While environmental risk assessment is typically based on toxicant concentrations in water and/or sediment, awareness is increasing that internal concentrations or body burdens are the key to understand adverse effects in organisms. In order to link environmental micropollutants as causes of observed effects, there is an increasing demand for methods to analyse these chemicals in organisms. Here, a multi-target screening method based on pulverised liquid extraction (PuLE) and a modified QuEChERS approach with an additional hexane phase was developed. It is capable to extract and quantify organic micropollutants of diverse chemical classes in freshwater invertebrates. The method was tested on gammarids from the Danube River (within the Joint Danube Survey 3) and target compounds were analysed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Furthermore, a non-target screening using high resolution-tandem mass spectrometry (LC-HRMS/MS) was conducted. A total of 17 pollutants were detected and/or quantified in gammarids at low concentrations. Pesticide concentrations ranged from 0.1 to 6.52 ng g−1 (wet weight), those of wastewater-derived pollutants from 0.1 to 2.83 ng g−1 (wet weight). The presence of wastewater-derived pollutants was prominent at all spots sampled. Using non-target screening, we could successfully identify several chlorinated compounds. These results demonstrate for the first time the presence of pesticides and wastewater-derived pollutants in invertebrates of the Danube River.

This study investigates PM2.5-bound PAHs for rural sites (Dacheng and Fangyuan) positioned close to heavy air-polluting industries in Changhua County, central Taiwan. A total of 113 PM2.5 samples with 22 PAHs collected from 2014 to 2015 were analyzed, and Positive Matrix Factorization (PMF) and diagnostic ratios of PAHs were applied to quantify potential PAH sources. The influences of local and regional sources were also explored using the conditional probability function (CPF) and potential source contribution function (PSCF) with PMF-modeled results, respectively. Annual mean concentrations of total PAHs were 2.91 ± 1.34 and 3.04 ± 1.40 ng/m3 for Dacheng and Fangyuan, respectively, and their corresponding BaPeq were measured at 0.534 ± 0.255 and 0.563 ± 0.273 ng/m3 in concentration. Seasonal variations with higher PAHs found for the winter than for the spring and summer were observed for both sites. The lifetime excess cancer risk (ECR) from inhalation exposure to PAHs was recorded as 4.7 × 10−5 overall. Potential sources of PM2.5-bound PAHs include unburned petroleum and traffic emissions (42%), steel industry and coal combustion (31%), and petroleum and oil burning (27%), and unburned petroleum and traffic emission could contribute the highest ECR (2.4 × 10−5). The CPF results show that directional apportionment patterns were consistent with the actual locations of local PAH sources. The PSCF results indicate that mainly northeastern regions of China have contributed elevated PM2.5-bound PAHs from long-range transports.

With current global changes, the combination of several stressors such as temperature and contaminants may impact species distribution and ecosystem functioning. In this study, we evaluated the combined impact of two metals (Ni and Cr) with a thermal stress (from 12 to 17 °C) on biomarker responses in two bivalves, Dreissena rostriformis bugensis and Dreissena polymorpha. Biomarkers are informative tools to evaluate exposure and effects of stressors on organisms. The set of 14 biomarkers measured here was representative of both physiologic (filtration activity) and cellular antioxidant and detoxification mechanisms. Our aim was to study the response pattern of both species, and its meaning in terms of invasive potential. The implications for the use of these mussels in environmental monitoring are also discussed. Results evidenced that the two species do not respond to multiple stressors in the same way. Indeed, the effects of contamination on biomarker responses were more marked for D. polymorpha, especially under nickel exposure. While we cannot conclude as to the effect of temperature, invasiveness could be influenced by species sensitivity to contaminants. The physiological and cellular differences between D. polymorpha and D. r. bugensis might also be of concern for environmental risk assessment. The two species present differential bioaccumulation patterns, filtration activity and cellular biomarker responses. If D. polymorpha populations decline, their substitution by D. r. bugensis for biomonitoring or laboratory studies will not be possible without a deeper understanding of biomarker responses of the new invasive.

The South East Asian Melanesian (SEAM) region contains the world's largest deposits of nickel lateritic ores. Environmental impacts may occur if mining operations are not adequately managed. Effects data for tropical ecosystems are required to assess risks of contaminant exposure and to derive water quality guidelines (WQG) to manage these risks. Currently, risk assessment tools and WQGs for the tropics are limited due to the sparse research on how contaminants impact tropical biota. As part of a larger project to develop appropriate risk assessment tools to ensure sustainable nickel production in SEAM, nickel effects data were required. The aim of this review was to compile data on the effects of nickel on tropical marine, estuarine, pelagic and benthic species, with a particular focus on SEAM.There were limited high quality chronic nickel toxicity data for tropical marine species, and even fewer for those relevant to SEAM. Of the data available, the most sensitive SEAM species to nickel were a sea urchin, copepod and anemone. There is a significant lack of high quality chronic data for several ecologically important taxonomic groups including cnidarians, molluscs, crustaceans, echinoderms, macroalgae and fish. No high quality chronic nickel toxicity data were available for estuarine waters or marine and estuarine sediments. The very sparse toxicity data for tropical species limits our ability to conduct robust ecological risk assessment and may require additional data generation or read-across from similar species in other databases (e.g. temperate) to fill data gaps. Recommendations on testing priorities to fill these data gaps are presented.

High levels of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were detected in free-range eggs, and these levels reached a concentration of 29.84 ± 7.45 pg of WHO-TEQ/g of fat. This value exceeded the EU maximum permitted level of 2.5 pg of WHO-TEQ/g of fat for PCDD/F congeners by twelve-fold. A chemical analysis (HRGC-HRMS) revealed elevated amounts of OCDD, OCDF, HxCDD, HpCDD and HpCDF. During the investigation, samples of feed, soil, wall scrapings, wooden ceiling of the henhouse and tissues from laying hens were examined for dioxin contents (30 samples altogether). The long and complicated investigation found that the source of dioxins in the poultry farm was pentachlorophenol-treated wood, which was used as structural components in the 40-year-old farm building adapted to a henhouse. The wooden building material contained PCDD/Fs at a concentration of 3922.60 ± 560.93 pg of WHO-TEQ/g and 11.0 ± 2.8 μg/kg of PCP. The potential risk associated with dioxin intake was characterized by comparing the theoretically calculated weekly and monthly intakes with the toxicological reference values (TRVs), namely the Tolerable Weekly Intake (TWI) and Provisional Tolerable Monthly Intake (PTMI) values of 14 pg of WHO-TEQ/kg of bw and 70 pg of WHO-TEQ/kg of bw, respectively. The intake of dioxins estimated for high egg consumers (approximately 5–6 eggs/week) exceeded the TWI and PTMI values, which may pose a risk of delayed adverse health effects. The estimated dose of PCDD/Fs and DL-PCBs for children consuming 5 eggs per week exceeded the TWI by as much as 450% because of their nearly 5-fold-lower body weight. Although the dioxin intake estimated for the average consumption of eggs in the general population did not exceed any of the TRVs applied (58.7% TWI and 51.1% PTMI), such a situation should be considered unacceptable from a public health perspective because eggs are not the only source of these contaminants.

Classical laboratory-based single-species sediment bioassays do not account for modifications to toxicity from bioturbation by benthic organisms which may impact predictions of contaminated sediment risk to biota in the field. This study aims to determine the effects of bioturbation on the toxicity of zinc measured in a standard laboratory bioassay conducted with chironomid larvae (Chironomus tepperi). The epi-benthic chironomid larvae were exposed to two different levels of sediment contamination (1600 and 1980 mg/kg of dry weight zinc) in the presence or absence of annelid worms (Lumbriculus variegatus) which are known to be tolerant to metal and to have a large impact on sediment properties through bioturbation.Chironomids had 5–6x higher survival in the presence of L. variegatus which shows that bioturbation had a beneficial effect on the chironomid larvae. Chemical analyses showed that bioturbation induced a flux of zinc from the pore water into the water column, thereby reducing the bioavailability of zinc in pore water to the chironomid larvae. This also suggested that pore water was the major exposure path for the chironomids to metals in sediment. During the study, annelid worms (Oligochaetes) produced a thin layer of faecal pellets at the sediment surface, a process known to: (i) create additional adsorption sites for zinc, thus reducing its availability, (ii) increase the microbial abundance that in turn could represent an additional food source for opportunistic C. tepperi larvae, and (iii) modify the microbial community’s structure and alter the biogeochemical processes it governs thus indirectly impact zinc toxicity.This study represents a contribution in recognising bioturbating organisms as “ecological engineers” as they directly and indirectly influence metal bioavailability and impact other sediment-inhabiting species. This is significant and should be considered in risk assessment of zinc levels (and other metals) in contaminated sediment when extrapolating from laboratory studies to the field.

The probabilistic ecological risk assessment using terrestrial toxicity data has been mainly based on microfauna or mesofauna. Soil algae, which are food source for microfauna and mesofauna, may be alternatively used for assessing soil toxicity. However, there are no internationally recommended guidelines for soil algal bioassays, and the collection of algae from the test soils has some limitations. In this study, we suggested the paper-disc method as an easy-to-use alternative. This method has been widely used for testing the antibacterial toxicity of various chemicals in agar media by measuring the diameter of the inhibition zone around the disc. We adapted the paper-disc method for screening the toxicity of copper (Cu) and nickel (Ni) to the soil alga Chlorococcum infusionum using various evaluation endpoints, such as growth zone, chlorophyll fluorescence, and photosynthetic activity. Chlorophyll fluorescence and photosynthetic activity decreased with the increasing concentrations of Cu+2 or Ni+2 contaminated soils. Algal growth zone was analyzed visually and showed similar results to those of chlorophyll fluorescence. The direct ethanol extraction method and indirect culture medium extraction method were similarly effective; however, the former was easier to perform, while the latter might facilitate the analysis of additional endpoints in future studies. Overall, the results suggested that the paper-disc method was not only a user-friendly assay for screening soil toxicity, but also effective due to its association with indirect soil quality indicators.

Short chain perfluoroalkyl acids (PFAAs) have been developed since 2002 by the major manufacturers to replace the conventional C8 and higher homologues, with much of the world production shifted to China in recent years. In this study, we conducted a continuous monitoring program over the period 2011–2014 with seasonal monitoring in 2013 for PFAAs emitted from two rapidly developing fluorochemical industry parks located in the Daling River Basin, Northern China. The trend of PFAA contamination was identified, dominated by perfluorobutane sulfonic acid (PFBS), perfluorobutanoic acid (PFBA) and perfluorooctanoic acid (PFOA), with the maximum concentrations of 3.78 μg/L, 3.70 μg/L, and 1.95 μg/L, respectively. Seasonal monitoring uncovered the occasional emission of perfluorooctane sulfonic acid (PFOS). Construction trends of new facilities and associated manufacturing capacity of the main products were also analyzed to assess correlations with PFAA emissions. An assessment of the data over the period 2011–2014 found a positive correlation with fluorocarbon alcohol (FCA) production and emission of PFAAs. Groundwater and tap water around the main source indicated that the dominant PFAAs had different diffusion behaviors. PFBS levels were higher in surface water, while PFBA was dominant in groundwater and tap water, with PFOA levels being higher in downstream groundwater. Considering the continuous expansion and development of fluorochemical industry in the Daling River Basin, this study will provide abundant information on the effectiveness of risk assessment and management.

Pesticides generate transformation products (TPs) when they are released into the environment. These TPs may be of ecotoxicological importance. Past studies have demonstrated how difficult it is to predict the occurrence of pesticide TPs and their environmental risk. The monitoring approaches mostly used in current regulatory frameworks target only known ecotoxicologically relevant TPs. Here, we present a novel combined approach which identifies and categorizes known and unknown pesticide TPs in soil by combining suspect screening time-of-flight mass spectrometry with in silico molecular typology. We used an empirical and theoretical pesticide TP library for compound identification by both non-target and target time-of-flight (tandem) mass spectrometry, followed by structural proposition through a molecular structure correlation program. In silico molecular typology was then used to group TPs according to common molecular descriptors and to indirectly elucidate their environmental parameters by analogy to known pesticide compounds with similar molecular descriptors. This approach was evaluated via the identification of TPs of the triazole fungicide tebuconazole occurring in soil during a field dissipation study. Overall, 22 empirical and 12 yet unknown TPs were detected, and categorized into three groups with defined environmental properties. This approach combining suspect screening time-of-flight mass spectrometry with molecular typology could be extended to other organic pollutants and used to rationalize the choice of TPs to be investigated towards a more comprehensive environmental risk assessment scheme.

Short-chain chlorinated paraffins (SCCPs) are ubiquitous in the environment and might cause adverse environmental and human health effects. Little is known about the relative toxicity of different SCCP compounds especially during development. The objective of this study was to characterize and compare effects of seven SCCP groups at environmentally relevant levels, using a zebrafish (Danio rerio) model. Observations on malformation, survival rates at 96 h post fertilization (hpf), and hatching rates at 72 hpf indicated that the C10- groups (C10H18Cl4, 1,2,5,6,9,10-C10H16Cl6 and C10H15Cl7) were more toxic than the C12- groups (C12H22Cl4, C12H19Cl7 and 1,1,1,3,10,12,12,12-C12H18Cl8) and Cereclor 63L. The C10- groups were also more potent than C12- groups and Cereclor 63L in decreasing thyroid hormone levels. Among the three compounds within the C10- group, the compounds with less chlorine content had stronger effects on sub-lethal malformations but less effects on triiodothyronine (T3) and tetraiodothyronine (T4). Only C10H18Cl4 significantly decreased the mRNA expression of tyr, ttr, dio2 and dio3 at a dose-dependent manner suggesting that the specific mode of actions differ with different congeners. The mechanisms of disruption of thyroid status by different SCCPs could be different. C10H18Cl4 might inhibit T3 production through the inhibition effect on dio2. These results indicate that SCCP exposure could alter gene expression in the hypothalamic-pituitary-thyroid (HPT) axis and thyroid hormone levels. The mechanisms of disruption of thyroid status by different SCCPs could be different. Our results on the relative developmental toxicities of SCCPs will be useful to reach a better understanding of SCCP toxicity supporting environmental risk evaluation and regulation and used as a guidance for environmental monitoring of SCCPs in the future.