Agricultural soils account for more than 50% of nitrogen leaching (LN) to groundwater in China. When excess levels of nitrogen accumulate in groundwater, it poses a risk of adverse health effects. Despite this recognition, estimation of LN from cropland soils in a broad spatial scale is still quite uncertain in China. The uncertainty of LN primarily stems from the shape of nitrogen leaching response to fertilizer additions (Nrate) and the role of environmental conditions. On the basis of 453 site-years at 51 sites across China, we explored the nonlinearity and variability of the response of LN to Nrate and developed an empirical statistical model to determine how environmental factors regulate the rate of N leaching (LR). The result shows that LN-Nrate relationship is convex for most crop types, and varies by local hydro-climates and soil organic carbon. Variability of air temperature explains a half (∼52%) of the spatial variation of LR. The results of model calibration and validation indicate that incorporating this empirical knowledge into a predictive model could accurately capture the variation in leaching and produce a reasonable upscaling from site to country. The fertilizer-induced LN in 2008 for China's cropland were 0.88 ± 0.23 TgN (1σ), significantly lower than the linear or uniform model, as assumed by Food and Agriculture Organization and MITERRA-EUROPE models. These results also imply that future policy to reduce N leaching from cropland needs to consider environmental variability rather than solely attempt to reduce Nrate.

Microcystin-LR (MC-LR), an important variant of cyanotoxin family, was frequently encountered in the contaminated aquatic environment and taken as a potent hepatotoxin. However, a little was known on the association between the long-term MC-LR exposure and lung damage. In this study, we investigated the changes of the pulmonary histopathology, mitochondrial DNA (mtDNA) integrity and the expression of mtDNA encoded genes in the mice with chronic exposed to MC-LR at different concentrations (1, 5, 10, 20 and 40 μg/L) for 12 months. Our results showed that the long-term and persistent exposure to MC-LR disturbed the balance of redox system, influenced mtDNA stability, changed the expression of mitochondrial genes in the lung cells. Notably, MC-LR exposure influenced the level of inflammatory cytokines and resulted in thickening of the alveolar septa. In conclusion, chronic exposure to MC-LR affected mtDNA maintenance, and caused lung impairment in mice.

Chlorothalonil is a broad spectrum fungicide with high annual production and environmental contamination. Despite its high consumption, studies regarding the potential ecological risks of chlorothalonil, especially its metabolites, to aquatic organisms are still limited. In this study, we selected the zebrafish (Danio rerio) as the in vivo model and first identified the metabolite (4-hydroxychlorothalonil) of chlorothalonil in zebrafish by tandem quadrupole/orthogonal-acceleration time-of-flight (Q-TOF). Then, the in vivo and in vitro models were applied to comprehensively estimate the embryo toxicity and potential endocrine effect of chlorothalonil and 4-hydroxychlorothalonil. The data from zebrafish embryo toxicity showed that the lowest observed effect concentrations of both chlorothalonil and 4-hydroxychlorothalonil were 50 μg/L after 96 h of exposure. The mortality rate of the 4-hydroxychlorothalonil was 2.6-fold higher than that of the parent compound at the concentration of 50 μg/L. Dual-luciferase reporter gene assays indicated that both chlorothalonil and 4-hydroxychlorothalonil exerted estrogen receptor α (ERα) agonist activity with REC20 values of 2.4 × 10−8 M and 3.6 × 10−8 M, respectively. However, only 4-hydroxychlorothalonil exhibited both thyroid receptor β (TRβ) agonistic and antagonistic activities. Lastly, we employed molecular docking to predict the binding affinity of chlorothalonil and 4-hydroxychlorothalonil with ERα or TRβ. The results revealed that the potential endocrine effect of chlorothalonil and 4-hydroxychlorothaloni might be attributed to the different binding affinities with the receptors. In conclusion, our studies revealed that 4-hydroxychlorothalonil exhibited potent endocrine-disrupting effects compared to its parent compound, chlorothalonil. The results provided here remind us that the assessment of the potential ecological and health risks of the metabolites of fungicides in addition to their parent compounds should arouse great concerns.

This study investigates, for the first time, the intestinal responses of European sea bass Dicentrarchus labrax chronically exposed to microplastics through ingestion. Fish (n = 162) were fed with 3 different treatment diets for 90 days: control, native polyvinyl chloride (PVC) and polluted polyvinyl chloride (PVC) pellets. Intestines were fixed and processed for histological analysis using standard techniques. Histopathological alterations were examined using a score value (from 0 to 4). The distal part of intestine in all samples proved to be the most affected by pathological alterations, showing a gradual change varying from moderate to severe related to exposure times. The histological picture that characterizes both groups especially after 90 days of exposure, suggests that the intestinal functions can be in some cases totally compromised.The worst condition is increasingly evident in the distal intestine of fish fed with polluted PVC pellets respect to control groups (p < 0.05) to different exposure times.These first results underline the need to assess the impact of increasing microplastics pollution on the marine trophic web.

Sediment samples collected from shelf, slope and interior basin of the northern Gulf of Mexico during 2011–2013, 1–3 years after the Deepwater Horizon (DWH) oil spill, were utilized to characterize PAH pollution history, in this region. Results indicate that the concentrations of surface ΣPAH43 and their accumulation rates vary between 44 and 160 ng g−1 and 6–55 ng cm−2 y−1, respectively. ΣPAH43 concentration profiles, accumulation rates and Δ14C values are significantly altered only for the sediments in the immediate vicinity of the DWH wellhead. This shows that the impact of DWH oil input on deep-sea sediments was generally limited to the area close to the spill site. Further, the PAHs source diagnostic analyses suggest a noticeable change in PAHs composition from higher to lower molecular weight dominance which reflects a change in source of PAHs in the past three years, back to the background composition. Results indicate low to moderate levels of PAH pollution in this region at present, which are unlikely to cause adverse effects on benthic communities.

Freshwater ecosystems are threatened by multiple anthropogenic stressors, which might be differentiated into two types: those that reduce biological activity at all concentrations (toxic contaminants), and those that subsidize biological activity at low concentrations and reduce it at high concentrations (assimilable contaminants). When occurring in mixtures, these contaminants can have either antagonistic, neutral or synergistic effects; but little is known on their joint effects. We assessed the interaction effects of a mixture of assimilable and toxic contaminants on stream biofilms in a manipulative experiment using artificial streams, and following a factorial design with three nutrient levels (low, medium or high) and either presence or absence of a mixture of emerging contaminants (ciprofloxacin, erythromycin, diclofenac, methylparaben, and sulfamethoxazole). We measured biofilm biomass, basal fluorescence, gross primary production and community respiration. Our initial hypotheses were that biofilm biomass and activity would: increase with medium nutrient concentrations (subsidy effect), but decrease with high nutrient concentrations (stress effect) (i); decrease with emerging contaminants, with the minimum decrease at medium nutrient concentrations (antagonistic interaction between nutrients subsidy and stress by emerging contaminants) and the maximum decrease at high nutrient concentrations (synergistic interaction between nutrients and emerging contaminants stress) (ii). All the measured variables responded linearly to the available nutrients, with no toxic effect at high nutrient concentrations. Emerging contaminants only caused weak toxic effects in some of the measured variables, and only after 3–4 weeks of exposure. Therefore, only antagonistic interactions were observed between nutrients and emerging contaminants, as medium and high nutrient concentrations partly compensated the harmful effects of emerging contaminants during the first weeks of the experiment. Our results show that contaminants with a subsidy effect can alleviate the effects of toxic contaminants, and that long-term experiments are required to detect stress effects of emerging contaminants at environmentally relevant concentrations.

This work develops a new approach for delineating sites that are contaminated by multiple soil heavy metals and applies it to a case study. First a number of contaminant sample data are transformed into multiple spatially un-correlated factors using Uniformly Weighted Exhaustive Diagonalization with Gauss iterations (U-WEDGE). Sequential Gaussian simulation (sGs) is then used to generate sets of realizations of each resultant factor. These are then transformed into sets of sGs contaminant distribution realizations, which are then used to analyze the local and spatial (global) uncertainties in the distribution and concentration of contaminants via joint simulation. Finally, Info-Gap Decision Theory (IGDT) is used to consider different monitoring and or remediation regimes based on the analysis of contaminant realization spatial uncertainty. In our case study each heavy metal contaminant was considered individually and together with all other heavy metals; as the number of heavy metals considered increased, higher critical proportion values of local probability were chosen to obtain a low global uncertainty (to provide high reliability). Info-Gap Decision Theory (IGDT) yielded the most appropriate critical proportion values which minimized information loss in terms of specific goals. When the false negative rate is set to zero, meaning that it is necessary to monitor all potentially polluted areas, the corresponding false positive rates are at least 63%, 65%, 66%, 68%, 70%, and 78% to yield robustness levels of 0.50, 0.60, 0.70, 0.80, 0.90, and 1.00 respectively. However, when the false negative rate tolerance threshold is raised to 50%, the false positive rate tolerance which yields robustness levels of 0.50, 0.60, 0.70, 0.80, 0.90 and 1.00 drop to 12%, 14%, 15%, 18%, 20%, and 39%. The case study demonstrates the effectiveness of the developed approach at making robust decisions concerning the delineation of sites contaminated by multiple heavy metals.

Application of empirical models to adsorption of contaminants on natural heterogeneous sorbents is often challenging due to the uncertainty associated with fitting experimental data and determining adjustable parameters. Sediment samples from contaminated and uncontaminated portions of a study site in Maine, USA were collected and investigated for adsorption of arsenate [As(V)]. Two kinetic models were used to describe the results of single solute batch adsorption experiments. Piecewise linear regression of data linearized to fit pseudo-first order kinetic model resulted in two distinct rates and a cutoff time point of 14–19 h delineating the biphasic behavior of solute adsorption. During the initial rapid adsorption stage, an average of 60–80% of the total adsorption took place. Pseudo-second order kinetic models provided the best fit to the experimental data (R2 > 0.99) and were capable of describing the adsorption over the entire range of experiments. Both Langmuir and Freundlich isotherms provided reasonable fits to the adsorption data at equilibrium. Langmuir-derived maximum adsorption capacity (St) of the studied sediments ranged between 29 and 97 mg/kg increasing from contaminated to uncontaminated sites. Solid phase As content of the sediments ranged from 3.8 to 10 mg/kg and the As/Fe ratios were highest in the amorphous phase. High-pH desorption experiments resulted in a greater percentage of solid phase As released into solution from experimentally-loaded sediments than from the unaltered samples suggesting that As(V) adsorption takes place on different reversible and irreversible surface sites.

Cytochrome P450 1A2 (CYP1A2) is an enzyme involved in the metabolic activation of certain carcinogens, and inducible by toxic substrates. To date, few studies have investigated in vivo CYP1A2 induction in humans and its relationship to polycylic aromatic hydrocarbons (PAHs) like benzo(a)pyrene (BaP). Non-smoking healthy male coke-oven workers (n = 30) were recruited as ‘exposure’ group, and non-smoking healthy office workers in the same city (n = 10) were selected as ‘control’ group, to test whether high inhalation exposure to PAHs can induce CYP1A2 activity in human livers. Significantly higher inhalation exposure of PAHs were found among the exposure group compared to the control. Inhalation BaP exposure concentration in the exposure group was more than 30 times higher than the control group (p < 0.001). However, the exposure group did not exhale significant higher levels of ¹³CO2/¹²CO2 in breath samples (p = 0.81), and no significant relationship was found between the inhaled BaP concentration and the ¹³CO2/¹²CO2 ratio (p = 0.91). A significant association was found between the ¹³CO2/¹²CO2 exhalation and dietary BaP intake level. Hepatic CYP1A2 activity/induction level was not effected by inhaled BaP but was altered by ingestion of BaP.

To determine if trinitrotoluene (TNT) forms nonextractable residues in mussels (Mytilus galloprovincialis) and fish (Cyprinodon variegatus) and to measure the relative degree of accumulation as compared to extractable TNT and its major metabolites, organisms were exposed to water fortified with 14C-TNT. After 24 h, nonextractable residues made up 75% (mussel) and 83% (fish) while TNT accounted for 2% of total radioactivity. Depuration half-lives for extractable TNT, aminodinitrotoluenes (ADNTs) and diaminonitrotoluenes (DANTs) were fast initially (<0.5 h), but slower for nonextractable residues. Nonextractable residues from organisms were identified as ADNTs and DANTs using 0.1 M HCL for solubilization followed by liquid chromatography-tandem mass spectrometry. Recovered metabolites only accounted for a small fraction of the bound residue quantified using a radiotracer likely because of low extraction or hydrolysis efficiency or alternative pathways of incorporation of radiolabel into tissue.