Trifluoroacetic acid (TFA) in the atmosphere is produced by degradation of hydrochlorofluorocarbons and hydrofluorocarbons. In recent years, TFA has attracted global attention because of increased environmental concentrations, biological toxicity and accumulation in aqueous environments. This study focused on the mechanisms underlying the adsorption of TFA by particulate matter to identify the appropriate descriptive model for this process and thus improve estimation of TFA adsorption in future environmental monitoring. Onsite gas and particle phase sampling in Beijing, China, and subsequent measurement of TFA concentrations indicated that the TFA concentration in the gas phase (1396 ± 225 pg m−3) was much higher than that in the particle phase (62 ± 8 pg m−3) and that monthly concentrations varied seasonally with temperature. Based on the field results and analysis, an adsorption experiment of TFA on soot was then conducted at three different temperatures (293, 303, and 313 K) to provide parameters for kinetic and thermodynamic modelling. The proportion of atmospheric TFA concentration in the gas phase increased with temperature, indicating that temperature affected the phase distribution of TFA. The subsequent kinetic and thermodynamic modelling showed that the adsorption of TFA by soot could be described well by the Bangham kinetic model. The adsorption was controlled by diffusion, and the key mechanism was physical adsorption. The adsorption behavior can be well described by the Langmuir isotherm model. The calculated thermodynamic parameters ΔG° (−2.34, −1.25, and −0.15 kJ mol−1 at 293, 303, and 313 K, respectively), ΔH° (−34.34 kJ mol−1), and ΔS° (−109.22 J mol−1 K−1) for TFA adsorption by soot were negative, indicating that adsorption was a spontaneous, exothermic process.

Zebra mussels (Dreissena polymorpha) were exposed to polyvinylpyrrolidone (PVP)-coated silver nanoparticles (AgNP; hydrodynamic diameter 80 nm; solid diameter 50 nm) to investigate the behavior of Ag in the tank water with respect to its uptake, bioaccumulation, elimination and subcellular distribution in the mussel soft tissue. Parallel experiments were performed with ionic Ag (AgNO3) to unravel possible differences between the metal forms. The recovery of the applied Ag concentration (500 μg/L) in the tank water was clearly affected by the metal source (AgNP < AgNO3) and water type (reconstituted water < tap water). Filtration (<0.45 μm) of water samples showed different effects on the quantified metal concentration depending on the water type and Ag form. Ag accumulation in the mussel soft tissue was neither influenced by the metal source nor by the water type. Ag concentrations in the mussel soft tissue did not decrease during 14 days of depuration. For both metal forms the Ag distribution within different subcellular fractions, i.e. metal-rich granules (MRG), cellular debris, organelles, heat-sensitive proteins (HSP) and metallothionein-like proteins (MTLP), revealed time-dependent changes which can be referred to intracellular Ag translocation processes. The results provide clear evidence for the uptake of Ag by the mussel soft tissue in nanoparticulate as well as in ionic form. Thus, zebra mussels could be used as effective accumulation indicators for environmental monitoring of both Ag forms.

Polyhalogenated carbazoles (PHCZs) have attracted mounting environmental concerns since they were recently discovered in sediments and soil. Current knowledge on their occurrence, environmental behavior and fate remains very limited in general. In the present study, 11 PHCZ congeners were screened in surface sediments of Lake Tai, an important freshwater system located in the Yangtze River Delta, China. Total concentrations of PHCZs (∑PHCZs) ranged up to 15.8 ng/g dry weight (median: 1.54 ng/g dw), rivaling those of polybrominated diphenyl ethers (∑PBDEs, 0.07–15.9 ng/g dw) in the same sediments. The PHCZ congener composition profiles revealed a dominance of 3,6-dichlorocarbazole and 3,6-dibromocarbazole with comparable concentrations. These two dominant congeners differed in spatial distribution patterns in Lake Tai, indicating different sources or origins. Potential toxic effects associated with the levels of PHCZs in the sediments were evaluated via the toxic equivalent (TEQ) approach. The TEQs of PHCZs in Lake Tai sediments ranged up to 1.36 pg TEQ/g dw. As the first report on the occurrence of PHCZs in an Asian waterbody, our findings suggest that PHCZs should be given more attention during environmental monitoring and risk assessments of hazardous chemicals, as they may represent another group of persistent organic pollutants with dioxin-like effects and wide distributions.

In this study, a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method coupled with UPLC-QqQ-MS/MS analysis was developed to detect tebuthiuron in sugarcane fields and the surrounding aquatic ecosystems. Methodological validation showed the method developed was of favorable sensitivity, reproducibility and accuracy. For assessment of its dietary and ecological risks, dissipation and occurrence of tebuthiuron in situ were further investigated through a supervised field trial and an aquatic environment monitoring carried out in six dominant sugarcane production regions in South China. After application at the range of recommended dose, tebuthiuron dominantly distributed in soil, and then dissipated in accordance with the first-order rate model with the half-lives of 12.2–21.5 d. At pre-harvest intervals (PHI), occurrence of tebuthiuron was found to be 0.718–1.366 mg/kg and 0.016–0.034 mg/kg, in sugarcane and soil, respectively. The supervised trials median residue (STMR) of tebuthiuron in sugarcane was thus 0.024 mg/kg and the dietary Risk Quotient (RQd) was accordingly calculated as 2.34 × 10−4, indicating safety on long-term consumption of sugarcane with tebuthiuron residues. Yet high risks of tebuthiuron towards soil ecosystems was noticed as it possessed maximum ecological Risk Quotient (RQe) at 1.97 to earthworms. In sugarcane field-surrounding aquatic environment, distribution of tebuthiuron was found to range from 0.007 mg/L to 0.022 mg/L, leading to high risk towards the aquatic ecosystem due to the maximum RQe at 440 to algae, irrespective of its low risks to invertebrate and fish. Taken together, our approach serve as an effective tool for monitoring residual tebuthiuron environmentally and also advance in-depth understanding of dietary and ecological risks posed by the phenylurea herbicide.

In response to the restrictions of polybrominated diphenyl ether (PBDE) flame retardants in various consumer products, alternative halogenated flame retardants have been subjected to increased use. Compared to aquatic ecosystems, relatively little information is available on the contamination of alternative flame retardants in terrestrial ecosystems, especially with regards to mammalian wildlife. In this study we used a top terrestrial carnivore, the bobcat (Lynx rufus), as a unique biomonitoring species for assessing flame retardant contamination in the Midwestern United States (U.S.) terrestrial ecosystems. Concentrations of ∑PBDEs (including all detectable PBDE congeners) ranged from 8.3 to 1920 ng/g lipid weight (median: 50.3 ng/g lw) in livers from 44 bobcats collected during 2013–2014 in Illinois. Among a variety of alternative flame retardants screened, Dechloranes (including anti- and syn-Dechlorane Plus and Dechlorane-602, 603, and 604), tetrabromo-o-chlorotoluene (TBCT), and hexabromocyclododecane (HBCD) were also frequently detected, with median concentrations of 28.7, 5.2, and 11.8 ng/g lw, respectively. Dechlorane analogue compositions in bobcats were different from what has been reported in other studies, suggesting species- or analogue-dependent bioaccumulation, biomagnification, or metabolism of Dechlorane chemicals in different food webs. Our findings, along with previously reported food web models, suggest Dechloranes may possess substantial bioaccumulation and biomagnification potencies in terrestrial mammalian food webs. Thus, attention should be given to these highly bioavailable flame retardants in future environmental biomonitoring and risk assessments in a post-PBDE era.

Microplastics (MPs) represent a matter of growing concern for the marine environment. Their ingestion has been documented in several species worldwide, but the impact of specific anthropogenic activities remains largely unexplored. In this study, MPs were characterized in different benthic fish sampled after 2.5 years of huge engineering operations for the parbuckling project on the Costa Concordia wreck at Giglio Island. Fish collected in proximity of the wreck showed a high ingestion of microplastics compared to both fish from a control area and values reported worldwide. Also the elevated percentage of nylon, polypropylene lines and the presence of polystyrene are quite unusual for marine organisms sampled in natural field conditions, thus supporting the possible relationship of ingested microplastics with maritime operations during wreck removal. On the other hand, the use of transplanted mussels revealed a lower frequency of ingested MPs, and did not discriminate differences between the wreck and the control area. Some variations were observed in terms of typology and size of particles between surface- and bottom-caged mussels highlighting the influence of a different distribution of MPs along the water column. In conclusion, this study demonstrated that MPs pollution in the area of Costa Concordia was more evident on benthonic environment than on seawater column, providing novel insights on the possibility of using appropriate sentinel organisms for monitoring specific anthropogenic sources of MPs pollution in the marine environment.

Invertebrate-mediated leaf litter decomposition is frequently used to assess stress-related implications in stream ecosystem integrity. In situ measures such as the mass loss from leaf bags or the feeding of caged invertebrates deployed for days or weeks may, however, fail to detect transient effects due to recovery or compensatory mechanisms. We assessed the relevance of transient effects using the peak exposure towards an insecticide (i.e., etofenprox) as a model scenario at three levels of complexity. These were 1) the assessment of the decomposition realised by invertebrate communities in stream mesocosms over 21 days via leaf bags, 2) 7-days lasting in situ bioassays quantifying the leaf consumption of Gammarus fossarum, and 3) a laboratory experiment determining the daily feeding rate of the same species over 7 days. Etofenprox did not trigger a significantly altered decomposition by invertebrate communities during the leaf bag assay, while in situ bioassays detected a significant reduction in gammarids’ feeding rate at the highest tested concentration. The laboratory bioassay suggests that observed mismatches might be explained by recovery and post-exposure compensation. As leaf-shredding invertebrates are likely in a vulnerable state following transient effects, biomonitoring for implications of peak exposures and other pulsed stress events must happen at an adequate temporal resolution.

Human presence in the Antarctic is increasing due to research activities and the rise in tourism. These activities contribute a number of potentially hazardous substances. The aim of this study is to conduct the first characterisation of the pharmaceuticals and recreational drugs present in the northern Antarctic Peninsula region, and to assess the potential environmental risk they pose to the environment. The study consisted of a single sampling of ten water samples from different sources, including streams, ponds, glacier drains, and a wastewater discharge into the sea. Twenty-five selected pharmaceuticals and 21 recreational drugs were analysed. The highest concentrations were found for the analgesics acetaminophen (48.74 μg L−1), diclofenac (15.09 μg L−1) and ibuprofen (10.05 μg L−1), and for the stimulant caffeine (71.33 μg L−1). All these substances were detected in waters that were discharged directly into the ocean without any prior purification processes. The hazard quotient (HQ) values for ibuprofen, diclofenac and acetaminophen were far in excess of 10 at several sampling points. The concentrations of each substance measured and used as measured environmental concentration values for the HQ calculations are based on a one-time sampling. The Toxic Unit values indicate that analgesics and anti-inflammatories are the therapeutic group responsible for the highest toxic burden.This study is the first to analyse a wide range of substances and to determine the presence of pharmaceuticals and psychotropic drugs in the Antarctic Peninsula region. We believe it can serve as a starting point to focus attention on the need for continued environmental monitoring of these substances in the water cycle, especially in protected regions such as the Antarctic. This will determine whether pharmaceuticals and recreational drugs are hazardous to the environment and, if so, can be used as the basis for risk-assessment studies to prioritise the exposure to risk.

In this study we examined 6080 data gathered by our research group during more than 20 years of research on the moss biomonitoring technique, in order to quantify the variability generated by different aspects of the protocol and to calculate the overall measurement uncertainty associated with the technique. The median variance of the concentrations of different pollutants measured in moss tissues attributed to the different methodological aspects was high, reaching values of 2851 (ng·g⁻¹)² for Cd (sample treatment), 35.1 (μg·g⁻¹)² for Cu (sample treatment), 861.7 (ng·g⁻¹)² and for Hg (material selection). These variances correspond to standard deviations that constitute 67, 126 and 59% the regional background levels of these elements in the study region. The overall measurement uncertainty associated with the worst experimental protocol (5 subsamples, refrigerated, washed, 5 × 5 m size of the sampling area and once a year sampling) was between 2 and 6 times higher than that associated with the optimal protocol (30 subsamples, dried, unwashed, 20 × 20 m size of the sampling area and once a week sampling), and between 1.5 and 7 times higher than that associated with the standardized protocol (30 subsamples and once a year sampling). The overall measurement uncertainty associated with the standardized protocol could generate variations of between 14 and 47% in the regional background levels of Cd, Cu, Hg, Pb and Zn in the study area and much higher levels of variation in polluted sampling sites. We demonstrated that although the overall measurement uncertainty of the technique is still high, it can be reduced by using already well defined aspects of the protocol. Further standardization of the protocol together with application of the information on the overall measurement uncertainty would improve the reliability and comparability of the results of different biomonitoring studies, thus extending use of the technique beyond the context of scientific research.

This study presents the occurrence and impact of 78 anticancer drugs compounds in Spanish river basins based on consumption data during the period 2010–2015 and calculation of the predicted environmental concentrations (PEC). The total consumption of anticancer drugs in Spanish pharmacies was of 23.4 tons in 2015, being mycophenolic acid and hydroxycarbamide the drugs with the highest prescription. Their PECs in river at national scale were up to 80 ng/L. However, the use of different dilution factors revealed major differences between hydrographic basins, and PECriver rose up to 68,014 ng/L in highly populated rivers with low flows. Concerning acute toxicity, there was no expected risk for the aquatic environment. However, chronic toxicity tests revealed possible long-term mutagenic effects for aquatic organisms. This study provides the tools for the estimation of PEC at river basin scale using time trend consumption data compilation. This information is very useful for prioritization of compounds of concern and permit to focus resources in environmental monitoring and risk evaluation.