Environmental Science: Processes & Impacts最新文献

While man-made chemicals in the environment are ubiquitous and a potential threat to human health and ecosystem integrity, the environmental fate of chemical contaminants such as pharmaceuticals is often poorly understood. Biodegradation processes driven by microbial communities convert chemicals into transformation products (TPs) that may themselves have adverse ecological effects. The detection of TPs formed during biodegradation has been continuously improved thanks to the development of TP prediction algorithms and analytical workflows. Here, we contribute to this advance by (i) reviewing past applications of TP identification workflows, (ii) applying an updated workflow for TP prediction to 42 pharmaceuticals in biodegradation experiments with activated sludge, and (iii) benchmarking 5 different pathway prediction models, comprising 4 prediction models trained on different datasets provided by enviPath, and the state-of-the-art EAWAG pathway prediction system. Using the updated workflow, we could tentatively identify 79 transformation products for 31 pharmaceutical compounds. Compared to previous works, we have further automatized several steps that were previously performed by hand. By benchmarking the enviPath prediction system on experimental data, we demonstrate the usefulness of the pathway prediction tool to generate suspect lists for screening, and we propose new avenues to improve their accuracy. Moreover, we provide a well-documented workflow that can be (i) readily applied to detect transformation products in activated sludge and (ii) potentially extended to other environmental studies.

Recent studies have reported that nanoparticles (NPs) released into the aquatic environment may interact with persistent organic pollutants such as brominated flame retardants, whereas the environmental processes and toxicological impacts induced by such binary NPs require further specification. This study investigated the ultrastructural damage of Chlorella vulgaris triggered by exposure to zinc oxide (ZnO) NPs, tetrabromobisphenol A (TBBPA), ZnO–TBBPA, and ZnO–TBBPA–humic acid (HA), clarified the uptake and distribution of ZnO NPs in cells, and explored the physiological toxicity and tolerance mechanism. The results demonstrated that ZnO NPs induced irregular morphology in algal cells, and the disruption of the cellular ultrastructure by binary ZnO–TBBPA was also extremely severe due to the excessive uptake of ZnO NPs, which resulted in strong oxidative stress responses. In particular, the accumulation of reactive oxygen species further exacerbated the reduction of total chlorophyll content and algal density. Moreover, the cluster heat map and correlation analysis revealed that superoxide dismutase activity played a critical role in alleviating lipid peroxidation damage and enhancing the tolerance of algal cells to the stress of binary ZnO NPs. More notably, the existence of HA intensified the dispersion stability of NP suspensions and significantly mitigated the synergistic toxicity of binary ZnO–TBBPA. This study provides new insights into the environmental behavior and biological impacts of binary NPs in the natural environment.

Rivers are important channels for the transport of microplastics (MPs) from land to sea. In this work, the temporal variation and risk assessment of MP pollution in the surface water of the Wei River, a typical seasonal river in northern China, were quantified. The number abundance of MPs in the dry season was significantly higher than that in the wet season (p < 0.05). Fiber was the most abundant type of MP in both dry and wet seasons. Infrared spectrometer and Raman spectroscopy identification showed that polypropylene (PP) and polyethylene (PE) were the major polymers found in both dry and wet seasons, and the mixture of different MP polymers was more diverse in the dry season. The risk assessment showed that the average pollution load index (PLI) and risk quotient (RQ) were 2.10 and 1.19 in the dry season, which significantly decreased to 1.25 and 0.74, respectively, in the wet season (p < 0.05). In total, the results from this study highlight the characteristics of seasonal rivers that influence the temporal distribution and risk assessment of microplastics, providing scientific reference for policymakers and river managers to effectively deal with MP pollution.

Temporal and spatial trends of 15 per- and polyfluoroalkyl substances (PFAS) were determined in white-tailed sea eagle (WTSE) eggs (Haliaeetus albicilla) from two inland and two coastal regions of Sweden between 1969 and 2021. PFAS concentrations generally increased from ∼1969 to ∼1990s–2010 (depending on target and site) and thereafter plateaued or declined, with perfluorooctane sulfonamide (FOSA) and perfluorooctane sulfonate (PFOS) declining faster than most perfluoroalkyl carboxylic acids (PFCAs). The net result was a shift in the PFAS profile from PFOS-dominant in 1969–2010 to an increased prevalence of PFCAs over the last decade. Further, during the entire period higher PFAS concentrations were generally observed in coastal populations, possibly due to differences in diet and/or proximity to more densely populated areas. Fluorine mass balance determination in pooled samples from three of the regions (2019–2021) indicated that target PFAS accounted for the vast majority (i.e. 81–100%) of extractable organic fluorine (EOF). Nevertheless, high resolution mass-spectrometry-based suspect screening identified 55 suspects (31 at a confidence level [CL] of 1–3 and 24 at a CL of 4–5), of which 43 were substances not included in the targeted analysis. Semi-quantification of CL ≤ 2 suspects increased the identified EOF to >90% in coastal samples. In addition to showing the impact of PFAS regulation and phase-out initiatives, this study demonstrates that most extractable organofluorine in WTSE eggs is made up of known (legacy) PFAS, albeit with low levels of novel substances.

Disposable surgical face masks extensively used during the COVID-19 outbreak would release microplastics into the aquatic environment. The increasing usage of titanium dioxide nanoparticles (nTiO₂) in various consumer items has led to its ubiquitous presence in freshwater systems. This study determined the quantity and kind of microplastics discharged from disposable surgical face masks. The mask-leached microplastics were identified to be polypropylene of varying shapes and sizes, spanning from 1 μm to 15 μm. In addition, heavy metals like Cd, Cr, and Hg leached from the face masks were quantified. Four concentrations of nTiO₂, 0.5, 1, 2, and 4 mg L⁻¹, were mixed with leached solution from the face masks to perform the combined toxicity test on freshwater algae, Scenedesmus obliquus. A dose-dependent decrease in algal cell viability was observed upon treatment with various concentrations of nTiO₂ individually. The mixtures of nTiO₂ and the leached solution from the face masks exhibited significantly more toxicity in the algal cells than in their pristine forms. nTiO₂ promoted increased production of oxidative stress and antioxidant enzyme activities resulting in cellular damage and decreased photosynthesis. These impacts were elevated when the algal cells were treated with the binary mixture. Furthermore, the heavy metal ions leached from face masks also contributed to the toxic effects. Our study shows that the leachates from disposable surgical face masks, combined with nTiO_2, may pose a severe environmental threat.

Forest–stream ecotones possess prominent detritus-based food webs, and ¹³⁷Cs-contaminated litter can influence the contamination levels of animals inhabiting such ecosystems. The effects of leaching on contaminated litter induce greater absolute differences between the ¹³⁷Cs concentrations of forest and stream litter in more contaminated sites. Because ¹³⁷Cs concentrations in litter can be attenuated temporally, spatiotemporal patterns in the differences in ¹³⁷Cs concentrations between forest and stream litter may vary depending on both the amount of ¹³⁷Cs deposition and the passage of time. To test this hypothesis, we sampled coniferous needle and broad-leaved deciduous litter in forests and streams at seven forested headwater sites affected by the Fukushima nuclear accident 3.24 and 11.24 years after the accident. We found that ¹³⁷Cs concentrations in the two litter types were one order of magnitude lower 11.24 years after the accident than 3.24 years afterwards. The absolute difference in ¹³⁷Cs activity concentrations of litter between forest and stream ecosystems was higher at more contaminated sites both 3.24 and 11.24 years after the accident. The spatiotemporal changes in litter contamination provide insight into ¹³⁷Cs dynamics and complex transfer in the detritus-based food webs of forest–stream ecotones.

Oxidized compounds in the atmosphere can occur as emitted primary compounds or as secondary products when volatile emitted precursors react with various oxidants. Due to the presence of polar functional groups, their vapor pressures decrease, and they condense onto small particles. Thereby, they have an effect on climate change by the formation of clouds and scattering solar radiation. The particles and oxidized compounds themselves can cause serious health problems when inhaled. Therefore, it is of utmost importance to study oxidized compounds in the atmosphere. Much ongoing research is focused on the discovery of new oxidized substances and on the evaluation of their sources and factors influencing their formation. Monitoring biogenic and anthropogenic primary oxidized compounds or secondary oxidized products in chamber experiments or field campaigns is common. New discoveries have been reported, including various oxidized compounds and a new group of compounds called highly oxidized organic molecules (HOMs). Analytics of HOMs are mainly focused on chromatography and high-resolution mass spectrometry employing chemical ionization for identifying and quantifying compounds at low concentrations. Oxidized compounds can also be monitored by spectrophotometric methods in which the determinations of total amounts are based on functional groups. This review highlights recent findings on oxidized organic compounds in the atmosphere and analytical methodologies used for their detection and quantification. The discussion includes gas and liquid chromatographic methods, sampling, extraction, concentration, and derivatization procedures involved, as well as mass spectrometric and spectrophotometric methods.

Lead (Pb²⁺) is an important developmental toxicant. The mitochondrial calcium uniporter (MCU) imports calcium ions using the mitochondrial membrane potential (MMP), and also appears to mediate the influx of Pb²⁺ into the mitochondria. Since our environment contains mixtures of toxic agents, it is important to consider multi-chemical exposures. To begin to develop generalizable, predictive models of interactive toxicity, we developed mechanism-based hypotheses about interactive effects of Pb²⁺ with other chemicals. To test these hypotheses, we exposed HepG2 (human liver) cells to Pb²⁺ alone and in mixtures with other mitochondria-damaging chemicals: carbonyl cyanide-p-trifluoromethoxyphenylhydrazone (FCCP), a mitochondrial uncoupler that reduces MMP, and Ruthenium Red (RuRed), a dye that inhibits the MCU. After 24 hours, Pb²⁺ alone, the mixture of Pb²⁺ and RuRed, and the mixture of Pb²⁺ and FCCP caused no decrease in cell viability. However, the combination of all three exposures led to a significant decrease in cell viability at higher Pb²⁺ concentrations. After 48 hours, the co-exposure to elevated Pb²⁺ concentrations and FCCP caused a significant decrease in cell viability, and the mixture of all three showed a clear dose-response curve with significant decreases in cell viability across a range of Pb²⁺ concentrations. We performed ICP-MS analyses on isolated mitochondrial and cytosolic fractions and found no differences in Pb²⁺ uptake across exposure groups, ruling out altered cellular uptake as the mechanism for interactive toxicity. We assessed MMP following exposure and observed a decrease in membrane potential that corresponds to loss of cell viability but is likely not sufficient to be the causative mechanistic driver of cell death. This research provides a mechanistically-based framework for understanding Pb²⁺ toxicity in mixtures with mitochondrial toxicants.

Elemental carbon (EC) and organic carbon (OC) exist ubiquitously and interact mutually in the environment. Simultaneous analysis of EC and OC will greatly advance our understanding of the behavior and fate of EC and OC, but is however still a great challenge due to the lack of suitable analytical tools. Here, we report a matrix-free laser desorption/ionization mass spectrometry (LDI-MS) method capable of simultaneous analysis of EC and OC by monitoring two independent groups of specific MS fingerprint peaks. We found that EC itself can generate carbon cluster peaks in the low mass range under laser excitation, and meanwhile it can also serve as a matrix to assist the ionization of OC in LDI-MS. By using per- and polyfluoroalkyl substances (PFASs) as a typical set of OC and carbon black (CB) as a model EC, we successfully monitored the adsorption process of PFASs on CB enabled by LDI-MS. We show that hydrophobic interaction dominates the sorption of PFASs to CB, which was affected by the functional groups and carbon chain length of PFASs. Furthermore, environmental substances in water such as humic acid (HA) and surfactants can significantly affect the adsorption of PFASs on CB probably by changing the adsorption sites of CB. Overall, we demonstrate that LDI-MS offers a versatile and high-throughput tool for simultaneous analysis of EC and OC species in real environmental samples, which makes it promising for investigating the environmental behaviors and ecological risks of pollutants.

Some studies of endocrine-disrupting polycyclic aromatic hydrocarbon (PAH) exposure and thyroid hormones (THs) are inconclusive. To assess the associations between PAHs and THs, and the influence of the iodine status on PAHs–THs, we employed 648 adolescents (12–19 years old) and 2691 adults from the National Health and Nutrition Examination Survey 2007–2008 and 2011–2012. PAH metabolites [1-hydroxynaphthalene (1-NAP), 2-NAP, 1-hydroxyphenanthrene (1-PHE), 2-PHE, 3-PHE, 2-hydroxyfluorene (2-FLU), 3-FLU, 9-FLU, and 1-hydroxypyrene (1-PYR)], THs [total and free thyroxine (TT4 and FT4), total and free triiodothyronine (TT3 and FT3), thyroid stimulating hormone (TSH), and thyroglobulin (Tg)], peripheral deiodinase activity (G_D) and thyroid's secretory capacity (G_T) were involved. Multiple linear regression and weighted quantile sum (WQS) regression models were used to assess PAH–TH associations and the interaction between PAHs and the iodine status. Stratification analyses were conducted based on sex, smoking and iodine status. For adolescents, in a multivariable-adjusted regression model (β; 95% CI), 1-PHE (4.08%; 1.01%, and 7.25%), 2-PHE (3.98%; 0.70%, and 7.25%) and 9-FLU (3.77%; 1.10%, 7.47%) were positively correlated with TT3; 3-PHE and 1-PYR interacted with the iodine status (P-int < 0.05); 9-FLU was positively correlated with G_D in both sexes. Combined exposure to PAHs was positively associated with Tg (0.137; 0.030, and 0.243), and negatively correlated with TSH (−0.087; −0.166, and −0.008). For adults, 2-NAP was positively correlated with FT3 (0.90%; 0.20%, and 1.61%), FT4 (1.82%; 0.70%, and 2.94%), TT3 (1.31%; 0.10%, and 2.63%), TT4 (2.12%; 0.90%, and 3.36%) and G_T (2.22%; 1.01%, and 3.46%), but negatively correlated with TSH (−4.97%; −8.33%, and −1.49%); 1-NAP interacted with the iodine status (P-int < 0.05); 1-PHE was inversely correlated with TT3 in males; 2-PHE was positively correlated with TT3 in females. Combined exposure to PAHs was positively associated with FT3 (0.008; 0.001, and 0.014). Combined exposure to PAHs was positively associated with FT3, TT3 and G_D, and negatively correlated with FT4, TT4 and G_T in non-smoking adults; but positively associated with Tg (β = 0.140; 95% CI: 0.042, 0.237) in smoking adults. Our results indicated that combined and individual PAH exposure might be related to THs, and the iodine status had an influence on PAH–TH associations. These associations were not identical between adolescents and adults, and there were sex and smoking status differences.