Recent efforts have been directed towards better understanding the persistency and toxicity of ionic liquids (ILs) in the context of the “benign-by-design” approach, but the assessment of their bioaccumulation potential remains neglected. This paper reports the experimental membrane partitioning of IL cations (imidazolium, pyridinium, pyrrolidinium, phosphonium), anions ([C(CN)3]-, [B(CN)4]-, [FSO2)2N]-, [(C2F5)3PF3]-, [(CF3SO2)2N]-) and their combinations as a measure for estimating the bioconcentration factor (BCF). Both cations and anions can have a strong affinity for phosphatidylcholine bilayers, which is mainly driven by the hydrophobicity of the ions. This affinity is often reflected in the ecotoxicological impact. Our data revealed that the bioconcentration potential of IL cations and anions is much higher than expected from octanol-water-partitioning based estimations that have recently been presented. For some ILs, the membrane-water partition coefficient reached levels corresponding to BCFs that might become relevant in terms of the “B” (bioaccumulation potential) classification under REACH. However, this preliminary estimation need to be confirmed by in vivo bioconcentration studies.

The presence of organic pollutants in the aquatic environment, usually found at trace concentrations (i.e., between ng L−1 and μg L−1 or even lower, known as micropollutants), has been highlighted in recent decades as a worldwide environmental concern due to their difficult elimination by conventional water and wastewater treatment processes. The relevant information on constructed wetlands (CWs) and their application for the removal of a specific group of pollutants, 41 organic priority substances/classes of substances (PSs) and 8 certain other substances with environmental quality standards (EQS) listed in Directive 2013/39/EU as well as 17 contaminants of emerging concern (CECs) of the Watch List of Decision 2015/495/EU, is herein reviewed. Studies were found for 24 PSs and 2 other substances with EQS: octylphenol, nonylphenol, perfluorooctane sulfonic acid, di(2-ethylhexyl)phthalate, trichloromethane, dichloromethane, 1,2-dichloroethane, pentachlorobenzene, benzene, polychlorinated dibenzo-p-dioxins, naphthalene, fluoranthene, trifluralin, alachlor, isoproturon, diuron, tributyltin compounds, simazine, atrazine, chlorpyrifos (chlorpyrifos-ethyl), chlorfenvinphos, hexachlorobenzene, pentachlorophenol, endosulfan, dichlorodiphenyltrichloroethane (or DDT) and dieldrin. A few reports were also published for 8 CECs: imidacloprid, erythromycin, clarithromycin, azithromycin, diclofenac, estrone, 17-beta-estradiol and 17-alpha-ethinylestradiol. No references were found for the other 17 PSs, 6 certain other substances with EQS and 9 CECs listed in EU legislation.

Much effort has been made to standardise sampling procedures, laboratory analysis, data analysis, etc. for semi volatile organic contaminants (SVOCs). Yet there are some unresolved issues in regards to comparing measurements from one of the most commonly used passive samplers (PAS), the polyurethane foam (PUF) disk PAS (PUF-PAS), between monitoring networks or different studies. One such issue is that there is no universal means to derive a sampling rate (Rs) or to calculate air concentrations (Cair) from PUF-PAS measurements for SVOCs. Cair was calculated from PUF-PAS measurements from a long-term monitoring program at a site in central Europe applying current understanding of passive sampling theory coupled with a consideration for the sampling of particle associated compounds. Cair were assessed against concurrent active air sampler (AAS) measurements. Use of “site-based/sampler-specific” variables: Rs, calculated using a site calibration, provided similar results for most gas-phase SVOCs to air concentrations derived using “default” values (commonly accepted Rs). Individual monthly PUF-PAS-derived air concentrations for the majority of the target compounds were significantly different (Wilcoxon signed-rank (WSR) test; p < 0.05) to AAS regardless of the input values (site/sampler based or default) used to calculate them. However, annual average PUF-PAS-derived air concentrations were within the same order of magnitude as AAS measurements except for the particle-phase polycyclic aromatic hydrocarbons (PAHs). Underestimation of PUF-derived air concentrations for particle-phase PAHs was attributed to a potential overestimation of the particle infiltration into the PUF-PAS chamber and underestimation of the particle bound fraction of PAHs.

Humpback whales, Megaptera novaeangliae, breeding off la Reunion Island (Indian Ocean) undergo large-scale seasonal migrations between summer feeding grounds near Antarctica and their reproductive winter grounds in the Indian Ocean. The main scope of the current study was to investigate chemical exposure of humpback whales breeding in the Indian Ocean by providing the first published data on this breeding stock concerning persistent organic pollutants (POPs), namely polychlorinated biphenyls (PCBs), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs), DDT and its metabolites (DDTs), chlordane compounds (CHLs), polybrominated diphenyl ethers (PBDEs), and methoxylated PBDEs (MeO-PBDEs). Analyses of stable isotopes δ13C and δ15N in skin resulted in further insight in their feeding ecology, which was in agreement with a diet focused mainly on low trophic level prey species, such as krill from Antarctica. POPs were measured in all humpback whales in the order of HCB > DDTs > CHLs > HCHs > PCBs > PBDEs > MeO-BDEs. HCB (median: 24 ng g−1 lw) and DDTs (median: 7.7 ng g−1 lw) were the predominant compounds in all whale biopsies. Among DDT compounds, p,p′-DDE was the major organohalogenated pollutant, reflecting its long-term accumulation in humpback whales. Significantly lower concentrations of HCB and DDTs were found in females than in males (p < 0.001). Other compounds were similar between the two genders (p > 0.05). Differences in the HCB and DDTs suggested gender-specific transfer of some compounds to the offspring. POP concentrations were lower than previously reported results for humpback whales sampled near the Antarctic Peninsula, suggesting potential influence of their nutritional status and may indicate different exposures of the whales according to their feeding zones. Further investigations are required to assess exposure of southern humpback whales throughout their feeding zones.

This study evaluates the in-situ use of field portable X-ray Fluorescence (pXRF) for metal-contaminated site assessments, and assesses the advantages of increased sampling to reduce risk, and increase confidence of decision making at a lower cost. Five metal-contaminated sites were assessed using both in-situ pXRF and ex-situ inductively coupled plasma mass spectrometry (ICP–MS) analyses at various sampling resolutions. Twenty second in-situ pXRF measurements of Mn, Zn and Pb were corrected using a subset of parallel ICP–MS measurements taken at each site. Field and analytical duplicates revealed sampling as the major contributor (>95% variation) to measurement uncertainties. This study shows that increased sampling led to several benefits including more representative site characterisation, higher soil-metal mapping resolution, reduced uncertainty around the site mean, and reduced sampling uncertainty. Real time pXRF data enabled efficient, on-site decision making for further judgemental sampling, without the need to return to the site. Additionally, in-situ pXRF was more cost effective than the current approach of ex-situ sampling and ICP–MS analysis, even with higher sampling at each site. Lastly, a probabilistic site assessment approach was applied to demonstrate the advantages of integrating estimated measurement uncertainties into site reporting.

Under global change organisms are exposed to multiple, potentially interacting stressors. Especially interactions between successive stressors are poorly understood and recently suggested to depend on their timing of exposure. We particularly need studies assessing the impact of exposure to relevant stressors at various life stages and how these interact. We investigated the single and combined impacts of a heat wave (mild [25 °C] and extreme [30 °C]) during the egg stage, followed by successive exposure to esfenvalerate (ESF) and a heat wave during the larval stage in damselflies. Each stressor caused mortality. The egg heat wave and larval ESF exposure had delayed effects on survival, growth and lipid peroxidation (MDA). This resulted in deviations from the prediction that stressors separated by a long time interval would not interact: the egg heat wave modulated the interaction between the stressors in the larval stage. Firstly, ESF caused delayed mortality only in larvae that had been exposed to the extreme egg heat wave and this strongly depended upon the larval heat wave treatment. Secondly, ESF only increased MDA in larvae not exposed to the egg heat wave. We found little support for the prediction that when there is limited time between stressors, synergistic interactions should occur. The intermediate ESF concentration only caused delayed mortality when combined with the larval heat wave, and the lowest ESF concentrations only increased oxidative damage when followed by the mild larval heat wave. Survival selection mitigated the interaction patterns between successive stressors that are individually lethal, and therefore should be included in a predictive framework for the time-scale dependence of the outcome of multistressor studies with pollutants. The egg heat wave shaping the interaction pattern between successive pesticide exposure and a larval heat wave highlights the connectivity between the concepts of ‘heat-induced pesticide sensitivity’ and ‘pesticide-induced heat sensitivity’.

Both air pollution and meteorological factors in metropolitan areas increased emergency department (ED) visits from people with chronic obstructive pulmonary disease (COPD). Few studies investigated the associations between air pollution, meteorological factors, and COPD-related health disorders in Asian countries. This study aimed to investigate the relationship between the environmental factors and COPD-associated ED visits of susceptible elderly population in the largest Taiwanese metropolitan area (Taipei area, including Taipei city and New Taipei city) between 2000 and 2013. Data of air pollutant concentrations (PM10, PM2.5, O3, SO2, NO2 and CO), meteorological factors (daily temperature, relative humidity and air pressure), and daily COPD-associated ED visits were collected from Taiwan Environmental Protection Administration air monitoring stations, Central Weather Bureau stations, and the Taiwan National Health Insurance database in Taipei area. We used a case-crossover study design and conditional logistic regression models with odds ratios (ORs), and 95% confidence intervals (CIs) for evaluating the associations between the environmental factors and COPD-associated ED visits. Analyses showed that PM2.5, O3, and SO2 had significantly greater lag effects (the lag was 4 days for PM2.5, and 5 days for O3 and SO2) on COPD-associated ED visits of the elderly population (65–79 years old). In warmer days, a significantly greater effect on elderly COPD-associated ED visits was estimated for PM2.5 with coexistence of O3. Additionally, either O3 or SO2 combined with other air pollutants increased the risk of elderly COPD-associated ED visits in the days of high relative humidity and air pressure difference, respectively. This study showed that joint effect of urban air pollution and meteorological factors contributed to the COPD-associated ED visits of the susceptible elderly population in the largest metropolitan area in Taiwan. Government authorities should review existing air pollution policies, and strengthen health education propaganda to ensure the health of the susceptible elderly population.

Short chain chlorinated paraffins (SCCPs) are under review for inclusion into the Stockholm Convention on Persistent Organic Pollutants. However, limited information is available on their bioaccumulation and biomagnification in ecosystems, which is hindering evaluation of their ecological and health risks. In the present study, wild aquatic organisms (fish and invertebrates), water, and sediment collected from an enclosed freshwater pond contaminated by electronic waste (e-waste) were analyzed to investigate the bioaccumulation, distribution, and trophic transfer of SCCPs in the aquatic ecosystem. SCCPs were detected in all of the investigated aquatic species at concentrations of 1700–95,000 ng/g lipid weight. The calculated bioaccumulation factors (BAFs) varied from 2.46 to 3.49. The relationship between log BAF and the octanol/water partition coefficient (log KOW) for benthopelagic omnivorous fish species followed the empirical model of bioconcentration, indicating that bioconcentration plays an important role in accumulation of SCCPs. In contrast, the relationship for the benthic carnivorous fish and invertebrates was not consistent with the empirical model of bioconcentration, implying that the bioaccumulation of SCCPs in these species could be more influenced by other complex factors (e.g., habitat and feeding habit). Preferential distribution in the liver rather than in other tissues (e.g., muscle, gills, skin, and kidneys) was noted for the SCCP congeners with higher log KOW, and bioaccumulation pathway (i.e. water or sediment) can affect the tissue distribution of SCCP congeners. SCCPs underwent trophic dilution in the aquatic food web, and the trophic magnification factor (TMF) values of SCCP congener groups significantly correlated with their corresponding log KOW values (p < 0.0001). The present study results improved our understanding on the environmental behavior and fate of SCCPs in aquatic ecosystem.

Knowledge of the heterogeneous distribution of humic substances (HS) reactivities along a continuum of molecular weight (MW) is crucial for the systems where the HS MW is subject to change. In this study, two dimensional correlation spectroscopy combined with size exclusion chromatography (2D-CoSEC) was first utilized to obtain a continuous and heterogeneous presence of copper binding characteristics within bulk HS with respect to MW. HS solutions with varying copper concentrations were directly injected into a size exclusion chromatography (SEC) system with Tris-HCl buffer as a mobile phase. Several validation tests confirmed neither structural disruption of HS nor competition effect of the mobile phase used. Similar to batch systems, fluorescence quenching was observed in the chromatograms over a wide range of HS MW. 2D-CoSEC maps of a soil-derived HS (Elliot soil humic acid) showed the greater fluorescence quenching degrees with respect to the apparent MW on the order of 12500 Da > 10600 Da > 7000 Da > 15800 Da. The binding constants calculated based on modified Stern-Volmer equation were consistent with the 2D-CoSEC results. More heterogeneity of copper binding affinities within bulk HS was found for the soil-derived HS versus an aquatic HS. The traditional fluorescence quenching titration method using ultrafiltered HS size fractions failed to delineate detailed distribution of the copper binding characteristics, exhibiting a much shorter range of the binding constants than those obtained from the 2D-CoSEC. Our proposed technique demonstrated a great potential to describe metal binding characteristics of HS at high MW resolution, providing a clear picture of the size-dependent metal-HS interactions.

Cadmium (Cd) is a toxic heavy metal and harmful to human health due to its ability to accumulate in organs. Previous studies have shown that Cd can induce DNA damage and autophagy. Autophagy can stabilize genetic material and DNA integrity. The aim of the present study was to determine the exact mechanism and role of autophagy induced by Cd in spermatozoa cells. Mouse spermatocyte-derived cells (GC-2) were treated with 20 μM Cd chloride for 24 h. The level of reactive oxygen species (ROS), DNA damage, autophagy and the expression of the molecular signaling pathway ATM/AMP-activated protein kinase (AMPK)/mTOR were determined. The results showed that Cd induced autophagy and DNA damage in GC-2 cells via ROS generation, and the autophagy signal pathway AMPK/mTOR was activated by ATM which is a DNA damage sensor. Melatonin, a well-known antioxidant, ameliorated DNA damage, and inhibited autophagy via the AMPK/mTOR signal pathway. Furthermore, after inhibition of autophagy by knockdown of AMPKα, increased DNA damage by Cd treatment was observed in GC-2 cells. These findings demonstrated the protective role of autophagy in DNA damage and suggested that the mechanism of autophagy induced by Cd was through the ATM/AMPK/mTOR signal pathway in spermatozoa cells.