Metal-organic frameworks (MOFs) are an emerging class of materials which have garnered increasing attention for their utility as adsorbents and photocatalysts in water treatment. Nevertheless, the environmental risks of MOFs, especially their underlying impacts on aquatic organisms, are not fully explored. Herein, the toxicity of multiple representative MOFs was systematically assessed using a freshwater green alga (Chlamydomonas reinhardtii) model. Six typical MOFs with different metal nodes or organic linkers, including four transition metal incorporated aluminum-based porphyrin MOFs [pristine Al-PMOF, Al-PMOF (Cu), Al-PMOF (Ni), and Al-PMOF (Co)], one amine-functionalized MOF NH₂-MIL-125 (Ti), and one bimetallic Hofmann MOF (NiCo-PYZ), were successfully synthesized and characterized. All the tested MOFs significantly reduced the chlorophyll content and inhibited the algal growth, with the most toxic materials being NiCo-PYZ and Al-PMOF (Cu). Distinct toxic mechanisms were observed for the tested MOFs. Metal ion release was the primary cause for algal toxicity induced by NiCo-PYZ. The algal toxicity induced by porphyrin MOFs could be explained by the combined effects of metal ion release and nutrient adsorption, agglomeration and physical interactions, and reactive oxygen species generation. NH₂-MIL-125 (Ti) showed higher stability and more biocompatibility than the other tested MOFs. MOFs concentrations with no harmful effects to algae can be taken as the threshold values for safe use and discharge of MOFs. The ecotoxicological risks of MOFs should be considered as the applied concentrations of MOFs at mg/mL levels in environmental remediation were much higher than the no harmful effect thresholds.

The anaerobic digestion of wastewater rich in volatile fatty acids (VFAs) provides a sustainable approach for methane production whilst reducing environmental pollution. However, the anaerobic digestion of VFAs may not be stable during long-term operation under a short hydraulic retention time. In this study, conductive carbon cloth was supplemented to investigate the impacts on the anaerobic digestion of VFAs in wastewater sourced from dark fermentation. The results demonstrated that the failure of anaerobic digestion could be avoided when carbon cloth was supplemented. In the stable stage, the methane production rate with carbon cloth supplementation was improved by 200–260%, and the chemical oxygen demand (COD) removal efficiency was significantly enhanced compared with that in the control without carbon cloth. The relative abundance of potential exoelectrogens on the carbon cloth was increased by up to 8-fold compared with that in the suspension. Electrotrophic methanogens on the carbon cloth were enriched by 4.2–17.2% compared with those in the suspension. The genera Ercella and Petrimonas along with the methanogenic archaea Methanosaeta and Methanosarcina on the carbon cloth may facilitate direct interspecies electron transfer, thereby enhancing methane production.

An industrial warehouse illegally storing a large quantity of unknown chemical and industrial waste ignited in an urban area in Melbourne, Australia. The multiday fire required firefighters to use large amounts of fluorine-free foam that carried contaminated firewater runoff into an adjacent freshwater creek. In this study, the occurrence and fate of 42 per- and polyfluoroalkyl substances (PFASs) was determined from triplicate surface water samples (n = 45) from five locations (upstream, point-source, downstream; 8 km) over three sampling campaigns from 2018 to 2020. Out of the 42 target PFASs, perfluorocarboxylates (PFCAs: C4–C14), perfluoroalkane sulfonates (PFSAs: C4–C10), and perfluoroalkyl acid precursors (e.g. 6:2 fluorotelomer sulfonate (6:2 FTSA)) were ubiquitously detected in surface waters (concentration ranges: <0.7–3000 ng/L). A significant difference in ΣPFAS concentration was observed at the point-source (mean 5500 ng/L; 95% CI: 4800, 6300) relative to upstream sites (mean 100 ng/L; 95% CI: 90, 110; p ≤ 0.001). The point-source ΣPFAS concentration decreased from 5500 ± 1200 ng/L to 960 ± 42 ng/L (−83%) after two months and to 430 ± 15 ng/L (−98%) two years later. 6:2 FTSA and perfluorooctanesulfonate (PFOS) dominated in surface water, representing on average 31% and 20% of the ΣPFAS, respectively. Emerging PFASs including a cyclic perfluoroalkanesulfonate (PFECHS) and a C4 perfluoroalkane sulfonamide (FBSA) were repeatedly present in surface water (concentration ranges <0.3–77 ng/L). According to the updated Australian PFAS guidelines for ecological conservation, the water samples collected at the time of monitoring may have posed a short-term risk to aquatic organisms in regard to PFOS levels. These results illustrate that acute high dose exposure to PFASs can result from industrial fires at sites storing or stockpiling PFAS-based waste products. Continued monitoring will be crucial to evaluate potential long-term risk to wildlife in the region.

Triclocarban (TCC), an antibacterial agent widely used in personal care products, can affect embryonic development. However, the specific molecular mechanism of TCC-induced embryonic developmental damage remains unclear. In this study, TCC exposure was found to increase the expression of tmbim4 gene in zebrafish embryos. The tmbim4 mutant embryos are more susceptible to TCC exposure than wild-type (WT) embryos, with tmbim4 overexpression reducing TCC-induced embryonic death in the former. Exposure of tmbim4 mutant larvae to 400 μg/L TCC substantially increased apoptosis in the hindbrain and eyes. RNA-sequencing of WT and tmbim4 mutant larvae indicated that knockout of the tmbim4 gene in zebrafish affects the autophagy pathway. Abnormalities in autophagy can increase apoptosis and TCC exposure caused abnormal accumulation of autophagosomes in the hindbrain of tmbim4 mutant zebrafish embryos. Pretreatment of TCC-exposed tmbim4 mutant zebrafish embryos with autophagosome formation inhibitors, substantially reduced the mortality of embryos and apoptosis levels. These results indicate that defects in the tmbim4 gene can reduce zebrafish embryo resistance to TCC. Additionally, apoptosis induced by abnormal accumulation of autophagosomes is involved in this process.

Ecological floating beds (EFBs) have become a superior method for treating secondary effluent from wastewater treatment plant. However, insufficient electron donor limited its denitrification efficiency. Iron scraps from lathe cutting waste consist of more than 95% iron could be used as electron donors to enhance denitrification. In this study, EFBs with and without iron scraps supplementation (EFB-Fe and EFB, respectively) were conducted to explore the impacts of iron scraps addition on nitrogen removal, nitrous oxide (N₂O) emissions and microbial communities. Results showed the total nitrogen (TN) removal in EFB-Fe improved to 79% while that in EFB was 56%. N₂O emission was 0–6.20 mg m⁻² d⁻¹ (EFB-Fe) and 1.74–15.2 mg m⁻² d⁻¹ (EFB). Iron scraps could not only improve nitrogen removal efficiency, but also reduce N₂O emissions. In addition, high-throughput sequencing analysis revealed that adding iron scraps could improve the sum of denitrification related genera, among which Novosphingobium accounted for the highest proportion (6.75% of PFe1, 4.24% of PFe2, 3.18% of PFe3). Iron-oxidizing bacteria and iron-respiring bacteria associated with and nitrate reducing bacteria mainly concentrated on the surface of iron scraps. Principal co-ordinates analysis (PCoA) indicated that iron scraps were the key factor affecting microbial community composition. The mechanism of iron scraps enhanced nitrogen removal was realized by enhanced biological denitrification process. Iron release dynamic from iron scraps was detected in bench-scale experiment and the electron transfer mechanism was that Fe⁰ transferred electrons directly to NO₃⁻-N, and biological iron nitrogen cycle occurred in EFB-Fe without secondary pollution.

Critical loads are thresholds of atmospheric deposition below which harmful ecological effects do not occur. Because lichens are sensitive to atmospheric deposition, lichen-based critical loads can foreshadow changes of other forest processes. Here, we derive critical loads of nitrogen (N) and sulfur (S) deposition for continental US and coastal Alaskan forests, based on nationally consistent lichen community surveys at 8855 sites. Across the eastern and western US ranges of 459 lichen species, each species' realized optimum was the N or S atmospheric deposition value at which it most frequently occurred. The mean of optima for all species at a site, weighted by their abundances, was defined as a community “airscore” indicative of species’ collective responses to atmospheric deposition. To determine critical loads for adverse community compositional shifts, we then modeled changes in airscores as a function of deposition, climate and forest habitat predictors in nonparametric multiplicative regression. Critical loads, indicative of initial shifts from pollution-sensitive toward pollution-tolerant species, occurred at 1.5 kg N ha⁻¹ y⁻¹ and 2.7 kg S ha⁻¹ y⁻¹. Importantly, these critical loads remain constant under any climate regime nationwide, suggesting both simplicity and nationwide applicability. Our models predict that preventing excess N deposition of just 0.2–2.0 kg ha⁻¹ y⁻¹ in the next century could offset the detrimental effects of predicted climate warming on lichen communities. Because excess deposition and climate warming both harm the most ecologically influential species, keeping conditions below critical loads would sustain both forest ecosystem functioning and climate resilience.

Vehicle emissions are an important source of particulate matter (PM) in urban areas and have well-known adverse health effects on human health. Oxidative potential (OP) is used as a quantification metric for indexing PM toxicity. In this study, by using a liquid spot sampler (LSS) and the dithiothreitol (DTT) assay, the diurnal OP variation was assessed at a ground-level urban monitoring station. Besides, since the monitoring station was adjacent to the main road, the correlation between OP and traffic volume was also evaluated. PM components, including metals, water-soluble inorganic aerosols (WSIAs), black carbon (BC), and polycyclic aromatic hydrocarbons (PAHs), were also simultaneously monitored. The daytime and evening mean ± std volume-normalized OP (OPv) were 0.46 ± 0.27 and 0.48 ± 0.26 nmol/min/m³, and exhibited good correlations with PM₁.₀ and BC; however, these concentrations were only weakly correlated with mass-normalized OP (OPm). The mean ± std OPm was higher in the daytime (41.3 ± 13.8 pmol/min/μg) than in the evening (36.1 ± 11.5 pmol/min/μg). According to the PMF analysis, traffic emissions dominated the diurnal OP contribution. Organic matter and individual metals associated with non-exhaust traffic emissions, such as Mn, Fe, and Cu, contributed substantially to OP. Diurnal variations of PAH concentrations suggest that photochemical reactions could enhance OP, highlighting the importance of atmospheric aging on PM toxicity.

Polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs (NPAHs) in PM₂.₅ were first observed at a background site (Yuzhong site: YZ site) in the northwestern highlands of China in five seasonal campaigns. Compared with major northwestern cities, PAHs and NPAHs at the YZ site were at a lower level but showed consistent seasonal differences. The PAH and NPAH concentrations peaked in the winter campaigns, which were 36.11 ± 6.54 ng/m³ and 418.11 ± 123.55 pg/m³, respectively, in winter campaign 1 and 28.97 ± 10.07 ng/m³ and 226.89 ± 133.54 pg/m³, respectively, in winter campaign 2. These values were approximately a dozen times larger those in other campaigns. The diagnostic ratios indicate that vehicle emissions were the primary source of the PAHs throughout the five campaigns, and coal and biomass combustion also contributed during the winter, summer, and fall campaigns. Among NPAHs, 2-nitrofluoranthene and 2-nitropyrene were generated through OH radical-initiated reactions during atmospheric transport, while 1-nitropyrene came from combustion sources. There is an observation worth pondering, which is that the ratio between pyrene and fluoranthene increased abnormally in the spring and fall campaigns, which is presumably caused by the burning of Tibetan barley straw in the northwestern highlands. The backward trajectories over Tibetan areas in Qinghai and southwestern Gansu are consistent with this hypothesis. In addition, this study reported for the first time that the burning of Tibetan barley straw has become a seasonal contributor to air pollution in northwestern China and is participating in the atmospheric transport of air pollutants driven by the monsoon in East Asia, which urgently requires further research.

HKUST-1 is currently studied for a very diverse range of applications. Despite its exciting potential, significant concerns remain regarding the safety of HKUST-1. Therefore, human embryonic kidney 293 (HEK293) cells were used to verify the renal toxicity of HKUST-1. In this study, HKUST-1 induced concentration-dependent cytotoxic effects in HEK293 cells. The depolarization of mitochondrial membrane potential and formation of apoptotic bodies and autophagic vesicles were observed in HKUST-1–treated HEK293 cells. Oxidative (oxidative stress and haem oxygenase-1 activation) and inflammatory responses (NF-κB and NLRP3 activation) in HEK293 cells were induced by HKUST-1 exposure. In addition, the observed reduction in NAD(P)H levels in HKUST-1–treated HEK293 cells may be attributable to PARP-1 activation following DNA single- and double-strand breaks. The HKUST-1–induced depletion of zonula occludens proteins in HEK293 cells might lead to altered renal barrier integrity. The variations of α1-antitrypsin, oxidised α1-antitrypsin and NLRP3 protein expression in HEK293 cells suggested that HKUST-1 increases the risk of chronic kidney diseases. However, most of these adverse effects were significantly induced only by high HKUST-1 concentration (100 μg/mL), which do not reflect the actual exposure. Thus, the toxic risk of HKUST-1 appears to be negligible.

A systematic investigation into bioaccessible heavy metals in shellfish Crassostrea ariakensis, Chlamys farreri, and Sinonovacula constricta from coastal cities Shenzhen, Zhoushan, Qingdao, and Dandong was carried out to assess the potential health risk to residents in coastal regions in China. The bioaccessible fractions of heavy metals were (μg‧g⁻¹): Zn (0.63–15.01), Cu (0.10–12.91), Cd (0.01–0.64), As (0.11–0.33), Cr (0.07–0.12), Pb (0.01–0.03). The bioaccessibilities of heavy metals were Cr 61.86%, inorganic As (iAs) 60.44%, Pb 55.74%, Cu 46.83%, Zn 28.16%, and Cd 24.99%. As for child and adult, the bioaccessibility-corrected estimated daily intakes were acceptable and the non-carcinogenic risks posed by heavy metals were not obvious. The carcinogenic risks posed by bioaccessible heavy metals at the fifth percentile were 10-fold higher than the acceptable level (10⁻⁴), with iAs and Cd to be the major contributors, regardless of child or adult. The probabilistic estimation showed the low risk of shellfish consumption, which was verified by higher values of maximum allowable consumption rate and monthly meals at the 95 percentile; while some control of consumption rate and monthly meals was necessary for reducing heavy metal exposure of most shellfish samples, except for the safe consumption of S. constricta for both child and adult in Qingdao and Shenzhen, China.