Reductive dissolution of As-bearing iron oxides: Mediating mechanism of fulvic acid and dissimilated iron reducing bacteria.

Fulvic acid (FA) and iron oxides often play regulating roles in the geochemical behavior and ecological risk of arsenic (As) in terrestrial ecosystems. FA can act as electron shuttles to facilitate the reductive dissolution of As-bearing iron (hydr)oxides. However, the influence of FA from different sources on the sequential conversion of Fe/As in As-bearing iron oxides under biotic and abiotic conditions remains unclear. In this work, we exposed prepared As-bearing iron oxides to FAs derived from lignite (FAL) and plant peat (FAP) under anaerobic conditions, tracked the fate of Fe and As in the aqueous phase, and investigated the reduction transformation of Fe(III)/As(V) with or without the presence of Shewanella oneidensis MR-1. The results showed that the reduction efficiency of Fe(III)/As(V) was increased by MR-1, through its metabolic activity and using FAs as electron shuttles. The reduction of Fe(III)/As(V) was closely associated with goethite being more conducive to Fe/As reduction compared to hematite. It is determined that functional groups such as hydroxy, carboxy, aromatic, aldehyde, ketone and aliphatic groups are the primary electron donors. Their reductive capacities rank in the following sequence: hydroxy> carboxy, aromatic, aldehyde, ketone> aliphatic group. Notably, our findings suggest that in the biotic reduction, Fe significantly reduction precedes As reduction, thereby influencing the latter's reduction process across all incubation systems. This work provides empirical support for understanding iron's role in modulating the geochemical cycling of As and is of significant importance for assessing the release risk of arsenic in natural environments.

Zero-valent iron (ZVI) facilitated in-situ selenium (Se) immobilization and its recovery by magnetic separation: Mechanisms and implications for microbial ecology.

Selenium (Se(VI)) is environmentally toxic. One of the most popular reducing agents for Se(VI) remediation is zero-valent iron (ZVI). However, most ZVI studies were carried out in water matrices, and the recovery of reduced Se has not been investigated. A water-sediment system constructed using natural sediment was employed here to study in-situ Se remediation and recovery. A combined effect of ZVI and unacclimated microorganisms from natural sediment was found in Se(VI) removal in the water phase with a removal efficiency of 92.7 ± 1.1% within 7 d when 10 mg L-1 Se(VI) was present. Soluble Se(VI) was removed from the water and precipitated to the sediment phase (74.8 ± 0.1%), which was enhanced by the addition of ZVI (83.3 ± 0.3%). The recovery proportion of the immobilized Se was 34.2 ± 0.1% and 92.5 ± 0.2% through wet and dry magnetic separation with 1 g L-1 ZVI added, respectively. The 16 s rRNA sequencing revealed the variations in the microbial communities in response to ZVI and Se, which the magnetic separation could potentially mitigate in the long term. This study provides a novel technique to achieve in-situ Se remediation and recovery by combining ZVI reduction and magnetic separation.

The fate of Arsenic associated with the transformation of iron oxides in soils: The mineralogical evidence.

The influence of iron (oxyhydr)oxides on the transformation and migration of arsenic(As) has garnered significant attention. Previous work has largely focused on the transformation of iron oxides related to As fate at molecular and mechanistic levels. However, studies examining the interplay between As concentration and iron oxides transformation within complex soil system are sparse. This study investigates the transformation of iron oxides in soils with varying As concentration during microbial dissimilatory iron reduction (DIR), employing humic acid (HA) as electron shuttle and assesses the impact on As speciation transformation. Comparative analyses indicate that in soils with high As concentration (>1000 mg/kg), the secondary transformation of iron (oxyhydr)oxides to other forms, such as the conversion of ferrihydrite to goethite and lepidocrocite, or schwertmannite to goethite, is impeded. Consequently, the formation of goethite and lepidocrocite, which would typically re-stabilize As, is inhibited, leading to elevated release of As(III). On the other hand, an increase in magnetite formation in soils with low As concentration (<100 mg/kg) appears to re-stabilize As effectively. Furthermore, the formation of new secondary iron (oxyhydr)oxides in soils with As concentration <200 mg/kg enhances fraction F5, which subsequently contributes to the re-immobilization of As, sequestering it within the soil matrix. This process results in a lower release of As(III) from soils with As concentration below 200 mg/kg. These findings enhance the understanding of the interdependent relationship between the transformation of iron oxides and the fate of As in complex soil systems.

Water-soluble brown carbon in atmospheric aerosols from the resource-dependent cities: Optical properties, chemical compositions and sources.

As a vital type of light-absorbing aerosol, brown carbon (BrC) presents inherent associations with atmospheric photochemistry and climate change. However, the understanding of the chemical and optical properties of BrC is limited, especially in some resource-dependent cities with long heating periods in northwest China. This study showed that the annual average abundances of Water-soluble BrC (WS-BrC) were 9.33±7.42 and 8.69±6.29 µg/m3 in Baotou and Wuhai and the concentrations, absorption coefficient (Abs365), and mass absorption efficiency (MAE365) of WS-BrC presented significant seasonal patterns, with high values in the heating season and low values in the non-heating season; while showing opposite seasonal trends for the Absorption Ångström exponent (AAE300-400). Comparatively, the levels of WS-BrC in developing regions (such as cities in Asia) were higher than those in developed regions (such as cities in Europe and Australia), indicating the significant differences in energy consumption in these regions. By combining fluorescence excitation-emission matrix (EEM) spectra with the parallel factor (PARAFAC) model, humic-like (C1 and C2) and protein-like (C3) substances were identified, and accounted for 61.40%±4.66% and 38.6%±3.78% at Baotou, and 60.33%±6.29% and 39.67%±4.17% at Wuhai, respectively. The results of source apportionment suggested that the potential source regions of WS-BrC varied in heating vs. non-heating seasons and that the properties of WS-BrC significantly depended on primary emissions (e.g., combustion emissions) and secondary formation.

Significant methane ebullition from large shallow eutrophic lakes of the semi-arid region of northern China.

Eutrophic lakes are a major source of the atmospheric greenhouse gas methane (CH4), and CH4 ebullition emissions from inland lakes have important implications for the carbon cycle. However, the spatio-temporal heterogeneity of CH4 ebullition emission and its influencing factors in shallow eutrophic lakes of arid and semi-arid regions remain unclear. This study aimed to determine the mechanism of CH4 emission via eutrophication in Lake Ulansuhai, a large shallow eutrophic lake in a semi-arid region of China.To this end, monthly field surveys were conducted from May to October 2021, and gas chromatography was applied using the headspace equilibrium technique with an inverted funnel arrangement. The total CH4 fluxes ranged from 0.102 mmol m-2 d-1 to 59.296 mmol m-2 d-1 with an average value of 4.984 ± 1.82 mmol m-2 d-1. CH4 ebullition emissions showed significant temporal and spatial variations. The highest CH4 ebullition emission was observed in July with a grand mean of 9.299 mmol m-2 d-1, and the lowest CH4 ebullition emissions occurred in October with an average of 0.235 mmol m-2 d-1. Among seven sites (S1-S7), the maximum (3.657 mmol m-2 d-1) and minimum (1.297 mmol m-2 d-1). CH4 ebullition emissions were observed at S2 and S7, respectively. As the main route of CH4 emission to the atmosphere in Lake Ulansuhai, the CH4 ebullition flux during May to October accounted for 69% of the total CH4 flux. Statistical analysis showed that CH4 ebullition was positively correlated with temperature (R = 0.391, P < 0.01) and negatively correlated with air pressure (R = 0.286, P < 0.00). Temperature and air pressure were found to strongly regulate the production and oxidation of CH4. Moreover, nutritional status indicators such as TP and NH4+-N significantly affect CH4 ebullition emissions (R = 0.232, P < 0.01; R = -0.241, P < 0.01). This study reveals the influencing factors of CH4 ebullition emission in Lake Ulansuhai, and provides theoretical reference and data support for carbon emission from eutrophic lakes. Nevertheless, research on eutrophic shallow lakes needs to be further strengthened. Future research should incorporate improved flux measurement techniques with process-based models to improve the accuracy from regional to large-scale estimation of CH4 emissions and clarify the carbon budget of aquatic ecosystems. In this manner, the understanding and predictability of CH4 ebullition emission from shallow lakes can be improved.

Geochemical characteristics and socioeconomic associations of carbonaceous aerosols in coal-fueled cities with significant seasonal pollution pattern.

Carbonaceous aerosols, comprising organic carbon (OC) and elemental carbon (EC), are critical component of fine particulate matter (PM2.5), with diverse impacts on air quality and human health. This study investigated the concentrations and seasonal patterns of carbonaceous species in PM2.5 during both the heating season (January 2021) and non-heating season (July 2021) in three coal-fueled cities in northern China, as well as the differences in carbonaceous aerosols and their associations with socioeconomic parameters in cities situated on either side of the "Hu Line" in China. The results showed that, owing to intensified coal combustion and unfavorable meteorological conditions, levels of OC, EC, and OC/EC ratios were higher in winter compared to summer. Moreover, the presence of dust (DU) and light pollution (LP) days resulted in elevated OC levels but decreased EC levels. The Char-EC/Soot-EC ratios were highest during LP, followed by CL and DU. A source apportionment analysis demonstrated that coal burning, vehicle exhaust, road dust, and biomass burning were the primary contributors to carbonaceous aerosols, as confirmed by diagnostic ratios, Char-EC/Soot-EC ratios, and PCA analysis. Furthermore, our study found that carbonaceous aerosols concentrations and source apportionment primarily varied with diurnal and seasonal trends and different pollution types. Additionally, at the national scale, population density and urban green space exhibited a positive correlation with OC/EC ratios (p < 0.05), while energy consumption per unit of GDP showed a negative correlation (p < 0.05). The observation that OC/EC ratios were lower in coal-fueled cities than in economy-based cities suggests a more severe pollution scenario. These findings highlight the importance of comprehending of the seasonal variation and chemical characteristics of carbonaceous aerosol for understanding air pollution sources and characteristics, which is essential for both air quality management and human health.

Fluxes in CO2 and CH4 and influencing factors at the sediment-water interface in a eutrophic saline lake.

Although saline aquatic ecosystems are significant emitters of greenhouse gases (GHGs), dynamic changes in GHGs at the sediment-water interface remain unclear. The present investigation carried out a total of four sampling campaigns in Daihai Lake, which is a eutrophic saline lake situated in a semi-arid area of northern China. The aim of this study was to investigate the spatio-temporal dynamics of carbon dioxide (CO2) and methane (CH4) fluxes at the sediment-water interface and the influencing factors. The mean concentrations of porewater CO2 and CH4 were 44.98 ± 117.99 µmol L-1 and 124.36 ± 97.00 µmol L-1, far exceeding those in water column of 11.14 ± 2.16 µmol L-1 and 0.33 ± 0.23 µmol L-1, respectively. The CO2 and CH4 fluxes at the sediment-water interface (FS-WCO2 and FS-WCH4) exhibited significant spatial and temporal variations, with mean values of 9.24 ± 13.84 µmol m-2 d-1 and 3.53 ± 4.36 µmol m-2 d-1, respectively, indicating that sediment is the source of CO2 and CH4 in the water column. However, CO2 and CH4 fluxes were much lower than those measured at the water-air interface in a companion study (17.54 ± 14.54 mmol m-2d-1 and 0.50 ± 0.50 mmol m-2d-1, respectively), indicating that the diffusive flux of gases at the sediment-water interface was not the primary source of CO2 and CH4 emissions to the atmosphere. Regression and correlation analyses revealed that salinity (Sal) and nutrients were the most influential factors on porewater gas concentrations, and that gas fluxes increased with increasing gas concentrations and porosity. The microbial activity of sediment is greatly affected by nutrients and Sal. Additionally, Sal has the ability to regulate biogeochemical processes, thereby regulating GHG emissions. The present investigation addresses the research gap concerning GHG emissions from sediments of eutrophic saline lakes. The study suggests that controlling the eutrophication and salinization of lakes could be a viable strategy for reducing carbon emissions from lakes. However, further investigations are required to establish more conclusive results.

A new method based on additive vegetation index for mapping Huangtai algae coverage in Lake Ulansuhai.

Huangtai algal blooms are key indicators of eutrophication and lake-ecosystem damage. Understanding the spatiotemporal heterogeneity of their growth is critical for preserving the ecological environment. The dimidiate pixel model is commonly used to estimate vegetation coverage; however, indices such as the normalized difference vegetation index have not been specifically constructed for the Huangtai algae spectrum and thus are not specific or sufficiently precise for use as indicators. Therefore, we propose a new dimidiate pixel model based on a novel additive vegetation index to calculate the Huangtai algal coverage for each pixel using Landsat multispectral satellite images with 30-m resolution. The results showed that the additive vegetation index with R2 = 0.994 is a better indicator than the normalized difference vegetation index, enhanced vegetative index, and ratio vegetative index, with the accuracy of the new model reaching 86.61%. Monthly Landsat images from 2006 to 2016 were used to calculate the Huangtai algal coverage. Analysis of the inter-monthly variation indicated increased coverage from May to July, with an annual maximum and minimum of 14.43% and 0.33% in 2008 and 2013, respectively. This study provides a new reference map of Huangtai algal cover, which is important for monitoring and protecting the Lake Ulansuhai environment.

Drivers of spatial and seasonal variations of CO2 and CH4 fluxes at the sediment water interface in a shallow eutrophic lake.

Shallow eutrophic lakes contribute disproportional to the emissions of CO2 and CH4 from inland waters. The processes that contribute to these fluxes, their environmental controls, and anthropogenic influences, however, are poorly constrained. Here, we studied the spatial variability and seasonal dynamics of CO2 and CH4 fluxes across the sediment-water interface, and their relationships to porewater nutrient concentrations in Lake Ulansuhai, a shallow eutrophic lake located in a semi-arid region in Northern China. The mean concentrations of CO2 and CH4 in porewater were 877.8 ± 31.0 µmol L-1 and 689.2 ± 45.0 µmol L-1, which were more than 50 and 20 times higher than those in the water column, respectively. The sediment was always a source of both gases for the water column. Porewater CO2 and CH4 concentrations and diffusive fluxes across the sediment-water interface showed significant temporal and spatial variations with mean diffusive fluxes of 887.3 ±124.7 µmol m-2 d-1 and 607.1 ± 68.0 µmol m-2 d-1 for CO2 and CH4, respectively. The temporal and spatial variations of CO2 and CH4 concentrations in porewater were associated with corresponding variations in dissolved organic carbon and dissolved nitrogen species. Temperature and dissolved organic carbon in surface porewater were the most important drivers of temporal variations in diffusive fluxes, whereas dissolved organic carbon and nitrogen were the main drivers of their spatial variations. Diffusive fluxes generally increased with increasing dissolved organic carbon and nitrogen in the porewater from the inflow to the outflow region of the lake. The estimated fluxes of both gases at the sediment-water interface were one order of magnitude lower than the emissions at the water surface, which were measured in a companion study. This indicates that diffusive fluxes across the sediment-water interface were not the main pathway for CO2 and CH4 emissions to the atmosphere. To improve the mechanistic understanding and predictability of greenhouse gas emissions from shallow lakes, future studies should aim to close the apparent gap in the CO2 and CH4 budget by combining improved flux measurement techniques with process-based modeling.

Arthroscopic reconstruction of anterior cruciate ligaments with allograft: single-tunnel single-bundle versus single-tunnel double-bundle techniques.

PURPOSE: To compare the clinical results of anterior cruciate ligament (ACL) reconstruction using the single-tunnel single-bundle (STSB) technique versus the single-tunnel double-bundle (STDB) technique. METHODS: This was a retrospective, single-center, single-surgeon study based on data collected from March 2012 to June 2013. According to our inclusion/exclusion criteria, a total of 78 patients (64 males, 14 females; mean age, 25.1 years) who underwent arthroscopic ACL reconstruction with anterior tibialis tendon allografts through either the STSB technique (36 cases) or the STDB technique (42 cases) in our department were recruited. The International Knee Documentation Committee (IKDC), Lysholm, and Tegner scores were used to evaluate the subjective function of the knee joint during the postoperative follow-up. The Lachman test and pivot shift test were used to objectively assess the stability of the knee. RESULTS: The average follow-up duration was 24.9 ± 1.8 months in the STSB group and 24.6 ± 1.7 months in the STDB group (P > 0.05). Patients in both groups recovered to the preoperative sports level with few complications. The postoperative Lysholm score (86.1 ± 7.5 vs. 47.7 ± 9.0 in the STSB group; 87.0 ± 7.1 vs. 48.2 ± 8.3 in the STDB group), IKDC score (87.8 ± 7.2 vs. 49.3 ± 6.1 in the STSB group; 88.7 ± 6.6 vs. 49.8 ± 6.3 in the STDB group), Tegner score (6.5 ± 1.3 vs. 2.5 ± 1.3 in the STSB group; 6.6 ± 1.2 vs. 2.6 ± 1.2 in the STDB group), Lachman test positive rate (8.3% vs. 89.9% in the STSB group; 7.1% vs. 85.7% in the STDB group), and pivot shift test positive rate (27.8% vs. 63.9% in the STSB group; 7.1% vs. 69.0% in the STDB group) were significantly improved compared to the preoperative status in both groups (P < 0.05). However, no statistically significant difference was observed between the two groups at the final follow-up (P > 0.05), except for the pivot shift test positive rate in the STDB group versus the STSB group (7.1% vs. 27.8%, P < 0.05). CONCLUSIONS: The STDB technique achieved a satisfactory clinical outcome with better rotational stability compared to the traditional STSB technique and therefore provided an effective option for ACL reconstruction. LEVEL OF EVIDENCE: Case series, Level IV.

Arsenic speciation transformation in soils with high geological background: New insights from the governing role of Fe.

In soils, the speciation transformation of As were inherently related to the behaviors of iron (oxyhydr) oxides. It is poorly understood that the effects of the transformation of iron (oxyhydr) oxides coupled with As speciation transformation during dissimilatory Fe(III) reduction (DIR) involving with humic substances (HS) as electron donor or shuttle in soils with high arsenic geological background. In this study, the relationships between the transformation of iron (oxyhydr)oxides and As speciation transformation were investigated according to the response between continuously As speciation monitoring and iron (oxyhydr) oxides identification during DIR in the soils. The results showed that F4 (arsenic incorporated with amorphous iron (oxyhydr)oxides including ferrihydrite and schwertmannite) and F5 (arsenic incorporated with crystalline iron (oxyhydr)oxides including hematite and magnetite) were the main source and sink for As(III)Dissolved during DIR. During the incubation period, Fe(II) was the dominant driving force for the reduction of As(V) in the water-soil system. The XRD analysis indicated the changes of iron oxides such as ferrihydrite, schwertmannite, hematite and magnetite were closely related to the release and reduction of As, and those iron oxides could play governing roles for As speciation transformation during DIR in soils. Different from the known mechanism in low As concentrations, a limiting effect of As concentration on iron oxides transformation was found in our incubation experiments using soils with high As geological background (∼1000 mg/kg). This work provides new insights for Fe as governing role in As speciation transformation in soils with high arsenic geological background by firstly identifying the corresponding iron (oxyhydr)oxides in operationally defined arsenic speciation incorporated with iron oxides.

Changes in stoichiometric characteristics of ambient air pollutants pre-to post-COVID-19 in China.

To prevent the Corona Virus Disease 2019 (COVID-19) spreading, Chinese government takes a series of corresponding measures to restrict human mobility, including transportation lock-down and industries suspension, which significantly influenced the ambient air quality and provided vary rare time windows to assess the impacts of anthropological activities on air pollution. In this work, we divided the studied timeframe (2019/12/24-2020/2/24) into four periods and selected 88 cities from 31 representative urban agglomerations. The indicators of PM2.5/PM10 and NO2/SO2 were applied, for the first time, to analyze the changes in stoichiometric characteristics of ambient air pollutants pre-to post-COVID-19 in China. The results indicated that the ratios of NO2/SO2 presented a responding decline, especially in YRD (-5.01), YH (-3.87), and MYR (-3.84), with the sharp reduction of traffic in post-COVID-19 periods (P3-P4: 2.34 ± 0.94 m/m) comparing with pre-COVID-19 periods (P1-P2: 4.49 ± 2.03 m/m). Whereas the ratios of PM2.5/PM10 increased in P1-P3, then decreased in P4 with relatively higher levels (>0.5) in almost all urban agglomerations. Furthermore, NO2 presented a stronger association with PM2.5/PM10 variation than CO; and PM2.5 with NO2/SO2 variation than PM10. In summary, the economic structure, lockdown measures and meteorological conditions could explain the noteworthy variations in different urban agglomerations. These results would be in great help for improving air quality in the post-epidemic periods.

Trends and environmental factors of arsenic in sediments from the five lake ecoregions, China.

The behavior and risk of arsenic (As) closely relate to its geochemical fractionation and environmental factors in sediments. The soluble (F1), reducible (F2), oxidizable (F3), and residual fraction (F4) of As were extracted in the sediments from Lake Hulun, Wuliangsuhai, and Dalinor of Inner Mongolia Plateau. Coupled with lakes from Eastern and Northeast Plain, Yunnan-Guizhou and Qinghai-Tibetan Plateau, the responses of As fractions to environmental conditions were investigated according to the spatial distribution of As fractionations in five lake ecoregions at a national scale of China. Generally, F1 was more sensitive to environmental changes, and the pH presented significantly negative effects on the amount of soluble As, while water depth played an important role in regulating the distribution of the fraction F2 and F4. The As pools in surface lake sediments presented a latitudinal zonation due to the gradient effects of climate and anthropogenic activities on nutrient decomposition, and their influence on the capacity of sediments holding As. This work indicated that nutrients played a coordinating role in regulating the impacts of climate and environmental factors on As fractionation in aquatic environments.

Heating events drive the seasonal patterns of volatile organic compounds in a typical semi-arid city.

The emission characteristics, source apportionment and chemical behavior of volatile organic compounds (VOCs) are important for strategy-making on ozone (O3) and fine particulate matter (PM2.5) control. Based on the continuous observation during four seasons, the seasonal characteristics, chemical reactivity and source apportionment of 116 VOCs species were studied in a typical semi-arid city with no relevant research. The results showed that the annual average concentrations of total volatile organic compounds (TVOCs) in Hohhot was 44.67 ± 46.59 ppbv with the predominant of alkanes and oxygenated volatile organic compounds (OVOCs). The sharp increment of TVOCs were explained by the elevating OVOCs and alkanes in autumn, while alkanes and alkenes in winter. The levels of alkenes presented negative and positive correlations with solar radiation and PM10, respectively. The mixing ratios accounted for 30% (alkanes) and 23% (alkenes and aromatics) of the TVOCs, respectively; while their ozone formation potential (OFP) ~15% and nearly 50% (even 75% in winter), respectively, indicating that the OFP of different VOCs species depends not only on their concentrations but more importantly on their chemical activity in atmosphere. According to the seasonal source apportionment, both the high levels of short-chain alkanes, alkenes and aromatics and the increasing coal sales volume suggested that the combustion sources were the predominant in heating seasons, while solvent uses was extracted as the most predominant during non-heating seasons. In non-heating seasons, the biogenic emission sources, ranking as the second contributor, were significantly higher than heating seasons. Isoprene was the most active biogenic VOCs species, bagging test results showed that deciduous trees were the predominant contributors for isoprene (~99%), while coniferous trees and shrub for monoterpenes (>95%). It will be helpful for understanding the characteristics of VOCs in Chinese national key development areas and informing policy to control semi-arid regional VOCs air pollution.

Distribution, sources, and ecological risk assessment of polycyclic aromatic hydrocarbons in the sediments of Daihai Lake in Inner Mongolia, China.

Polycyclic aromatic hydrocarbons (PAHs) are typical toxic organic pollutants that can accumulate in sediments and may be toxic to aquatic organisms. In the present study, the contamination level, composition pattern, and sources of sixteen PAHs listed by the United States Environmental Protection Agency were investigated in surface sediments and a sediment core from Daihai Lake, which is located in a typical semiarid area of Inner Mongolia, China, and the ecological risk of these PAHs was assessed. The results show that the total concentration of PAHs in the surface sediments ranged from 204.6 to 344.5 ng/g with an average value of 287.2 ng/g and that compared with other aquatic systems, the level of PAHs in the sediments from Daihai Lake was low. However, a general upward trend was observed for the concentrations of PAHs in the sediment core, which might be related to the increase in human activities in the area. Moreover, the PAH concentrations were significantly positively correlated with the total organic carbon (TOC) content in the sediments, and it is thus inferred that TOC regulates the distribution of PAHs in Daihai Lake. Three-ring and four-ring PAHs were found to be predominant in all the sediment samples, and phenanthrene (Phe) was the most abundant compound. According to the composition of PAHs and the anthracene (Ant)/(Ant+Phe) or fluoranthene (Flt)/(Flt+pyrene (Pyr)) ratios, the PAHs in Daihai Lake mainly originated from the combustion of domestic coal, grass, and wood, and petroleum cannot be ignored as a source considering the growth of industry. Risk assessment based on a comparison of PAH concentrations and the effect range low (ERL) and effect range median (ERM) values demonstrated that acenaphthene (Ace) at 11 sites and fluorene (Flu) at 7 sites had occasional adverse biological effects.

Factors and pathways regulating the release and transformation of arsenic mediated by reduction processes of dissimilated iron and sulfate.

The driving process and explanatory factors regulating the transformation and migration of arsenic (As) mediated by dissimilatory iron reducing bacteria (DFeRB) and sulfate reducing bacteria (SRB) remain poorly understood. The novelty of this study is to explore the driving process and key environmental factors governing As mobilization mediated by DFeRB and SRB based on continuous As speciation and environmental parameter monitoring in a sediment-water system. The results illustrate the reduction process mediated by DFeRB and SRB significantly promotes the reduction of As(V) and the endogenous release of As. However, in the DFeRB and SRB mediated reductions, the main driving process and key explanatory factors that dominate the As mobility are significantly different. DFeRB has significant effects on the reductive dissolution and re-distribution of Fe(III) oxyhydroxides and As-containing Fe(III) minerals and on adsorption-desorption, which in turn influenced the transformation of iron species and the release and ecotoxicity of As. Meanwhile, the environmental factors that affect As mobility depend on Fe2+ and Fe3+ in DFeRB-induced reduction, presenting two main pathways: the process of As mobilization mediated by DFeRB, and the process influenced by the inorganic phosphorus involved in the competitive adsorption and anion exchange. Significantly different from DFeRB, the effects of SRB on As behavior mainly occur by influencing the adsorbed As, pyrite, and As sulfides in the sediments and through the formation of sulfides during the sulfate reduction. The main pathways of As mobilization reflect the direct effects of SRB, S2-, and Fe2+. In addition, the role of NH4+-N in the driving process of As mobility is more pronounced in SRB-induced reduction. NO3--N is an essential factor affecting As mobility, but the effects of NO3--N on As lead to non-significant pathways. This work provides insights into the environmental effects of DFeRB and SRB on the biogeochemical cycle of As.

Stoichiometric characteristics and economic implications of water-soluble ions in PM2.5 from a resource-dependent city.

The stoichiometric characteristics of water-soluble ions (WSIs) in PM2.5, which can be used as an indicator socioeconomic development level, are mostly depending on the sources and formation mechanism of PM2.5. This work presents the stoichiometric characteristics and socioeconomic linkage of WSIs in PM2.5 from a resource-dependent city. The relationship between NO3-/SO42- and car parc indexes the contribution of mobile emission source. The equivalent ratio of WSIs suggested that aerosol particles were weak acidic due to the deficiency of cations in PM2.5, which was consistent with the average annual pH (6.27) of precipitation in Wuhai in 2015. NH4+ neutralizes PM2.5 acidity in clean and polluted days, while Ca2+ and NH4+ in dust storm days. Furthermore, the PCA analysis indicated the multi-sources pollution characteristics from Spring to Fall, which was related the small build-up area (only 62.30 km2) and the close-set of various industrial enterprises in Wuhai. The ratios of NO2/SO2 may not work effectively to identify the importance of mobile versus stationary pollution emission sources when the heavy emission from the secondary industry, especially the proportion of secondary industry higher than 65% and the ratios of NO2/SO2 lower than 0.4. This work contributes to more effective control strategies for PM2.5 in resource-dependent areas.

Transformation pathways of arsenic species: SRB mediated mechanism and seasonal patterns.

Sulfate reducing bacteria (SRB) mediated reduction plays a key role in the biological cycling of As, which inherently associates with the transformation of As species. However, the potential pathways of As species transformation, the predominant driving process and their explanatory factors regulating seasonal As mobility mediated by SRB remains poorly understood. This study explored the possible pathways of seasonal As species transformation mediated by SRB, and identified the predominant driving process and key environmental factors in response to As mobilization in different seasons. SRB-mediated reduction governed the seasonal mobilization of As, significantly promoted reduction of As (V) and endogenous release of As, and exhibited strong seasonal variability. The flux of As(III) and TAs in group SRB in summer were 1.92-3.53 times higher than those during the ice-bound period. The results showed two distinct stages namely release and re-immobilization both in summer and ice-bound period. While As was easier to be gradually transformed into a more stable state in SRB reduction process during ice-bound period. Both in summer and ice-bound period, SRB presented significant regulating effects on As behavior by influencing loosely adsorbed As, pyrite and As sulfides in sediments as well as the formation of sulfide during the process of SRB reduction. The main effecting pathways on As mobilization were the direct effects of SRB, S2- and Fe2+ in summer, but IP was also an important pathway affecting As mobility during ice-bound period. This work provides new insights into mechanisms responsible for seasonal As mobilization.

Geochemical characteristics of rare earth elements in windowsill dust in Baotou, China: influence of the smelting industry on levels and composition.

Smelting is one of the main sources of rare earth elements (REEs) in large scale smelting regions that have been neglected before. To provide experimental evidence on the influence of smelting processes on REEs in windowsill dust, this study investigated the concentration, chemical fractions, and spatial distribution of 14 REEs in windowsill dust and assessed the possible influence of smelting processes on the geochemical behavior of these REEs. A total of 46 windowsill dust samples were collected from different locations in Baotou, a typical industrial city for large-scale smelting. The fractions of REEs were analyzed by Tessier sequential extraction analysis. The enrichment factor (EF) was adopted to assess the contribution of anthropogenic emissions of REEs. The loess-normalized REE patterns of windowsill dust are similar to those of the iron ore of the Bayan Obo mine, but differ from those of the local soil. The concentrations of La, Ce, Pr, Nd, and ∑REEs in the residual fraction and total digestion decrease gradually with the increase in distance from the smelter in the downwind direction. These results suggested that the accumulation and fractionation of REEs in windowsill dust are considerably influenced by smelting. The emission of smelting is the main source of REEs for windowsill dust in Baotou.

Employing bacterial mutations for the elucidation of photo-Fenton disinfection: Focus on the intracellular and extracellular inactivation mechanisms induced by UVA and H2O2.

The bacterial inactivation mechanisms by solar light and the photo-Fenton process is still a matter of debate. In this study, we bring evidence towards the elucidation of the mechanisms that govern photo-Fenton disinfection at near-neutral pH. With the use of porin-deficient and catalase over-producing E. coli strains, in conjunction with measurements of cell wall oxidation and permeability, we are able to i) highlight the role of the aforementioned components in bacterial inactivation and ii) localize the damages in the intracellular domain, despite the addition of the Fenton reagents in the bulk. We report that H2O2 oxidizes cell walls but under light the process is of low significance; UVA initiated an intracellular oxidation process based on excess accumulated H2O2, while the UVA+H2O2 and UVA+H2O2+Fe2+ processes have the same effect with light, albeit enhanced, as shown by malondialdehyde (MDA) production and ONPG hydrolysis rates. Finally, compared to the UVA-assisted photo-Fenton process, its solar counterpart is enhanced by the direct UVB effects on bacterial DNA. In conclusion, we have sufficient evidence to postulate that the photo-Fenton process is intracellular and propose the pathways that form the integrated bacterial inactivation mechanism by photo-Fenton.