Occurrence, Spatial Distribution, and Bioaccumulation of Dissolved Synthetic Musks in Freshwaters across China.

Commercial chemicals, such as synthetic musks, are of global concern, but data on their occurrence and spatial distribution in aquatic environments of large scale are scarce. Two sampling campaigns were conducted in the present study to measure freely dissolved synthetic musks in freshwaters across China using passive samplers, along with biological coexposure at selected sites. Polycyclic musks (PCMs) dominated synthetic musks, with a detection frequency of 95%. Higher concentrations of PCMs were observed in densely populated Mid, East, and South China compared to less populated regions, indicating the significance of anthropogenic activities for synthetic musks in water. The concentration ratios of galaxolide (HHCB)/tonalide (AHTN) were significantly higher in low-latitude areas than in high-latitude areas from June to September, suggesting that solar radiation played an important role in the degradation of HHCB/AHTN. Significant correlations were found between dissolved concentrations of HHCB and AHTN and their lipid-normalized concentrations in coexposed fish and clam. The estimated hazard quotients for HHCB and AHTN in freshwater fish consumed by humans were less than 0.01 at all sampling sites except the Yangtze River Basin. These results help to understand the environmental fate and ecological risks of synthetic musks on a large geographical scale.

Modeled Pathways and Fluxes of PCB Dechlorination by Redox Potentials.

Dechlorination is one of the main processes for the natural degradation of polychlorinated biphenyls (PCBs) in an anaerobic environment. However, PCB dechlorination pathways and products vary with PCB congeners, types of functional dechlorinating bacteria, and environmental conditions. The present study develops a novel model for determining dechlorination pathways and fluxes by tracking redox potential variability, transforming the complex dechlorination process into a stepwise sequence. The redox potential is calculated via the Gibbs free energy of formation, PCB concentrations in reactants and products, and environmental conditions. Thus, the continuous change in the PCB congener composition can be tracked during dechlorination processes. The new model is assessed against four measurements from several published studies on PCB dechlorination. The simulation errors in all four measurements are calculated between 2.67 and 35.1% under minimum (n = 0) and maximum (n = 34) numbers of co-eluters, respectively. The dechlorination fluxes for para-dechlorination pathways dominate PCB dechlorination in all measurements. Furthermore, the model also considers multiple-step dechlorination pathways containing intermediate PCB congeners absent in both the reactants and the products. The present study indicates that redox potential might be an appropriate indicator for predicting PCB dechlorination pathways and fluxes even without prior knowledge of the functional dechlorinating bacteria.

Use of machine learning to identify key factors regulating volatilization of semi-volatile organic chemicals from soil to air.

Volatilization from soil to air is a key process driving the distribution and fate of semi-volatile organic contaminants. However, quantifying this process and the key environmental governing factors remains difficult. To address this issue, the volatilization fluxes of polybrominated diphenyl ethers (PBDEs) and organophosphate esters (OPEs) from soil were determined in 16 batch experiments orthogonally with six variables (chemical property, soil concentration, air velocity, ambient temperature, soil porosity, and soil moisture) and analyzed with machine learning methods. The results showed that gradient-boosting regression tree models satisfactorily predicted the volatilization fluxes of PBDEs (r2 = 0.82 ± 0.07) and OPEs (r2 = 0.62 ± 0.13). Permutation importance analysis showed that partitioning potential of chemicals between soil and air was the most important factor regulating the volatilization of the target compounds from soil. Temperature and soil porosity played a secondary role in controlling the migration of PBDEs and OPEs, respectively, due to higher volatilization enthalpies of PBDEs than those of OPEs and dominant adsorption of OPEs on mineral surface. The effect of soil moisture was negative and positive for the volatilization fluxes of PBDEs and OPEs, respectively. These results suggested different responses in the soil-air diffusive transport of PBDEs and OPEs to high temperature and rainstorm induced by climate change.

Fluorescent Visualization of Chemical Profiles across the Air-Water Interface.

Chemical transfer across the air-water interface is one of the most important geochemical processes of global significance. Quantifying such a process has remained extremely challenging due to the lack of suitable technologies to measure chemical diffusion across the air-water microlayer. Herein, we present a fluorescence optical system capable of visualizing the formation of the air-water microlayer with a spatial resolution of 10 µm and quantifying air-water diffusion fluxes using pyrene as a target chemical. We show for the first time that the air-water microlayer is composed of the surface microlayer in water (∼290 ± 40 µm) and a diffusion layer in air (∼350 ± 40 µm) with 1 µg L-1 of pyrene. The diffusion flux of pyrene across the air-water interface is derived from its high-resolution concentration profile without any pre-emptive assumption, which is 2 orders of magnitude lower than those from the conventional method. This system can be expanded to visualize diffusion dynamics of other fluorescent chemicals across the air-water interface and provides a powerful tool for furthering our understanding of air-water mass transfer of organic chemicals related to their global cycling.

Particle transfer mediates dermal exposure of consumers to plasticizers in eraser and pen accessories.

Dermal exposure to chemicals released from daily consumer products is a rising concern, particularly for children who are susceptible to unintentional hand-to-mouth transfer and related chemical exposure risk. However, chemical transfer induced by tiny particles of intact products has yet to be adequately addressed. The objective of the present study was to determine the potentiality of particles release from intact erasers and pen grips upon dermal contact by measuring the migration rates of the embedded plasticizers (phthalates and its alternatives). The results showed that billions of particles were released from erasers (0.6-1.2 × 109) and pen grips (0.2-1.6 × 108) upon dermal contact at ambient temperature, with sizes mainly smaller than 1 µm. The composition of eraser leachates was identical to that of the corresponding bulk eraser, as confirmed by Fourier-transform infrared spectroscopy and pyrolysis. Migrated hydrophobic plasticizers may be used as indicators of particle release from erasers and pen grips. The potentiality of particle release was negatively correlated with the total plasticizer contents (r = -0.51; p < 0.05) for both erasers and pen grips. These findings indicated that particles directly released from school supplies and accessories could be a non-negligible source of human exposure to plasticizers.

Hydrophobic organic contaminants affiliated with polymer-specific microplastics in urban river tributaries and estuaries.

Exposure to microplastics (MPs) and hydrophobic organic contaminants (HOCs) combined at high concentrations may induce adverse effects to aquatic organisms in laboratory-scale studies. To determine environmentally relevant concentrations of HOCs in MPs, it is essential to understand the occurrence of MP-affiliated HOCs in the aquatic environment. Here we report the occurrences of HOCs affiliated with polymer-specific floating MPs from 12 tributaries and three estuaries in the Pearl River Delta, South China. Target HOCs include nine synthetic musks (SMs), 14 ultraviolet adsorbents (UVAs), 15 polycyclic aromatic hydrocarbons (PAHs), eight polybrominated diphenyl ethers (PBDEs), and 14 polychlorinated biphenyls (PCBs). Average concentrations of MP-affiliated ∑9SM, ∑14UVA, ∑15PAH, ∑8PBDE, and ∑14PCB were 1790, 5550, 1090, 412, and 107 ng g-1, respectively. The average concentrations of HOCs affiliated with MPs of different polymer types were 9790, 7220, 72,500, and 55,800 ng g-1 for polyethylene (PE), polypropylene, polystyrene, and other MPs, respectively. As the concentration of PE was the highest among all MPs at the average concentration of 0.77 mg m-3, the monthly outflow of PE-affiliated HOCs accounted for the largest proportion (46 %) in the outflow of MP-affiliated HOCs (2.8 g) to the coastal ocean via three estuaries. These results suggest that HOCs were highly concentrated in MPs and varied among different chemicals and polymer types. Due to the differences of polymer characteristics and half-life of affiliated chemicals, future toxicology studies concerning exposure to these combined pollutants may need to specify polymer types and their affiliated chemicals.

Passive-Sampler-Derived PCB and OCP Concentrations in the Waters of the World─First Results from the AQUA-GAPS/MONET Network.

Persistent organic pollutants (POPs) are recognized as pollutants of global concern, but so far, information on the trends of legacy POPs in the waters of the world has been missing due to logistical, analytical, and financial reasons. Passive samplers have emerged as an attractive alternative to active water sampling methods as they accumulate POPs, represent time-weighted average concentrations, and can easily be shipped and deployed. As part of the AQUA-GAPS/MONET, passive samplers were deployed at 40 globally distributed sites between 2016 and 2020, for a total of 21 freshwater and 40 marine deployments. Results from silicone passive samplers showed α-hexachlorocyclohexane (HCH) and γ-HCH displaying the greatest concentrations in the northern latitudes/Arctic Ocean, in stark contrast to the more persistent penta (PeCB)- and hexachlorobenzene (HCB), which approached equilibrium across sampling sites. Geospatial patterns of polychlorinated biphenyl (PCB) aqueous concentrations closely matched original estimates of production and use, implying limited global transport. Positive correlations between log-transformed concentrations of Σ7PCB, ΣDDTs, Σendosulfan, and Σchlordane, but not ΣHCH, and the log of population density (p < 0.05) within 5 and 10 km of the sampling sites also supported limited transport from used sites. These results help to understand the extent of global distribution, and eventually time-trends, of organic pollutants in aquatic systems, such as across freshwaters and oceans. Future deployments will aim to establish time-trends at selected sites while adding to the geographical coverage.

Effects of organic carbon/elemental carbon and particle size on inhalation bioaccessibility of particle-bound PAHs.

Bioaccessible fractions of particle-bound hydrophobic organic compounds (HOCs) are critical to evaluating human inhalation exposure risk. However, the key factors for controlling the release of HOCs into the lung fluid are not adequately examined. To address this issue, eight particle size fractions (0.056-18 µm) from different particle emission sources (barbecue and smoking) were collected and incubated with an in vitro method for determining inhalation bioaccessibilities of polycyclic aromatic hydrocarbons (PAHs). The bioaccessible fractions of particle-bound PAHs were 35-65% for smoke-type charcoal, 24-62% for smokeless-type charcoal, and 44-96% for cigarette. The size distributions of bioaccessible fractions of 3-4 ring PAHs were symmetric with the patterns of their masses, characterized as a unimodal distribution with both the trough and peak at 0.56-1.0 µm. Analysis from machine learning showed that chemical hydrophobicity appeared to be the most significant factor affecting inhalation bioaccessibility of PAHs, followed by organic carbon and elemental carbon contents. Particle size seemed to have little effect on the bioaccessibility of PAHs. A compositional analysis of human inhalation exposure risk from total concentration, deposition concentration, and bioaccessible deposition concentration in alveolar region showed a shift in the key particle size from 0.56-1.0 µm to 1.0-1.8 µm and an increasing in the contributions of 2-3 ring PAHs to risk for cigarette due to the high bioaccessible fractions. These results suggested the significance of particle deposition efficiency and bioaccessible fractions of HOCs in risk assessment.

Plastic waste discharge to the global ocean constrained by seawater observations.

Marine plastic pollution poses a potential threat to the ecosystem, but the sources and their magnitudes remain largely unclear. Existing bottom-up emission inventories vary among studies for two to three orders of magnitudes (OMs). Here, we adopt a top-down approach that uses observed dataset of sea surface plastic concentrations and an ensemble of ocean transport models to reduce the uncertainty of global plastic discharge. The optimal estimation of plastic emissions in this study varies about 1.5 OMs: 0.70 (0.13-3.8 as a 95% confidence interval) million metric tons yr-1 at the present day. We find that the variability of surface plastic abundance caused by different emission inventories is higher than that caused by model parameters. We suggest that more accurate emission inventories, more data for the abundance in the seawater and other compartments, and more accurate model parameters are required to further reduce the uncertainty of our estimate.

Joint effects of temperature and copper exposure on developmental and gene-expression responses of the marine copepod Tigriopus japonicus.

There is growing contamination of copper (Cu) in the marine environment, particularly after the ban of organotin compounds and the increase of the use of Cu-based antifouling paints. Although there are increasing research interests in temperature-dependent chemical toxicity to aquatic organisms, most existing studies focused on acute impacts of chemicals at high concentrations. This study aimed to investigate the interacting effect of temperature and copper exposure at environmentally relevant concentrations on survival and development in the marine copepod Tigriopus japonicus with a partial life-cycle toxicity test. Expressions of five stress response genes in the copepod, namely two glutathione S-transferases (GST-S and GST-O), two heat shock proteins (HSP70 and HSP90), and glutathione reductase (GR) were also investigated. The copepod's survival was significantly impaired at 15 °C after development to adult stage, while its developmental time reduced significantly with increasing temperature. Copper at the two environmentally relevant test concentrations had no significant impacts on these apical endpoints whereas the interaction between Cu and temperature was more significant in modulating gene expressions. GST-S, GST-O and HSP90 genes in copepods exposed to 100 µg Cu L-1 were significantly upregulated at 20 °C. At 32 °C, most genes were either insignificantly expressed or down-regulated, compared to the control, likely suggesting that thermal stress inhibited the copepod's antioxidative defense system. Overall, the results revealed that the joint Cu and thermal stresses have significantly elicited antioxidative system in the copepods. It clearly demonstrated the need for more fundamental studies about potential impacts of different environmental factors such as temperature on chemical toxicity under realistic scenario of marine pollution.

Country-specific riverine contributions to marine plastic pollution.

Marine plastic debris are mainly derived from land-based sources, and the transport of plastics via global rivers is of great concern. Ample efforts have been made in estimating the land-based contributions of plastic to the global oceans, but quantifying country-specific (and per capita) riverine outflows is an important step toward the development of a globally integrated framework to mitigate marine plastic pollution. To estimate the country-specific riverine contributions to global marine plastic pollution, we built a River-to-Ocean model framework. In 2016, the median annual country-specific riverine plastic outflows and related per capita values for 161 countries varied between 0.76 and 103,000 metric tons (MT) and 0.83-248 g, respectively. India, China, and Indonesia were the top three contributors to riverine plastic outflows, whereas Guatemala, Philippines, and Colombia had the highest per capita riverine plastic outflows. The total riverine plastic outflow from 161 countries was in the range of 0.15-0.53 million MT annually, accounting for 0.4 %-1.3 % of the 40 million MT plastic waste generated yearly by more than seven billion humans. Population, plastic waste generation, and Human Development Index are the dominant factors influencing riverine plastic outflows to global oceans from individual countries. Our findings provide an important basis for launching effective plastic pollution management and control measures in global countries.

Environmental fate of microplastics in an urban river: Spatial distribution and seasonal variation.

Rivers are recognized as an important pathway for transport of microplastics (MPs) from land to sea, but limited information is available on the spatial distribution and seasonal variation of riverine MPs from upper reaches to estuaries. Such information is critical for source apportionment and development of effective management measures for riverine MPs. To fill the knowledge gap, we investigated the occurrence of MPs in surface water along an urban river in Guangzhou, southern China in wet and dry seasons. The abundances of MPs from 16 sampling sites in the wet and dry seasons varied from 0.123 to 1.84 particles m-3 and from 0.046 to 4.21 particles m-3, respectively. The spatial distribution of MP abundances showed an increasing trend from upstream to midstream and a decreasing trend from midstream to downstream and estuaries. The abundances of MPs peaked at the midstream, which is surrounded by a highly urbanized region with high population density (∼2530 persons per km2). The large surface water runoff during the wet season elevated the MP abundance in riverine water, except for that flowing through the central urban area where the abundance of MPs collected in the dry season was higher than that in the wet season. This was mainly ascribed to the large input from extensive anthropogenic activities and slow water flow rate in urban areas. The estimated monthly riverine MP fluxes from Humen, Hongqili, and Jiaomen were 7.42, 2.38, and 2.3 billion particles, respectively, in the wet season, and 0.86, 0.71, and 0.19 billion particles, respectively, in the dry season. An increase of riverine MP fluxes from Humen, Hongqili, and Jiaomen in the past three years was evident. The results from the present study provide valuable information for source apportionment of riverine MPs and support the initialization of possible MPs controlling measures.

Size-resolved gas-particle partitioning characteristics of typical semi-volatile organic compounds in urban atmosphere.

Understanding particle size distribution and size-resolved gas-particle partitioning of semi-volatile organic compounds (SVOCs) is important for characterizing their fate in atmosphere. However, the size-resolved gas-particle partitioning characteristics of SVOCs has not been adequately considered. To address this issue, the present study collected gaseous and size-fractioned particulate samples both in and outside of schools, offices, and residences in three districts of different urbanization levels in a megacity, Guangzhou, South China during two seasons. Typical SVOCs, including 15 polycyclic aromatic hydrocarbons (PAHs), six organophosphate esters and seven phthalic acid esters were measured. Emission sources, physicochemical properties, and environmental conditions at the sampling sites considerably impacted the spatiotemporal distribution patterns and particle size distribution of target SVOCs. Not all observed gas-particle partition coefficients (Kp) of target SVOCs were negatively correlated with subcooled liquid-vapor pressures (PL0), probably because certain factors, such as the non-exchangeable part of the particle-bound SVOCs, were not considered in traditional gas-particle partition theories. Particle size was an important factor affecting gas-particle partitioning. Adsorption was the dominant mechanism for PAHs with high molecular weight in different particle modes. A new model was established to predict size-resolved Kp of PAHs with high molecular weight based on PL0 and particle size.

Impact of iron/aluminum (hydr)oxide and clay minerals on heteroaggregation and transport of nanoplastics in aquatic environment.

Nanoplastics (NPs) are emerging contaminants in the environment, where the transport and fate of NPs would be greatly affected by interactions between NPs and minerals. In the present study, the interactions of two types of polystyrene nanoplastics (PSNPs), i.e., bare-PSNPs and carboxylated PSNPs-COOH, with iron (hydr)oxides (hematite, goethite, magnetite, and ferrihydrite), aluminum (hydr)oxides (boehmite and gibbsite), and clay minerals (kaolinite, montmorillonite, and illite) were investigated. The positively charged iron/aluminum (hydr)oxide minerals could form heteroaggregates with negatively charged PSNPs. Electrostatic and hydrophobic interaction dominate for the heteroaggregation of bare-PSNPs with iron/aluminum (hydr)oxide minerals, while ligand exchange and electrostatic interaction are involved in the heteroaggregation of PSNPs-COOH with iron/aluminum (hydr)oxides minerals. However, heteroaggregation between PSNPs and negatively charged clay minerals was negligible. Humic acid markedly suppressed such heteroaggregation between PSNPs and minerals due to enhanced electrostatic repulsion, steric hindrance, and competition of surface attachment sites. The heteroaggregation rates of both bare-PSNPs and PSNPs-COOH with hematite decreased with increasing solution pH. Increased ionic strength enhanced the heteroaggregation of PSNPs-COOH but inhibited that of bare-PSNPs. The results of the present study suggested that the heteroaggregation of PSNPs in environments could be strongly affected by minerals, solution pH, humic acid, and ionic strength.

Insufficient evidence to link human exposure to heavy metals with biomarkers of glioma.

Information on molecular mechanisms has implicated potential association between the concentrations of heavy metals and incidences of glioma, but experimental data on human brain tissue remain sparse. To address this data gap, 13 heavy metals were measured in 137 glioma and 35 non-glioma samples collected from 161 alive patients in Guangdong Province, China in 2019 - 2020. All target heavy metals were detected, suggesting they could cross the blood-brain barrier. Concentrations of Mn, Cu, and Zn were higher in glioma than in non-glioma samples, while those of Ni and Se were higher in non-glioma samples, probably suggesting that these five heavy metals are more prone to be altered by changing pathological conditions. In addition, Cu/Zn, Cr/Mn, Cr/Se, Ni/Se, Pb/Mn, and Pb/Se were statistically different between glioma and non-glioma samples by a difference test and a multiple logistic regression model. These concentration ratios may serve as chemical markers to assist pathological analysis for differentiating between tumor and healthy tissues. However, no direct link between heavy metal concentrations or concentration ratios and biomarkers of glioma (i.e., tumor grade, P53, and Ki-67) was observed. No sufficient evidence was obtained to implicate the role of heavy metals in inducing glioma, largely caused by the limited number of samples. Different concentrations and concentration ratios of heavy metals may be the consequence rather than the cause of pathological changes in brain tumors.

Glioma is associated with exposure to legacy and alternative per- and polyfluoroalkyl substances.

Data on the occurrences of legacy and alternative per- and polyfluoroalkyl substances (PFASs) in glioma are scarce. It remains unclear if PFASs exposure is related to the prevalence of glioma. A total of 137 glioma and 40 non-glioma brain tissue samples from patients recruited from the Nanfang Hospital, South China were analyzed for 17 PFAS compounds. Perfluorohexanoic acid, perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS), perfluorooctane sulfonamide (FOSA), and 6:2 chlorinated polyfluorinated ether sulfonate were frequently detected (> 60 %) in glioma. The total concentrations (range; median) of 17 PFASs in glioma (0.20-140; 3.1 ng g-1) were slightly higher than those in non-glioma (0.35-32; 2.2 ng g-1), but without statistical significance. The PFAS concentrations in males were statistically higher (p < 0.05) than those in females. Elevated glioma grades were associated with higher concentrations of PFOA, PFOS, and FOSA. Positive correlations were observed between PFAS concentrations (especially for PFOA) and Ki-67 or P53 expression, pathological molecular markers of glioma. Our findings suggested that exposure to PFASs might increase the probability to develop glioma. This is the first case study demonstrating associations between PFASs exposure and brain cancer. More evidences and potential pathogenic mechanisms warranted further investigations.

Predicted health and environmental hazards of liquid crystal materials via quantitative structure-property relationship modeling.

Liquid crystal materials (LCMs) are considered as emerging contaminants with high persistent and bioaccumulative potentials, but their toxicological effects are not well understood. To address this issue, a list of 1431 LCMs commercially available in the market was established through literature reviews and surveys of LCM suppliers. Toxicological properties of 221 target LCMs were derived from the Classification and Labeling Inventory by the European Chemicals Agency. More than 80 % of target LCMs likely pose adverse effects on human health or aquatic ecosystems. Two quantitative structure-property relationship (QSPR) models developed from the toxicological properties of LCMs achieved approximately 90 % accuracy in external data sets. The probability-based approach was more efficient in defining the applicability domain for the QSPR models than a range- or distance-based approach. The highest accuracy was achieved for chemicals within the probability-based applicability domain. The QSPR models were applied to predict health and environmental hazards of 1210 LCMs that had not been notified to the Classification and Labeling Inventory, and 301 and 94 LCMs were recognized as posing potential hazards to human health and the environment, respectively. The present study highlights the potential detrimental effects of LCMs and offers a specific in silico technique for screening hazardous LCMs.

Transfer of Frictional Contact Derived Phthalates from Pad Surface Enhances Dermal Exposure.

Dermal exposure to chemicals derived from object surface contact is an important contributor to increased health risk. However, chemical transfer induced by mechanical friction between dermal and object surface has yet to be adequately addressed. To fill this knowledge gap, rubbing fabrics were used as surrogate skins to stimulate dermal mechanical friction with pad products with phthalates as target analytes. The results showed that the amounts of phthalates transferred increased linearly with contact burden (50-1000 g), contact duration (1-10 min), and sliding speed (3.0-9.0 cm s-1). The surface texture of surrogate skins dictated the accumulation of phthalates. Net/pocket micro-surface structures of rubbing fabrics induced a higher accumulation of phthalates than U-shape structures of fabrics with a similar surface roughness. Covering of the pad surface by a layer of textile was effective in minimizing the transfer of phthalates induced by mechanical motion. The estimated transfer efficiency of bis(2-ethylhexyl) ester (DEHP) derived from rubbing friction (0.005-0.05%) upon the pad surface over 8 h was greater than those for gas-phase emission (0.00002-0.0005% over 24 h) and sweat transfer (0.008-0.012% over 24 h). These results indicated that dermal frictional contact with the surface of pad products was an important exposure pathway.

Decadal Journey of E-Waste Recycling: What Has It Achieved?

E-waste recycling has been a hot topic around the world. This Feature revisits the issues raised by our previous Feature 10 years ago, i.e., the environmental, economic, and social benefits of e-waste recycling, using China as an example. The decadal journey of e-waste recycling has witnessed a giant leap from haphazard disposal initially to regulated disassembly presently. Specific successful stories include cleaned environment and reduced human exposure, significant advantages of urban mining over mineral mining, additional employment opportunities, and improved legislation system related to e-waste recycling. Strict legislation systems related to e-waste management based on the principle of Extended Producer Responsibility are key to the sustainable development of the e-waste recycling sector in China. The experiences and lessons learned in China would provide valuable guidelines for other developing countries.