Reservoirs located in middle and high latitudes freeze for months in winter, where the accumulation characteristics of pollutants are changed by superimposed influence of salt exclusion from ice on the surface and pollution release from sediments at the bottom. Taking total nitrogen (TN) of Biliuhe reservoir in Northeast China as an example, we developed a model to simulate TN accumulation characteristics influenced by ice and sediments during the freezing period (NACISF), and quantified contributions of TN from ice and sediments. Model parameters of ice and sediments were determined by laboratory freeze-up simulation experiment and sediment release flux simulation experiment, and water quality data were obtained from field investigations. Results showed that the annual average amount of TN input during the ice-covered period from 2015 to 2020 was 220.77 t, the output was 400.11 t, and the accumulated amount was 589.52 t. TN excluded from ice and released from sediments contributed 8.12% and 7.17% of the total TN inputs in winter, respectively. Analysis showed that the TN excluded from ice was positively correlated with ice thickness and initial TN concentration. The maximum ice thickness of Biliuhe reservoir had a 13 year cyclic feature, and the proportion of TN excluded from ice to the total TN inputs in different periods ranged from 10.68% to 17.30% (mean 13.18%). Meanwhile, TN accumulated seasonally as summer > autumn > winter > spring. The TN exclusion effect in 2050 would be weakened when considering the combined effects of climate change and human activities, with a reduction of about 40.85% compared to the current. It is concluded that the NACISF model took into account the influences of both ice and sediments, which provided a detailed understanding of the accumulation characteristics of TN during freezing period, and had important reference significance for water quality management in winter.

Nitrous acid (HONO), an essential precursor of hydroxyl radicals (OH) in the troposphere, plays an integral role in atmospheric photochemistry. However, potential HONO sources remain unclear, particularly in rural areas, where long-term (including seasonal) measurements are scarce. HONO and related parameters were measured at a rural site in the North China Plain (NCP) during the winter of 2017 and summer and autumn of 2020. The mean HONO level was higher in winter (1.79 ± 1.44 ppbv) than in summer (0.67 ± 0.50 ppbv) and autumn (0.83 ± 0.62 ppbv). Source analysis revealed that the heterogeneous conversion (including photo-enhanced conversion) of NO₂ on the ground surface dominated the daytime HONO production in the three seasons (43.1% in winter, 54.3% in summer, and 62.0% in autumn), and the homogeneous reaction of NO and OH contributed 37.8, 12.2, and 28.4% of the daytime HONO production during winter, summer, and autumn, respectively. In addition, the total contributions of other sources (direct vehicle emissions, particulate nitrate photolysis, NO₂ uptake and its photo-enhanced reaction on the aerosol surface) to daytime HONO production were less than 5% in summer and autumn and 12.0% in winter. Unlike winter and autumn, an additional HONO source was found in summer (0.45 ± 0.21 ppbv h⁻¹, 31.4% to the daytime HONO formation), which might be attributed to the HONO emission from the fertilized field. Among the primary radical sources (photolysis of HONO, O₃, and formaldehyde), HONO photolysis was dominant, with contributions of 82.6, 49.3, and 63.2% in winter, summer, and autumn, respectively. Our findings may aid in understanding HONO formation in different seasons in rural areas and may highlight the impact of HONO on atmospheric oxidation capacity.

No anthropogenic pollutant is more widespread in the aquatic and terrestrial environment than microplastic; however, there are large knowledge gaps regarding its origin, fate, or temporal variations in the oceans. In this study, we analyzed sediment trap material from the deep subtropical Northeast Atlantic (2000 m) in a long-term record (2003–2015) to assess the role of the deep ocean as a potential sink of microplastics. Microplastic particles were identified in all 110 analyzed samples with flux rates of 1.13–3146.81 items d⁻¹ m⁻². Calculated microplastic mass fluxes ranged between 0.10 and 1977.96 μg d⁻¹ m⁻², representing up to 8% of the particle flux. Between years, the composition of the different polymers changed significantly, dominated by polyethylene, whose amount was correlated with the lithogenic input. The correlation between polyethylene and the lithogenic fraction was attributed to an air transport pathway from northeast Africa and surrounding regions. The second most abundant polymer detected in our study was polyvinyl chloride, which is not correlated with lithogenic or biogenic particle flux fractions. Instead, we observed seasonality for polyvinyl chloride with recurring high fluxes in winter before the plankton bloom and significantly lower amounts in summer. Other polymers identified were polypropylene, polyethylene terephthalate, and lower numbers of polystyrene and polymethyl methacrylate. The average microplastic particle size for all samples and polymers was 88.44 ± 113.46 μm, with polyethylene and polyvinyl chloride having the highest proportion of small particles (<100 μm). Our findings provide first insights into temporal variations of sinking microplastics, which are crucial for understanding the fate of plastic in the oceans.

In peri-urban critical zones, soil ecosystems are highly affected by increasing urbanization, causing probably an intense interaction between dissolved organic matter (DOM) and heavy metals in soil. Such interaction is critical for understanding the biogeochemical cycles of both organic matter and heavy metals in these zones. However, limited research has reported the correlative distribution of DOM and heavy metals at high seasonal and spatial resolutions in peri-urban critical zones. In this study, 160 soil samples were collected from the farmland and forestland of Zhangxi watershed, in Ningbo, eastern China during spring, summer, fall and winter four seasons. UV–visible absorption and fluorescent spectroscopy were used to explore the optical characteristics of DOM. The results indicated a mixture of exogenous and autogenous sources of DOM in the Zhangxi watershed, while DOM in farmland exhibited a higher degree of aromaticity and humification than that in forestland. Fluorescent results showed that humic acid-like, fulvic acid-like and microbial-derived humic-like fractions were mostly affected by seasons. The distribution of heavy metals was affected mainly by land-use changes and seasons. Correlation analysis between heavy metals and DOM characteristics and components suggested that aromatic and humic substances were more favorable in binding with EDTA extractable Ni, Cu, Zn and Cd. The bioavailable Cd and Pb decreased due to binding with humic fractions, indicating its great effects on the bioavailability of Cd and Pb. Overall, these findings provide an insight into the correlative distributions of DOM and heavy metals in peri-urban areas, thereby highlighting their biogeochemical cycling in the soil environment.

South Korea has experienced a rapid increase in ozone concentrations in surface air together with China for decades. Here we use a 3-D global chemical transport model, GEOS-Chem nested over East Asia (110 E - 140 E, 20 N–50 N) at 0.25° × 0.3125° resolution, to examine locally controllable (domestic anthropogenic) versus uncontrollable (background) contributions to ozone air quality at the national scale for 2016. We conducted model simulations for representative months of each season: January, April, July, and October for winter, spring, summer, and fall and performed extensive model evaluation by comparing simulated ozone with observations from satellite and surface networks. The model appears to reproduce observed spatial and temporal ozone variations, showing correlation coefficients (0.40–0.87) against each observation dataset. Seasonal mean ozone concentrations in the model are the highest in spring (39.3 ± 10.3 ppb), followed by summer (38.3 ± 14.4 ppb), fall (31.2 ± 9.8 ppb), and winter (24.5 ± 7.9 ppb), which is consistent with that of surface observations. Background ozone concentrations obtained from a sensitivity model simulation with no domestic anthropogenic emissions show a different seasonal variation in South Korea, showing the highest value in spring (46.9 ± 3.4 ppb) followed by fall (38.2 ± 3.7 ppb), winter (33.0 ± 1.9 ppb), and summer (32.1 ± 6.7 ppb). Except for summer, when the photochemical formation is dominant, the background ozone concentrations are higher than the seasonal ozone concentrations in the model, indicating that the domestic anthropogenic emissions play a role as ozone loss via NOₓ titration throughout the year. Ozone air quality in South Korea is determined mainly by year-round regional background contributions (peak in spring) with summertime domestic ozone formation by increased biogenic VOCs emissions with persistent NOₓ emissions throughout the year. The domestic NOₓ emissions reduce MDA8 ozone around large cities (Seoul and Busan) and hardly increase MDA8 in other regions in spring, but it increases MDA8 across the country in summer. Therefore, NOₓ reduction can be effective in control of MDA8 ozone in summer, but it can have rather countereffect in spring.

Air pollution and extreme heat have been responsible for more than a million deaths in China every year, especially in densely urbanized regions. While previous studies intensively evaluated air pollution episodes and extreme heat events, a limited number of studies comprehensively assessed atmospheric hot-and-polluted-episodes (HPE) – an episode with simultaneously high levels of air pollution and temperature – which have potential adverse synergic impacts on human health. This study focused on the Pearl River Delta (PRD) region of China due to its high temperature in summer and poor air quality throughout a year. We employed geostatistical downscaling to model meteorology at a spatial resolution of 1 km, and applied a machine learning algorithm (XGBoost) to estimate a high-resolution (1 km) daily concentration of particulate matter with an aerodynamic diameter ≤2.5 μm (PM₂.₅) and ozone (O₃) for June to October over 20 years (2000–2019). Our results indicate an increasing trend (∼50%) in the frequency of HPE occurrence in the first decade (2000–2010). Conversely, the annual frequency of HPE occurrence reduced (16.7%), but its intensity increased during the second decade (2010–2019). The northern cities in the PRD region had higher levels of PM₂.₅ and O₃ than their southern counterparts. During HPEs, regional daily PM₂.₅ exceeded the World Health Organization (WHO) and Chinese guideline levels by 75% and 25%, respectively, while the O₃ exceeded the WHO O₃ standard by up to 69%. Overall, 567,063 (95% confidence interval (CI): 510,357–623,770) and 52,231 (95%CI: 26,116–78,346) excessive deaths were respectively attributable to exposure to PM₂.₅ and O₃ in the PRD region. Our findings imply the necessity and urgency to formulate co-benefit policies to mitigate the region's air pollution and heat problems.

The coastal megacity Shanghai is located in the center of the Yangtze River Delta, a dominant flame retardants (FRs) production region in China, especially for organophosphate esters (OPEs). This prompted us to investigate occurrence and seasonal changes of atmospheric OPEs in Shanghai, as well as to evaluate their sources, environmental behavior and fate as a case study for global coastal regions. Atmospheric gas and particle phase OPEs were weekly collected at two coastal sites - the emerging town Lingang New Area (LGNA), and the chemical-industry zone Jinshan Area (JSA) from July 2016–June 2017. Total atmospheric concentrations of the observed OPEs were significantly higher in JSA (median of 1800 pg m⁻³) than LGNA (median of 580 pg m⁻³). Tris(1-chloro-2-propyl) phosphate (TCPP) was the most abundant compound, and the proportion of three chlorinated OPEs were higher in the particle phase (55%) than in the gas phase (39%). The year-round median contribution of particle phase OPEs was 33%, which changed strongly with seasons, accounting for 10% in summer in contrast to 62% in winter. Gas and particle phase OPEs in JSA exhibited significant correlations with inverse of temperature, respectively, indicating the importance of local/secondary volatilization sources. The estimated fluxes of gaseous absorption were almost 2 orders of magnitude higher than those of particle phase deposition, which could act as sources of organic phosphorus to coastal and open ocean waters.

Industrial parks emit large amounts of anthropogenic heat and aggravate the urban heat island effect, which has become a severe environmental problem worldwide. Few studies explored if the warming effect generated by concentrated industrial facilities (i.e., steel plants in this study) produces an intra-heat island effect in urban built-up areas. Sufficient evidence of an industrial heat island (IHI) effect is lacking, and new quantitative methods are urgently needed to address these issues. Therefore, we proposed a new scheme to quantify the warming effect of large, heat-emitting urban objects versus complex surroundings, and the IHI effect was accordingly defined at a finer scale. This study separated the industrial park from other artificial lands and comprehensively estimated the IHI effects' spatiotemporal variation. The IHI intensities were measured based on varied natural and urbanized references, which provided new evidence for the existence of the IHI effect over space and seasons. The land surface temperature (LST) profiles delineated the downward trend in LST variation from inside to surroundings in the IHI cases on both spatial and temporal scales. The time-series analysis revealed that the IHI effects demonstrated more significant disparities regarding the LSTs between the industrial parks and their surrounding backgrounds during warm seasons than in cold seasons. And a more severe IHI effect was observed in spring and summer, and the weakest IHI intensity occurred in winter. Moreover, the IHI intensity is positively associated to the anthropogenic heat, indicating that the industrial activities contribute to the increased LSTs of the industrial park to a great extent. The rationale of the IHI effect can broaden insight for understanding how urban industrial heat sources influence the regional thermal environment, especially at a finer scale.

Laboratory experiments and point observations, for instance in wetlands, have shown evidence that microbial sulfate reduction (MSR) can lower sulfate and toxic metal concentrations in acid mine drainage (AMD). We here hypothesize that MSR can impact the fate of AMD in entire catchments. To test this, we developed a sulfur isotope fractionation and mass-balance method, and applied it at multiple locations in the catchment of an abandoned copper mine (Nautanen, northern Sweden). Results showed that MSR caused considerable, catchment-scale immobilization of sulfur corresponding to a retention of 27 ± 15% under unfrozen conditions in the summer season, with local values ranging between 13 ± 10% and 53 ± 18%. Present evidence of extensive MSR in Nautanen, together with previous evidence of local MSR occurring under many different conditions, suggest that field-scale MSR is most likely important also at other AMD sites, where retention of AMD may be enhanced through nature-based solutions. More generally, the developed isotope fractionation analysis scheme provides a relatively simple tool for quantification of spatio-temporal trends in MSR, answering to the emerging need of pollution control from cumulative anthropogenic pressures in the landscape, where strategies taking advantage of MSR can provide viable options.

Atmospheric peroxyacetyl nitrate (PAN) and ozone (O₃) are two typical indicators for photochemical pollution that have adverse effects on the ecosystem and human health. Observation networks for these pollutants have been expanding in developed regions of China, such as North China Plain (NCP) and Pearl River Delta (PRD), but are sparse in Yangtze River Delta (YRD), meaning their concentration and influencing factors remain poorly understood. Here, we performed a one-year measurement of atmospheric PAN, O₃, particulate matter with aerodynamic diameter smaller than 2.5 μm (PM₂.₅), nitrogen oxides (NOₓ), carbon monoxide (CO), and meteorological parameters from December 2016 to November 2017 in Shanghai. Overall, high hourly maximum PAN and O₃ were found to be 7.0 and 185 ppbv in summer, 6.2 and 146 ppbv in autumn, 5.8 and 137 ppbv in spring, and 6.0 and 76.7 ppbv in winter, respectively. Continental air masses probably carried atmospheric pollutants to the sampling site, while frequent maritime winds brought in less polluted air masses. Furthermore, positive correlations (R: 0.72–0.85) between PAN and O₃ were found in summer, indicating a predominant role of photochemistry in their formation. Unlike in summer, weak or no correlations between PAN and O₃ were featured during the other seasons, especially in winter, due to their different loss pathways. Unexpectedly, positive correlations between PAN and PM₂.₅ were found in all seasons. During summer, moderate correlation could be attributed to the strong photochemistry acting as a common driver in the formation of secondary aerosols and PAN. During winter, high PM₂.₅ might promote PAN production through HONO production, hence resulting in a good positive correlation. Additionally, the loss of PAN by thermal decomposition (TPAN) only accounted for a small fraction (ca. 1%) of the total (PAN + TPAN) during a typical winter episode, while it significantly reached 14.4 ppbv (71.1% of the total) in summer.