharge of seven antibiotics were monitored at two trickling filter sewage treatment plants of 6000 and 11,000 population equivalents (PE) and two activated sludge plants of 33,000 and 162,000 PE in Southern England. The investigation consisted of 24 h composite samples taken on two separate days every summer from 2012 to 2015 and in the winter of 2015 (January) from influent and effluent. The average influent concentrations generally matched predictions based on England-wide prescription data for trimethoprim, sulfamethoxazole, azithromycin, oxytetracycline and levofloxacin (within 3-fold), but were 3–10 times less for clarithromycin, whilst tetracycline influent concentrations were 5–17 times greater than expected. Over the four years, effluent concentrations at a single sewage plant varied by up to 16-fold for clarithromycin, 10-fold for levofloxacin and sulfamethoxazole, 7-fold for oxytetracycline, 6-fold for tetracycline, 4-fold for azithromycin and 3-fold for trimethoprim. The study attempted to identify the principal reasons for this variation in effluent concentration. By measuring carbamazepine and using it as a conservative indicator of transport through the treatment process, it was found that flow and hence concentration could alter by up to 5-fold. Measuring influent and effluent concentrations allowed assessments to be made of removal efficiency. In the two activated sludge plants, antibiotic removal rates were similar for the tested antibiotics but could vary by several-fold at the trickling filter plants. However, for clarithromycin and levofloxacin the variations in effluent concentration were above that which could be explained by either flow and/or removal alone so here year on year changes in consumption are likely to have played a role.

The limited spatial coverage of the air pollution data available from regulatory air quality monitoring networks hampers national-scale epidemiological studies of air pollution. The present study aimed to develop a national-scale exposure prediction model for estimating annual average concentrations of PM10 and NO2 at residences in South Korea using regulatory monitoring data for 2010. Using hourly measurements of PM10 and NO2 at 277 regulatory monitoring sites, we calculated the annual average concentrations at each site. We also computed 322 geographic variables in order to represent plausible local and regional pollution sources. Using these data, we developed universal kriging models, including three summary predictors estimated by partial least squares (PLS). The model performance was evaluated with fivefold cross-validation. In sensitivity analyses, we compared our approach with two alternative approaches, which added regional interactions and replaced the PLS predictors with up to ten selected variables. Finally, we predicted the annual average concentrations of PM10 and NO2 at 83,463 centroids of residential census output areas in South Korea to investigate the population exposure to these pollutants and to compare the exposure levels between monitored and unmonitored areas. The means of the annual average concentrations of PM10 and NO2 for 2010, across regulatory monitoring sites in South Korea, were 51.63 μg/m3 (SD = 8.58) and 25.64 ppb (11.05), respectively. The universal kriging exposure prediction models yielded cross-validated R2s of 0.45 and 0.82 for PM10 and NO2, respectively. Compared to our model, the two alternative approaches gave consistent or worse performances. Population exposure levels in unmonitored areas were lower than in monitored areas. This is the first study that focused on developing a national-scale point wise exposure prediction approach in South Korea, which will allow national exposure assessments and epidemiological research to answer policy-related questions and to draw comparisons among different countries.