Mercury (Hg) concentrations in freshwater fish relates to aquatic Hg concentrations, which largely derives from soil stores of accumulated atmospheric deposition. Hg in catchment soils as a source for aquatic Hg is poorly studied. Here we test if i) peatland soils produce more methylmercury (MeHg) than forest soils; ii) total Hg (THg) concentrations in top soils are determined by atmospheric inputs, while MeHg is produced in the soils; and iii) soil disturbance promotes MeHg production. In two small boreal catchments, previously used in a paired-catchment forest harvest manipulation study, forest soils and peatlands were sampled and analysed for Hg species and additional soil chemistry. In the undisturbed reference catchment, soils were sampled in different vegetation types, of varying productivity as reflected in tree density, where historical data on precipitation and throughfall Hg and MeHg fluxes were available. Upper soil THg contents were significantly correlated to throughfall inputs of Hg, i.e. lowest in the tree-less peatland and highest in the dense spruce forest. For MeHg, top layer concentrations were similar in forest soils and peatlands, likely related to atmospheric input and local production, respectively. The local peatland MeHg production was documented through significantly higher MeHg-to-THg ratios in the deeper soil layer samples. In the disturbed catchment, soils were sampled in and just outside wheeltracks in an area impacted by forest machinery. Here, MeHg concentrations and the MeHg-to-THg ratios in the upper 5 cm were weakly significantly (p = 0.07) and significantly (p = 0.04) different in and outside of the wheeltracks, respectively, suggesting that soil disturbance promotes methylation. Differences in catchment Hg and MeHg streamwater concentrations were not explained by soil Hg and MeHg information, perhaps because hydrological pathways are a stronger determinant of streamwater chemistry than small variations in soil chemistry driven by disturbance and atmospheric inputs of Hg.

Elevated manganese (Mn) in drinking water has been reported worldwide. While, naturally occurring Mn in groundwater is generally the major source, anthropogenic contamination by Mn-containing fungicides such as mancozeb may also occur. The main objective of this study was to examine factors associated with Mn and ethylenethiourea (ETU), a degradation product of mancozeb, in drinking water samples from villages situated near banana plantations with aerial spraying of mancozeb. Drinking water samples (n = 126) were obtained from 124 homes of women participating in the Infants' Environmental Health Study (ISA, for its acronym in Spanish), living nearby large-scale banana plantations. Concentrations of Mn, iron (Fe), arsenic (As), lead (Pb), cadmium (Cd) and ethylenethiourea (ETU), a degradation product of mancozeb, were measured in water samples. Only six percent of samples had detectable ETU concentrations (limit of detection (LOD) = 0.15 μg/L), whereas 94% of the samples had detectable Mn (LOD = 0.05 μg/L). Mn concentrations were higher than 100 and 500 μg/L in 22% and 7% of the samples, respectively. Mn was highest in samples from private and banana farm wells. Distance from a banana plantation was inversely associated with Mn concentrations, with a 61.5% decrease (95% CI: −97.0, −26.0) in Mn concentrations for each km increase in distance. Mn concentrations in water transported with trucks from one village to another were almost 1000 times higher than Mn in water obtained from taps in houses supplied by the same well but not transported, indicating environmental Mn contamination. Elevated Mn in drinking water may be partly explained by aerial spraying of mancozeb; however, naturally occurring Mn in groundwater, and intensive agriculture may also contribute. Drinking water risk assessment for mancozeb should consider Mn as a health hazard. The findings of this study evidence the need for health-based World Health Organization (WHO) guidelines on Mn in drinking water.

Mining activities have introduced various pollutants to surrounding aquatic and terrestrial environments, causing adverse impacts to the environment. Indigenous microbial communities are responsible for the biogeochemical cycling of pollutants in diverse environments, indicating the potential for bioremediation of such pollutants. Antimony (Sb) has been extensively mined in China and Sb contamination in mining areas has been frequently encountered. To date, however, the microbial composition and structure in response to Sb contamination has remained overlooked. Sb and As frequently co-occur in sulfide-rich ores, and co-contamination of Sb and As is observed in some mining areas. We characterized, for the first time, the microbial community profiles and their responses to Sb and As pollution from a watershed heavily contaminated by Sb tailing pond in Southwest China. The indigenous microbial communities were profiled by high-throughput sequencing from 16 sediment samples (535,390 valid reads). The comprehensive geochemical data (specifically, physical-chemical properties and different Sb and As extraction fractions) were obtained from river water and sediments at different depths as well. Canonical correspondence analysis (CCA) demonstrated that a suite of in situ geochemical and physical factors significantly structured the overall microbial community compositions. Further, we found significant correlations between individual phylotypes (bacterial genera) and the geochemical fractions of Sb and As by Spearman rank correlation. A number of taxonomic groups were positively correlated with the Sb and As extractable fractions and various Sb and As species in sediment, suggesting potential roles of these phylotypes in Sb biogeochemical cycling.

There is limited information on the BDE-209 relative bioavailability (RBA) of indoor dust and the absorption of BDE-209 after in vitro digestion was seldom studied. In the present study, BDE-209 RBA in 6 household dust samples measured using an in vivo mouse model was compared to BDE-209 bioaccessibility determined using physiologically based extraction test (PBET) and solubility bioaccessibility research consortium method (SBRC) assays. BDE-209 RBA obtained ranged from 45.9 ± 16.1 to 96.0 ± 17.4% and exhibited a significant relationship with PBET gastric phase (r2 = 0.578, p = 0.080), small intestinal phase (r2 = 0.728, p = 0.031) and total BDE-209 bioaccessibility (r2 = 0.728, p = 0.031), which indicated PBET assay can serve as a surrogate to predict BDE-209 RBA to refine human health exposure. In addition, the absorption of BDE-209 by Caco-2 cell line was assessed. With the consideration of the corresponding bioaccessibility and absorption of BDE-209 by Caco-2 cell line, the human daily intake of BDE-209 via dust ingestion for adults and children was much lower than that estimated by total concentration.

Polycyclic aromatic hydrocarbons (PAHs) in the atmosphere can partition into agricultural crops, which poses a potential risk to human health through the food chain. In this study, controlled chamber experiments were conducted to investigate the kinetic uptake of anthracene (Ant), phenanthrene (Phe), fluoranthene (Fla) and pyrene (Pyr), individually or as a mixture, by the leaf surfaces of living soybean and corn seedlings using the excitation-emission matrix (EEM) coupled with three-way parallel factor analysis (PARAFAC) and n-way partial least squares (n-PLS). The four selected PAHs achieved equilibrium between the air and the two living crop leaf surfaces over the 15-day monitoring period. Inter-species and inter-chemical variability existed in terms of the time required to achieve equilibrium, mass transfer coefficients (kAL) and the equilibrated adsorption capacity (EAC), which was mainly attributed to the different lg KOA values among the four PAHs and the variable leaf-wax content between the soybean and corn species. Compared with when the PAHs existed singly, the time required to achieve adsorption equilibrium was longer while the EAC was reduced for each of the four PAHs in a mixture, which was attributed to competitive adsorption among the coexisting components. These findings prove that the novel analytical method provides a novel platform for the in situ characterization of the environmental behaviors of multiple PAHs, with their spectra overlapping, between the air and plant skin. The coexistence of multiple PAHs in the air inhibits their individual uptake capacity by crop leaf skin, but increases the total adsorption of PAHs, potentially reducing crop security and increasing human health risk via the terrestrial food web.

It has been hypothesised that, if ingested, plastic debris could act as vector for the transfer of chemical contaminants from seawater to organisms, yet modelling suggest that, in the natural environment, chemical transfer would be negligible compared to other routes of uptake. However, to date, the models have not incorporated consideration of the role of gut surfactants, or the influence of pH or temperature on desorption, whilst experimental work has shown that these factors can enhance desorption of sorbed contaminants several fold. Here, we modelled the transfer of sorbed organic contaminants dichlorodiphenyltrichloroethane (DDT), phenanthrene (Phe) and bis-2-ethylhexyl phthalate (DEHP) from microscopic particles of polyvinylchloride (PVC) and polyethylene (PE) to a benthic invertebrate, a fish and a seabird using a one-compartment model OMEGA (Optimal Modelling for EcotoxicoloGical Applications) with different conditions of pH, temperature and gut surfactants. Environmental concentrations of contaminants at the bottom and the top of published ranges were considered, in combination with ingestion of either 1 or 5% by weight of plastic. For all organisms, the combined intake from food and water was the main route of exposure for Phe, DEHP and DDT with a negligible input from plastic. For the benthic invertebrate, predictions including the presence of contaminated plastic resulted in very small increases in the internal concentrations of DDT and DEHP, while the net change in the transfer of Phe was negligible. While there may be scenarios in which the presence of plastic makes a more important contribution, our modelling study suggests that ingestion of microplastic does not provide a quantitatively important additional pathway for the transfer of adsorbed chemicals from seawater to biota via the gut.

In 2014, as an attempt to address the Zika health crisis by controlling the mosquito population, Brazil took the unprecedented action of applying a chemical larvicide, pyriproxyfen, to drinking water sources. The World Health Organization has established an acceptable daily intake of pyriproxyfen to be 100 μg per kg of body weight per day, but studies have demonstrated that at elevated doses (>5000 mg/kg), there are adverse effects in mice, rats and dogs. To better understand the potential developmental toxicity of pyriproxyfen, we utilized the embryonic zebrafish. Our results demonstrate that the concentration resulting in 50% of animals presenting adverse morphological effects (EC50), including craniofacial defects, was 5.2 μM for daily renewal exposure, and above this concentration, adverse behavioral effects were also observed in animals that followed a static exposure regimen. Thus, zebrafish data suggest that the developmental toxicity of pyriproxyfen may not be limited to insects.

The unintended influence of exhaust plumes emitted from a vehicle ahead to on-road air quality surveying data measured with a mobile laboratory (ML) at 20–40 km h−1 in dense traffic areas was investigated by experiment and life-sized computational fluidic dynamics (CFD) simulation. The ML equipped with variable sampling inlets of five columns by four rows was used to measure the spatial distribution of CO2 and NOx concentrations when following 5–20 m behind a sport utility vehicle (SUV) as an emitter vehicle equipped with a portable emission monitoring system (PEMS). The PEMS measured exhaust gases at the tailpipe for input data of the CFD simulations. After the CFD method was verified with experimental results of the SUV, dispersion of exhaust plumes emitted from a bus and a sedan was numerically analyzed.More dilution of the exhaust plume was observed at higher vehicle speeds, probably because of eddy diffusion that was proportional to turbulent kinetic energy and vehicle speed. The CO2 and NOx concentrations behind the emitter vehicle showed less overestimation as both the distance between the two vehicles and their background concentrations increased. If the height of the ML inlet is lower than 2 m and the ML travels within 20 m behind a SUV and a sedan ahead at 20 km h−1, the overestimation should be considered by as much as 200 ppb in NOx and 80 ppm in CO2. Following a bus should be avoided if possible, because effect of exhaust plumes from a bus ahead could not be negligible even when the distance between the bus and the ML with the inlet height of 2 m, was more than 40 m. Recommendations are provided to avoid the unintended influence of exhaust plumes from vehicles ahead of the ML during on-road measurement in urban dense traffic conditions.

Trace element profiling in the incrementally formed dentine of mammalian teeth can be applied to reconstruct temporal variation of incorporation of these elements into the tissue. Using an electron microprobe, this study analysed fluoride distribution in dentine of first and third mandibular molars of free-ranging eastern grey kangaroos inhabiting a high-fluoride area, to assess temporal variation in fluoride uptake of the animals. Fluoride content in the early-formed dentine of first molars was significantly lower than in the late-formed dentine of these teeth, and was also lower than in both, the early and the late-formed dentine of third molars. As early dentine formation in M1 takes place prior to weaning, this finding indicates a lower dentinal fluoride uptake during the pre-weaning compared to the post-weaning period. This is hypothetically attributed to the action of a partial barrier to fluoride transfer from blood to milk in lactating females and a low bioavailability of fluoride ingested together with milk. Another factor contributing to lower plasma fluoride levels in juveniles compared to adults is the rapid clearance of fluoride from blood plasma in the former due to their intense skeletal growth. The combined action of these mechanisms is considered to explain why in kangaroos from high-fluoride areas, the (early-formed) first molars are not affected by dental fluorosis while the (later-formed) third and fourth molars regularly exhibit marked to severe fluorotic lesions.

The second‒order rate constants (k) of hydroxyl radical (·OH) with polychlorinated biphenyls (PCBs) in the gas phase are of scientific and regulatory importance for assessing their global distribution and fate in the atmosphere. Due to the limited number of measured k values, there is a need to model the k values for unknown PCBs congeners. In the present study, we developed a quantitative structure–activity relationship (QSAR) model with quantum chemical descriptors using a sequential approach, including correlation analysis, principal component analysis, multi−linear regression, validation, and estimation of applicability domain. The result indicates that the single descriptor, polarizability (α), plays an important role in determining the reactivity with a global standardized function of lnk = −0.054 × α ‒ 19.49 at 298 K. In order to validate the QSAR predicted k values and expand the current k value database for PCBs congeners, an independent method, density functional theory (DFT), was employed to calculate the kinetics and thermodynamics of the gas‒phase ·OH oxidation of 2,4′,5-trichlorobiphenyl (PCB31), 2,2′,4,4′-tetrachlorobiphenyl (PCB47), 2,3,4,5,6-pentachlorobiphenyl (PCB116), 3,3′,4,4′,5,5′-hexachlorobiphenyl (PCB169), and 2,3,3′,4,5,5′,6-heptachlorobiphenyl (PCB192) at 298 K at B3LYP/6–311++G**//B3LYP/6–31 + G** level of theory. The QSAR predicted and DFT calculated k values for ·OH oxidation of these PCB congeners exhibit excellent agreement with the experimental k values, indicating the robustness and predictive power of the single–descriptor based QSAR model we developed.