Sulfate radical (SO₄⁻)-based advanced oxidation processes (SR-AOPs) are promising in-situ chemical oxidation technologies widely applied for soil/groundwater remediation. The presence of non-target water constituents may interfere the abatement of contaminants by SR-AOPs as well as result in the formation of unintended byproducts. Herein, we reported the formation of toxic chloronitrophenols during thermally activated persulfate oxidation of 2-chlorophenol (2CP) in the presence of nitrite (NO₂⁻). 2-Chloro-4-nitrophenol (2C4NP) and 2-chloro-6-nitrophenol (2C6NP) were identified as nitrated byproducts of 2CP with total yield up to 90%. The formation of nitrated byproducts is a result of coupling reaction between 2CP phenoxyl radical (ClPhO) and nitrogen dioxide radical (NO₂). As a critical step, the formation of ClPhO was supported by density functional theory (DFT) computation. Both 2C4NP and 2C6NP could convert to 2-chloro-4,6-dinitrophenol (2C46DNP) upon further treatment via a denitration-renitration process. The formation rate of 2C4NP and 2C6NP was closely dependent on the concentration of NO₂⁻, solution pH, and natural water constituents. ECOSAR calculation suggests that chloronitrophenols are generally more hydrophobic and ecotoxic than 2CP. Our result therefore reveals the potential risks in the abatement of chlorophenols by SR-AOP, particularly when high level of NO₂⁻ is present in water matrix.

Air pollution is one of the most important branches of environmental science as it affects human health, climate and ecosystems. Emissions of air pollutants from transport (vehicles and ships) in port cities strongly affect air quality at local scales, warranting for a combination of theoretical and experimental studies to identify pollution hotspots. The purpose of this paper is to provide a methodology for developing a hybrid emission inventory from transport sector for two port cities located respectively on the Northern Aegean islands of Chios and Lesvos. Emission inventories were constructed for the year 2014 based on top-down and bottom-up approaches. Official data from local authorities and survey results were used for the calculation of emissions. Traffic emissions were spatially allocated to the road network based on population data and hourly traffic counts, and distributed over time (on an hourly basis) with the use of local temporal coefficients.Regarding carbon monoxide road emissions, the highest quantities are mainly emitted by Passenger Cars (43%,32% in Chios and Lesvos respectively) while for PM₁₀ emissions, trucks have the largest share (66% in Chios and 86% in Lesvos). The pollutants that are emitted in greater quantities from the ships at the ports of Mytilene and Chios are NOₓ, followed by SO₂ and CO. Most of the ship emissions in the ports occur by the ships at berth, as they remain berthed for hours whereas maneuvering lasts 15–20 min. As for the daily contribution of the two transport sources to the pollution profile of Mytilene, road emissions are higher for almost all pollutants. However, the contribution of ship emissions is not negligible, especially during the touristic period when marine traffic increases and emissions close to the port area become more important than those from road transport.

This study investigates the characteristics of PCN emission and removal from two secondary copper metallurgical processes (plants A and B) equipped with different air pollution control devices (APCDs). Different operating conditions and feeding materials result in varying emission factors of PCNs from two plants. The average PCN concentration emitted from plant B (7597 ng Nm⁻³) is significantly higher than that emitted from plant A (32.5 ng Nm⁻³) and those reported in China (5.8–2845 ng Nm⁻³). Similar trend is found for fly ash samples collected from two plants. Low chlorinated homologues (Mono-to Tri-CNs) are the major contributors to total PCNs measured in flue gas, fly ash and slag samples. Combination of semi-dry absorber, activated carbon injection and baghouse is effective for PCN removal in plant A, with the overall removal efficiency of 98%. The overall removal efficiency of PCNs achieved with APCDs equipped in plant B is 90%, however, increases of some homologues as the flue gases passing through baghouse and wet scrubber are found, suggesting the occurrence of memory effect within baghouse and wet scrubber.

Both microplastics and persistent organic pollutants (POPs) are ubiquitously present in natural water environment, posing a potential threat to aquatic organisms. While it has been suggested that the immune responses of aquatic organisms could be hampered by exposure to microplastics and POPs, the synergistic immunotoxic impact of these two types of pollutants remain poorly understood. In addition, little is known about the mechanism behind the immunotoxic effect of microplastics. Therefore, in the present study, the immunotoxicity of microplastics and two POPs, benzo[a]pyrene (B[a]P) and 17β-estradiol (E2), were investigated alone or in combination in a bivalve species, Tegillarca granosa. Evident immunotoxicity, as indicated by alterations of haemocyte count, blood cell composition, phagocytic activity, intracellular content of ROS, concentration of Ca²⁺ and lysozyme, and lysozyme activity, was revealed for both microplastics and the two POPs examined. In addition, the expression of six immune-, Ca²⁺ signalling-, and apoptosis-related genes was significantly altered by exposure of clams to the contaminants studied. Furthermore, the toxicity of POPs was generally aggravated by smaller microplastics (500 nm) and mitigated by larger ones (30 μm). This size dependent effect on POP toxicity may result from size dependent interactions between microplastics and POPs. Data obtained in this study also indicate that similar to exposure to B[a]P and E2, exposure to microplastics may hamper the immune responses of clams through a series of interdependent physiological and molecular processes.

The effect of relative humidity and temperature on the submicron aerosol variability and its ageing process was studied over a high altitude site, Mahabaleshwar in south-west India. The mass composition of non-refractory particulate matter of 1 μm (NR-PM₁) size was obtained using Time of Flight Aerosol Chemical Speciation Monitor (ToF-ACSM) along with the measurements on a few trace gases during winter (December 2017–February 2018) and summer season (20th March - 5th May 2018). Sulfate exhibited strong dependence on the relative humidity (RH) as its mass fraction increased with the increase in RH. The Sulfate oxidation ratio (SOR) calculated during summer season also showed an increasing trend with RH indicating the influence of aqueous phase oxidation on sulfate fraction. On the other hand, OOA showed remarkable enhancement in its mass fraction with the increase in temperature along with the corresponding increase in f₄₄ and tropospheric ozone. OOA, ozone and f₄₄ ratio increased 14–34%, 8–26% and 25–43% respectively with the increase in temperature from 18 to 30 °C. This is indicative of the dominance of photochemical ageing processes during high temperature conditions. The extent of photochemical ageing was found to be higher during summer season (mean temperature ∼25.4 ± 2.6 °C) as compared to winter season (mean temperature ∼20.5 ± 2.6 °C). The nitrate diurnal was majorly governed by gas to particle partitioning process during winter season, whereas the summertime nitrate diurnal was influenced primarily by its formation rate. The non parametric wind regression analysis revealed that the mass concentration during winter was majorly contributed by distant sources from north east direction while during summer the local sources were more dominant.

This three-decade long study was conducted in the Pearl River Delta (PRD), a rapidly urbanizing region in southern China. Extensive soil samples for a diverse land uses were collected in 1989 (113), 2005 (1384), 2009 (521), and 2018 (421) for heavy metals of As, Cr, Cd, Cu, Hg, Ni, Pb and Zn. Multiple pollution indices and Structural Equation Models (SEMs) were used in attribution analysis and comprehensive assessments. Data showed that majority of the sampling sites was contaminated by one or more heavy metals, but pollutant concentrations had not reached levels of concerns for food security or human health. There was an increasing trend in heavy metal contamination over time and the variations of soil contamination were site-, time- and pollutant-dependent. Areas with high concentrations of heavy metals overlapped with highly industrialized and populated areas in western part of the study region. A dozen SEMs path analyses were used to compare the relative influences of key environmental factors on soil contamination across space and time. The high or elevated soil contaminations by As, Cr, Ni, Cu and Zn were primarily affected by soil properties during the study period, except 1989–2005, followed by land use patterns. Parent materials had a significant effect on elevated soil contamination of Cd, Cr, Ni, Pb and overall soil pollution during 1989–2005. We hypothesized that other factors not considered in the present study, such as atmospheric deposition, sewage irrigation, and agrochemical uses, may be also important to explain the variability of soil contamination. This study implied that strategies to improve soil physiochemical properties and optimize landscape structures are viable methods to mitigate soil contamination. Future studies should monitor pollutant sources identified by this study to fully understand the causes of heavy metal contamination in rapidly industrialized regions in southern China.

Cadmium (Cd) exposure poses a serious environmental problem due to the metal’s bioaccumulation and difficult to eliminate from body. Understanding the mechanisms of Cd detoxification and resistance can provide insights into methods to protect against the damaging effects of the heavy metal. In the present study, we found that heat shock (HS) pretreatment increased Cd resistance of the nematode Caenorhabditis elegans by reducing the bagging phenotype and protecting the integrity of the intestinal barrier. HS pretreatment increased the expression of heat shock protein-16.2 (HSP-16.2) prior to Cd exposure, and HS-induced Cd resistance was absent in worms with hsp-16.2 loss-of-function mutation. Worm strain with daf-2(e1370) mutation presented enhanced HS-induced Cd resistance, which was eliminated in worm strains of daf-16(mu86) and hsf-1(sy441). HS pretreatment increased DAF-16 nuclear localization and HSF-1 granule formation prior to Cd exposure. DAF-16 and HSF-1 was essential in reducing bagging formation and protecting the integrity of intestinal barrier after HS pretreatment. In conclusion, the present study demonstrated that HS-induced Cd resistance in C. elegans is regulated by the DAF-16/FOXO and HSF-1 pathways through regulation of HSP-16.2 expression.

17β-estradiol (E2) often coexists with tetracyclines (TCs) in wastewater lagoons at intensive breeding farms, threatening the quality of surrounding water bodies. Microbial degradation is vital in E2 removal, but it is unclear how TCs affect E2 biodegradation. This primary study investigated the mechanisms of E2 degradation by Novosphingobium sp. ES2-1 in the presence of TCs and assessed the removal efficiency of E2 by strain ES2-1 in natural waters containing TCs. E2 biodegradation was unaffected at TCs concentrations below 0.1 mg L⁻¹ yet significantly inhibited at TCs above 10 mg L⁻¹. As elevation of TCs, E2 biodegradation rate constant decreased, and the biodegradation kinetics equation gradually deviated from the pseudo-first-order dynamics model. Importantly, the presence of TCs, especially at high-level concentrations, significantly hindered E2 ring-opening process but promoted the condensation of some phenolic ring-opening products with NH₃, thereby increasing the abundance of pyridine derivatives, which were difficult to decompose over time. Additionally, strain ES2-1 could remove 52.1–100% of nature estrogens in TCs-contaminated natural waters within 7 d. Results revealed the mechanisms of TCs in E2 biodegradation and the performance of a functional strain in estrogen removal in realistic TCs-contaminated aqueous solution.

Rapid response to underground natural gas leaks could mitigate methane emissions and reduce risks to the environment, human health and safety. Identification of large, potentially hazardous leaks could have environmental and safety benefits, including improved prioritization of response efforts and enhanced understanding of relative climate impacts of emission point sources. However, quantitative estimation of underground leakage rates remains challenging, considering the complex nature of methane transport processes. We demonstrate a novel method for estimating underground leak rates based on controlled underground natural gas release experiments at the field scale. The proposed method is based on incorporation of easily measurable field parameters into a dimensionless concentration number, ε, which considers soil and fluid characteristics. A series of field experiments was conducted to evaluate the relationship between the underground leakage rate and surface methane concentration data over varying soil and pipeline conditions. Peak surface methane concentrations increased with leakage rate, while surface concentrations consistently decreased exponentially with distance from the source. Deviations between the estimated and actual leakage rates ranged from 9% to 33%. A numerical modeling study was carried out by the TOUGH3 simulator to further evaluate how leak rate and subsurface methane transport processes affect the resulting methane surface profile. These findings show that the proposed leak rate estimation method may be useful for prioritizing leak repair, and warrant broader field-scale method validation studies. A method was developed to estimate fugitive emission rates from underground natural gas pipeline leaks. The method could be applied across a range of soil and surface covering conditions.

Hexavalent chromium, Cr(VI), is a heavy metal contaminant and the reduction of Cr(VI) is accompanied by large isotopic fractionation. In this study, the sources of Cr were explored using the Cr isotopic composition of sediments from the Xiaoqing River, a heavily polluted river located in the Shandong Province of China, which flows into Laizhou Bay. The results show that δ⁵³Cr values of the sediments are the highest upstream near the pollution source, and gradually decrease along the river toward the range for igneous reservoirs observed near the estuary. Based on the calculation of authigenic Cr isotopic composition (δ⁵³Crₐᵤₜₕ) using the detrital index and leaching experiments, we suggest that the authigenic Cr in the sample near the pollution source with the highest δ⁵³Crₐᵤₜₕ value mainly comes from the reduction of Cr(VI) discharged by anthropogenic activity, and authigenic Cr in other samples in the midstream with δ⁵³Crₐᵤₜₕ values slightly higher than the range of igneous reservoirs may come from natural oxidative Cr weathering products. By introducing a Rayleigh model, we calculate that at least 31%–55% of Cr(VI) in the river water had been reduced to Cr(III) near the pollution source. Due to the self-purification ability of the river, Cr(VI) was reduced; thus, there is no record of high δ⁵³Crₐᵤₜₕ values in the downstream of the Xiaoqing River and Laizhou Bay, indicating no obvious Cr pollution in these locations. The limited variation of δ⁵³Cr values for samples from a sediment core in Laizhou Bay is also indicative of no obvious Cr pollution in the history. The Cr isotopic compositions of the river sediments are useful for the identification of Cr sources and can be used to advise environmental remediation on Cr pollution.