Accelerated biological aging mediated associations of ammonium, sulfate in fine particulate matter with liver cirrhosis.

BACKGROUND: Although both air pollution and aging are related to the development of liver cirrhosis, the role of biological aging in association of the mixture of fine particulate matter (PM2.5) and its constituents with liver cirrhosis was unknown. METHODS: This case-control retrospective study included 100 liver cirrhosis patients and 100 control subjects matched by age and sex. The concentrations of PM2.5 and its constituents were estimated for patients using machine-learning methods. The clinical biomarkers were used to calculate biological age using the Klemera-Doubalmethod (KDM) algorithms. Individual associations of PM2.5 and its constituents or biological age with liver cirrhosis were analyzed by generalized linear models. WQS and BKMR were applied to analyze association of mixture of PM2.5 and its constituents with liver cirrhosis. The mediation effect of biological age on associations of PM2.5 and its constituents with liver cirrhosis was further explored. RESULTS: we found that each 1-unit increment in NH4+, NO3-, SO42- and biological age were related to 3.618-fold (95%CI: 1.896, 6.904), 1.880-fold (95%CI: 1.319, 2.680), 2.955-fold (95%CI: 1.656, 5.272) and 1.244-fold (95%CI: 1.093, 1.414) increased liver cirrhosis. Both WQS and BKMR models showed that the mixture of PM2.5 and its constituents was related to increased liver cirrhosis. Furthermore, the mediated proportion of biological age on associations of NH4+ and SO42- with liver cirrhosis were 14.7 % and 14.6 %, respectively. CONCLUSIONS: Biological aging may partly explain the exposure to PM2.5 and its constituents in association with increased risk for liver cirrhosis, implying that delaying the aging process may be a key step for preventing PM2.5-related liver cirrhosis risk.

Personal exposure monitoring of fine and coarse particulate matter using exposure assessment models for elderly residents in Hong Kong.

This study investigated the determinants of personal exposures (PE) to coarse (PM2.5-10) and fine particulate matter (PM2.5) for elderly communities in Hong Kong. The mean PE PM2.5 and PM2.5-10 were 23.6 ± 10.8 and 13.5 ± 22.1 µg/m3, respectively during the sampling period. Approximately 76% of study subjects presented statistically significant differences between PE and ambient origin for PM2.5 compared to approximately 56% for PM2.5-10, possibly due to the coarse-size particles being more influenced by similar sources (road dust and construction dust emissions) compared to the PM2.5 particles. Individual PE to ambient (P/A) ratios for PM2.5 all exceeded unity (≥1), suggesting the dominant influences of non-ambient particles contributed towards total PE values. There were about 80% individual P/A ratios (≤1) for PM2.5-10, implying possible effective infiltration prevention of larger size particulate matter particles leading to dominant influences from the outdoor sources. The higher concentration of NO3- and SO42- in PM2.5-10 compared to PM2.5 suggests possible heterogeneous reactions of alkaline minerals leading to the formation of NO3- and SO42- in PM2.5-10 particles. The PE and ambient OC/EC ratios in PM2.5 (8.8 ± 3.3 and 10.4 ± 22.4, respectively) and in PM2.5-10 (6.0 ± 1.9 and 3.0 ± 1.1, respectively) suggest possible secondary formed OC from surrounding rural areas. Heterogeneous distributions (COD >0.2) between the PE and ambient concentrations were found for both the PM2.5 and PM2.5-10 samples. The calibration coefficient as the association between personal and surrogate exposure measure of PE to PM2.5 (0.84) was higher than PM2.5-10 (0.52). The findings further confirm that local sources were the dominant contributor to the coarse particles and these coefficients can potentially be used to estimate different PE to PM2.5 and PM2.5-10 conditions. A comprehensive understanding of the PE to determinants in coarse particles is essential to further reduce potential exposure misclassification.

Toxic Potencies of Particulate Matter from Typical Industrial Plants Mediated with Acidity via Metal Dissolution.

Acidity is an important property of particulate matter (PM) in the atmosphere, but its association with PM toxicity remains unclear. Here, this study quantitively reports the effect of the acidity level on PM toxicity via pH-control experiments and cellular analysis. Oxidative stress and cytotoxicity potencies of acidified PM samples at pH of 1-2 were up to 2.8-5.2 and 2.1-13.2 times higher than those at pH of 8-11, respectively. The toxic potencies of PM samples from real-world smoke plumes at the pH of 2.3 were 9.1-18.2 times greater than those at the pH of 5.6, demonstrating a trend similar to that of acidified PM samples. Furthermore, the impact of acidity on PM toxicity was manifested by promoting metal dissolution. The dramatic increase by 2-3 orders of magnitude in water-soluble metal content dominated the variation in PM toxicity. The significant correlation between sulfate, the pH value, water-soluble Fe, IC20, and EC1.5 (p < 0.05) suggested that acidic sulfate could enhance toxic potencies by dissolving insoluble metals. The findings uncover the superficial association between sulfate and adverse health outcomes in epidemiological research and highlight the control of wet smoke plume emissions to mitigate the toxicity effects of acidity.

Abundance and sources of particulate polycyclic aromatic hydrocarbons and aromatic acids at an urban site in central China.

We conducted a simultaneous field study of PM2.5-bound particulate polycyclic aromatic hydrocarbons (PAHs) and aromatic acids (AAs) in a polluted city Zhengzhou to explore the concentration, sources and potential conversion pathways between PAHs and AAs in different seasons. The average concentrations of PM2.5, 28PAHs and 8AAs during the sampling period were 77 µg/m3, 75 ng/m3, and 283 ng/m3, respectively. The concentration of both 28PAHs and 8AAs were highest in winter and lowest in summer with ratios of 6.3 and 2.3, respectively. PAHs with 5-7 rings were the main components of PAHs (52%), followed by 4 rings PAHs (30%) and 2-3 rings PAHs (18%). According to the source appointment results obtained by positive matrix factorization, the main sources of PAHs were combustion and vehicle emissions, which account for 37% and 34%, respectively. 8AAs were divided into three groups, including four benzene dicarboxylic acids (B2CAs), three benzene tricarboxylic acids (B3CAs) and one benzene tetracarboxylic acid (B4CA). And interspecies correlation analysis with PM2.5 source markers were used to investigate potential sources. Phthalic acid (o-Ph) was the most abundant specie of 8AAs (157 ng/m3, 55% of 8AAs), which was well correlated with sulfate. Meanwhile, B3CAs and B4CA were highly correlated with sulfate and weakly correlated with levoglucosan, suggesting that secondary formation was their main source. As logical oxidation products of PAHs, o-Ph and B3CAs showed good correlations with a number of PAHs, indicating possible photochemical oxidation pathway by PAHs. In addition, O3, NO2, temperature and relative humidity have positive effects on the secondary formation of B3CAs.

Feasibility of sulfated BPA and BPS as wastewater-based epidemiology biomarkers: Insights from wastewater and reported human urine analysis.

In wastewater-based epidemiology (WBE), the selection of appropriate biomarkers presents a significant challenge. Recently, sulfated bisphenols have garnered attention as potential WBE biomarkers due to their increased stability in wastewater compared to glucuronide conjugates. This study aims to comprehensively assess the feasibility of employing sulfated BPA and BPS as WBE biomarkers by analyzing both WBE and human biomonitoring data. To conduct this research, wastewater samples were collected from six domestic wastewater treatment plants in Guangzhou, China, and urinary concentration of BPA and BPS were obtained from peer-reviewed literature. The results revealed that mean urinary concentrations of BPA and BPS, calculated using Monte Carlo simulations, significantly exceeded those reported in human biomonitoring studies. Furthermore, the per capita mass load ratio of sulfated BPA and BPS in human urine to the mass load in wastewater was found to be below 10 %. This outcome suggests that the excretion of BPA-S and BPS-S in urine does not make a substantial contribution to wastewater, hinting at the existence of other notable sources. Consequently, our study concludes that sulfated BPA-S and BPS-S are not suitable candidates as WBE biomarkers. This work provides a referenceable analytical framework for evaluating the feasibility of WBE biomarkers and emphasizes the necessity for caution when utilizing WBE to assess human exposure to chemicals.

Sulfate-reducing bacteria unearthed: ecological functions of the diverse prokaryotic group in terrestrial environments.

Sulfate-reducing prokaryotes (SRPs) are essential microorganisms that play crucial roles in various ecological processes. Even though SRPs have been studied for over a century, there are still gaps in our understanding of their biology. In the past two decades, a significant amount of data on SRP ecology has been accumulated. This review aims to consolidate that information, focusing on SRPs in soils, their relation to the rare biosphere, uncultured sulfate reducers, and their interactions with other organisms in terrestrial ecosystems. SRPs in soils form part of the rare biosphere and contribute to various processes as a low-density population. The data reveal a diverse range of sulfate-reducing taxa intricately involved in terrestrial carbon and sulfur cycles. While some taxa like Desulfitobacterium and Desulfosporosinus are well studied, others are more enigmatic. For example, members of the Acidobacteriota phylum appear to hold significant importance for the terrestrial sulfur cycle. Many aspects of SRP ecology remain mysterious, including sulfate reduction in different bacterial phyla, interactions with bacteria and fungi in soils, and the existence of soil sulfate-reducing archaea. Utilizing metagenomic, metatranscriptomic, and culture-dependent approaches will help uncover the diversity, functional potential, and adaptations of SRPs in the global environment.

Single Droplet Tweezer Revealing the Reaction Mechanism of Mn(II)-Catalyzed SO2 Oxidation.

Sulfate aerosol is one of the major components of secondary fine particulate matter in urban haze that has crucial impacts on the social economy and public health. Among the atmospheric sulfate sources, Mn(II)-catalyzed SO2 oxidation on aerosol surfaces has been regarded as a dominating one. In this work, we measured the reaction kinetics of Mn(II)-catalyzed SO2 oxidation in single droplets using an aerosol optical tweezer. We show that the SO2 oxidation occurs at the Mn(II)-active sites on the aerosol surface, per a piecewise kinetic formulation, one that is characterized by a threshold surface Mn(II) concentration and gaseous SO2 concentration. When the surface Mn(II) concentration is lower than the threshold value, the reaction rate is first order with respect to both Mn(II) and SO2, agreeing with our traditional knowledge. But when surface Mn(II) concentration is above the threshold, the reaction rate becomes independent of Mn(II) concentration, and the reaction order with respect to SO2 becomes greater than unity. The measured reaction rate can serve as a tool to estimate sulfate formation based on field observation, and our established parametrization corrects these calculations. This framework for reaction kinetics and parametrization holds promising potential for generalization to various heterogeneous reaction pathways.

Biomarkers identification in follicular fluid in relation to live birth in in vitro fertilization of women with polycystic ovary syndrome in different subtypes by using UPLC-MS method.

BACKGROUND: Polycystic ovary syndrome (PCOS) is a common infertility disorder which affects reproductive-aged women. However, metabolic change profiles of follicular fluid (FF) in lean and obese women diagnosed with and without PCOS remains unclear. METHODS: 95 infertile women were divided into four subgroups: LC (lean control), OC (overweight control), LP (lean PCOS), and OP (overweight PCOS). The FF samples were collected during oocyte retrieval and assayed by ultra-performance liquid chromatography coupled with mass spectrometry (UPLC-MS) metabolomics. RESULTS: A total of 236 metabolites were identified by metabolic analysis. The pathway enrichment analysis revealed that the glycerophospholipid metabolism (impact = 0.11182), ether lipid metabolism (impact = 0.14458), and primary bile acid biosynthesis (impact = 0.03267) were related to metabolic pathway between PCOS and control. Correlation analyses showed that epitestosterone sulfate was found positively correlated with fertilization rate in PCOS, while falcarindione, lucidone C. and notoginsenoside I was found to be negatively correlated. The combined four biomarkers including lucidone C, epitestosterone sulfate, falcarindione, and notoginsenoside I was better in predicting live birth rate, with AUC of 0.779. CONCLUSION: The follicular fluid of women with PCOS showed unique metabolic characteristics. Our study provides better identification of PCOS follicular fluid metabolic dynamics, which may serve as potential biomarkers of live birth.

Multi-approach assessment of groundwater biogeochemistry: Implications for the site characterization of prospective spent nuclear fuel repository sites.

The disposal of spent nuclear fuel in deep subsurface repositories using multi-barrier systems is considered to be the most promising method for preventing radionuclide leakage. However, the stability of the barriers can be affected by the activities of diverse microbes in subsurface environments. Therefore, this study investigated groundwater geochemistry and microbial populations, activities, and community structures at three potential spent nuclear fuel repository construction sites. The microbial analysis involved a multi-approach including both culture-dependent, culture-independent, and sequence-based methods for a comprehensive understanding of groundwater biogeochemistry. The results from all three sites showed that geochemical properties were closely related to microbial population and activities. Total number of cells estimates were strongly correlated to high dissolved organic carbon; while the ratio of adenosine-triphosphate:total number of cells indicated substantial activities of sulfate reducing bacteria. The 16S rRNA gene sequencing revealed that the microbial communities differed across the three sites, with each featuring microbes performing distinctive functions. In addition, our multi-approach provided some intriguing findings: a site with a low relative abundance of sulfate reducing bacteria based on the 16S rRNA gene sequencing showed high populations during most probable number incubation, implying that despite their low abundance, sulfate reducing bacteria still played an important role in sulfate reduction within the groundwater. Moreover, a redundancy analysis indicated a significant correlation between uranium concentrations and microbial community compositions, which suggests a potential impact of uranium on microbial community. These findings together highlight the importance of multi-methodological assessments in better characterizing groundwater biogeochemical properties for the selection of potential spent nuclear fuel disposal sites.

Protein intake affects erythrocyte glutathione synthesis in healthy adults aged ≥60 years in a repeated-measures trial.

BACKGROUND: Protein recommendations for older adults are based on nitrogen balance data from young adults. Physiological studies using the indicator amino acid oxidation method suggest they need 30% to 50% more protein than current recommendations. We herein present glutathione (GSH) as a physiological estimate of protein adequacy in older adults. OBJECTIVES: The objective was to measure GSH kinetics in response to varying protein intakes in a repeated-measures design in healthy adults aged ≥60 y using the precursor-product method. METHODS: Sixteen healthy older adults (n = 8 male and n = 8 female; body mass index ≤30 kg/m2) were studied. Each received 4 of 6 protein intakes in random order (0.66, 0.8, 0.9, 1.1, 1.3 and 1.5 g⋅kg-1⋅d-1). At each intake level, participants underwent isotope infusion studies of 7 h duration following a 3-d adaptation to the test level of protein. On the fourth day, GSH fractional (FSR) and absolute synthesis (ASR) rates were quantified by measuring the incorporation of U-[13C2-15N]glycine into GSH at isotopic steady state. A mixed-effect change-point regression model was used to determine a breakpoint in FSR and ASR. Secondary outcomes included plasma concentrations of oxidative stress markers, homocysteine, 5-L-oxoproline (5-OP), and urinary sulfate. The effect of secondary outcomes on GSH kinetics was analyzed using a joint linear mixed-effect model and Tukey's post hoc test. RESULTS: A protein intake of 1.08 g⋅kg-1⋅d-1 (95% confidence interval [CI]: 0.83, 1.32; Rm2 = 0.207; Rc2 = 0.671; P < 0.001) maximized GSH FSR. There was no effect of protein intake on concentrations of erythrocyte GSH, plasma homocysteine, oxidative stress markers, or 5-OP (P > 0.05). Protein intake had a positive effect on urinary sulfate excretion (P < 0.0001). CONCLUSION: A protein intake of 1.08 g⋅kg-1⋅d-1 from a high-quality protein maximized GSH synthesis in adults ≥60 y. This lends support to data suggesting a requirement higher than the current recommendation. This study was registered at clinicaltrials.gov as NCT02971046.

Non-mercury methylating microbial taxa are integral to understanding links between mercury methylation and elemental cycles in marine and freshwater sediments.

The goal of this study was to explore the role of non-mercury (Hg) methylating taxa in mercury methylation and to identify potential links between elemental cycles and Hg methylation. Statistical approaches were utilized to investigate the microbial community and biochemical functions in relation to methylmercury (MeHg) concentrations in marine and freshwater sediments. Sediments were collected from the methylation zone (top 15 cm) in four Hg-contaminated sites. Both abiotic (e.g., sulfate, sulfide, iron, salinity, total organic matter, etc.) and biotic factors (e.g., hgcA, abundances of methylating and non-methylating taxa) were quantified. Random forest and stepwise regression were performed to assess whether non-methylating taxa were significantly associated with MeHg concentration. Co-occurrence and functional network analyses were constructed to explore associations between taxa by examining microbial community structure, composition, and biochemical functions across sites. Regression analysis showed that approximately 80% of the variability in sediment MeHg concentration was predicted by total mercury concentration, the abundances of Hg methylating taxa, and the abundances of the non-Hg methylating taxa. The co-occurrence networks identified Paludibacteraceae and Syntrophorhabdaceae as keystone non Hg methylating taxa in multiple sites, indicating the potential for syntrophic interactions with Hg methylators. Strong associations were also observed between methanogens and sulfate-reducing bacteria, which were likely symbiotic associations. The functional network results suggested that non-Hg methylating taxa play important roles in sulfur respiration, nitrogen respiration, and the carbon metabolism-related functions methylotrophy, methanotrophy, and chemoheterotrophy. Interestingly, keystone functions varied by site and did not involve carbon- and sulfur-related functions only. Our findings highlight associations between methylating and non-methylating taxa and sulfur, carbon, and nitrogen cycles in sediment methylation zones, with implications for predicting and understanding the impact of climate and land/sea use changes on Hg methylation.

Constraining East Asia ammonia emissions through satellite observations and iterative Finite Difference Mass Balance (iFDMB) and investigating its impact on inorganic fine particulate matter.

Uncertainty in ammonia (NH3) emissions causes the inaccuracy of fine particulate matter simulations, which is associated with human health. To address this uncertainty, in this work, we employ the iterative finite difference mass balance (iFDMB) technique to revise NH3 emissions over East Asia using the Cross-track Infrared Sounder (CRIS) satellite for July, August, and September 2019. Compared to the emissions, the revised NH3 emissions show an increase in China, particularly in the North China Plain (NCP) region, corresponding to agricultural land use in July, August, and September and a decrease in South Korea in September. The enhancement in NH3 emissions resulted in a remarkable increase in concentrations of NH3 by 5 ppb. in July and September, there is an increase in ammonium (NH4+) and nitrate (NO3-) concentrations by 5 µg/m3, particularly in the NCP region, while in August, both NH4+ and NO3- concentrations exhibit a decrease. For sulfate (SO42-), in August and September, the concentrations decreased over most regions of China and Taiwan, as a result of the production of ammonium sulfate; increased concentrations of SO42-, however, were simulated over South Korea, Japan, and the southern region of Chengdu, caused by higher relative humidity (RH). In contrast, during the month of July, our simulations showed an increase in SO42- concentrations over most regions of China. To gain a more comprehensive understanding, we defined a sulfur conversion ratio ( [Formula: see text] ), which explains how changes in sulfur in the gas phase affect changes in sulfate concentrations. A subsequent sensitivity analysis performed in this study indicated the same relationship between changes in ammonia and its effect on inorganic fine particulate matter (PM2.5). This study highlights the challenge of controlling and managing inorganic PM2.5 and indicates that reducing the emissions of air pollutants do not necessarily lead to a reduction in their concentrations.

PM2.5 constituents associated with childhood obesity and larger BMI growth trajectory: A 14-year longitudinal study.

BACKGROUND: The association of specific PM2.5 chemical constituents with childhood overweight or obesity (OWOB) remain unclear. Furthermore, the long-term impacts of PM2.5 exposure on the trajectory of children's body mass index (BMI) have not been explored. METHODS: We conducted a longitudinal study among 1,450,830 Chinese children aged 6-19 years from Beijing and Zhongshan in China during 2005-2018 to examine the associations of PM2.5 and its chemical constituents with incident OWOB risk. We extracted PM2.5 mass and five main component exposure from Tracking Air Pollution in China (TAP) dataset. Cox proportional hazards models were applied to quantify exposure-response associations. We further performed principal component analysis (PCA) to handle the multi-collinearity and used quantile g-computation (QGC) approach to analyze the impacts of exposure mixtures. Additionally, we selected 125,863 children with at least 8 physical examination measurements and combined group-based trajectory models (GBTM) with multinomial logistic regression models to explore the impacts of exposure to PM2.5 mass and five constituents on BMI and BMI Z-score trajectories during 6-19 years. RESULTS: We observed each interquartile range increment in PM2.5 exposure was significantly associated with a 5.1 % increase in the risk of incident OWOB (95 % confidence Interval [CI]: 1.036-1.066). We also found black carbon, sulfate, organic matter, often linked to fossil combustion, had comparable or larger estimates of the effect (HR = 1.139-1.153) than PM2.5. Furthermore, Exposure to PM2.5 mass, sulfate, nitrate, ammonium, organic matter and black carbon was significantly associated with an increased odds of being in a larger BMI trajectory and being assigned to persistent OWOB trajectory. CONCLUSIONS: Our findings provide evidence that the constituents mainly from fossil fuel combustion may have a perceptible influence on increased OWOB risk associated with PM2.5 exposure in China. Moreover, long-term exposure to PM2.5 contributes to an increased odds of being in a lager BMI and a persistent OWOB trajectories.

Elucidating the Mechanism on the Transition-Metal Ion-Synergetic-Catalyzed Oxidation of SO2 with Implications for Sulfate Formation in Beijing Haze.

Currently, atmospheric sulfate aerosols cannot be predicted reliably by numerical models because the pathways and kinetics of sulfate formation are unclear. Here, we systematically investigated the synergetic catalyzing role of transition-metal ions (TMIs, Fe3+/Mn2+) in the oxidation of SO2 by O2 on aerosols using chamber experiments. Our results showed that the synergetic effect of TMIs is critically dependent on aerosol pH due to the solubility of Fe(III) species sensitive to the aqueous phase acidity, which is effective only under pH < 3 conditions. The sulfate formation rate on aerosols is 2 orders of magnitude larger than that in bulk solution and increases significantly on smaller aerosols, suggesting that such a synergetic-catalyzed oxidation occurs on the aerosol surface. The kinetic reaction rate can be described as R = k*[H+]-2.95[Mn(II)][Fe(III)][S(IV)] (pH ≤ 3.0). We found that TMI-synergetic-catalyzed oxidation is the dominant pathway of sulfate formation in Beijing when haze particles are very acidic, while heterogeneous oxidation of SO2 by NO2 is the most important pathway when haze particles are weakly acidic. Our work for the first time clarified the role and kinetics of TMI-synergetic-catalyzed oxidation of SO2 by O2 in haze periods, which can be parameterized into models for future studies of sulfate formation.

Characterization of carbonaceous particles by single particle aerosol mass spectrometer in the urban area of Chengdu, China.

Carbonaceous particles are an important chemical component of atmospheric fine particles. In this study, a single particle aerosol mass spectrometer was used to continuously measure the carbonaceous particles in Chengdu, one of the megacities most affected by haze in China, from January 22 to March 3, 2021. During the observation period, the average mass concentration of PM2.5 was 62.3 ± 37.2 µg m-3, and the emissions from mobile sources were more prominent. Carbonaceous particles accounted for 68.6% of the total particles and could be classified into 10 categories, with elemental carbon (EC) mixed with sulfate (EC-S) particles making the highest contribution (33.1%). EC particles rich in secondary components and organic carbon (OC) particles rich in secondary component exhibited different diurnal variations, suggesting different sources and mixing mechanisms. From "excellent" to "polluted" days, the contributions of EC-S, EC mixed with sulfate and nitrate (EC-SN) and OC mixed with EC (OC-EC) particles increased by 9.8%, 4.5% and 6.6%, respectively, and thus these particles are key targets for future pollution control. The potential source contribution of the southwest area was stronger than that of other areas, and the potential contribution of regional transport to EC-related particles was stronger than to OC-related particles. Most particles were highly mixed with sulfate or nitrate, and the level of secondary mixing further enhanced as pollution worsened.

Fluoride and acid enrichment in coal fire sponges in the Wuda coalfield, Inner Mongolia, Northern China.

Coal fire sponges (CFSs) are a type of sponge-like contaminated soil bulge common in coal fire areas. However, the impacts of CFSs on the local environment are not yet understood. Thus, this study investigated soil samples from CFSs in the Wuda coalfield, Inner Mongolia, China, focusing on the acidity, sulfate, and fluorine content. The results showed that the CFSs were highly acidic, with an average pH of 0.76, and contained high levels of SO42- (257.29 × 103 µg/g), total fluorine (TF, 2011.6 µg/g), and water-soluble fluorine (WF, 118.94 µg/g), significantly exceeding those in the regional background soil and indicating that CFSs are a point source of heavy pollution. Soils in the 8000 m2 reclamation zone showed elevated acidity and high SO42- (129.6 × 103 µg/g), TF (1237.8 µg/g), and WF (43.05 µg/g) levels, which was likely the result of the weathering and dissemination of CFS. The CFS samples were rich in hydrogen fluoride, releasing 202.05 ppb of it when heated to 40 °C. Correlation analysis indicated that the acid sulfate soils in CFSs are likely caused by HSO4-/SO42-. Time-of-flight secondary ion mass spectrometry detected four characteristic ions (F-, H3O+, H2SO4+, and HSO4-) in all micro-domains of each sample, indicating that ionic fluorine compounds and sulfuric acid hydrate were found in the CFS samples. Sulfate minerals detected in CFSs included CaSO4, Fe2(SO4)3, CdSO4, NH4HSO4, and Na2SO4. Thus, the results identified CFSs as a transmission channel for contamination, with erosional surface soils as the carrier, for the first time. CFSs pose a serious threat of contamination, albeit over limited areas.

Tracing sulfate sources and transformations of surface water using multiple isotopes in a mining-rural-urban agglomeration area.

Rapid urbanization and mining activities are exacerbating sulfate (SO42-) pollution in surface water, and the information on its sources and transformations is crucial for understanding the sulphur cycle in mining areas. In this study, the SO42- in the surface water of Huaibei mining area were monitored and the main sources of pollution and biogeochemical processes were identified using stable isotopes (δD, δ18O-H2O, δ34S-SO42- and δ18O-SO42-) and water chemistry. The results demonstrated the SO42- content in the Huihe River and Linhuan subsidence water area (SWA) is higher than that in other rivers and SWAs, which exceeded the environmental quality standard of surface water. The SO42- content of different rivers and SWAs showed seasonal differences, and the dry season was higher than the wet season. In addition, the SO42- in Tuohe River and Suihe River is primarily caused by urban sewage and agriculture activities, while in Zhonghu and Shuoxihu SWA is mainly contributed by natural evaporate dissolution. Notably, the input of SO42- in the Huihe River and Linhuan SWA caused by mining activities cannot be disregarded. The aerobic environment and isotopic fractionation of surface water indicate that sulfide oxidation is not the major cause of SO42- formation. This work has revealed the multiple sources and transformation mechanisms of SO42-, and provided a reference for the development of comprehensive management and effective remediation strategies of SO42- contamination in surface water around mining areas.

Sulfated polysaccharides of Laetiporus sulphureus fruiting bodies exhibit anti-breast cancer activity through cell cycle arrest, apoptosis induction, and inhibiting cell migration.

ETHNOPHARMACOLOGICAL RELEVANCE: Laetiporus sulphureus has long been used as an edible and medicinal mushroom in Asia, America, and Europe. Its fruiting bodies are widely used in folk medicine for treating cancer, gastric diseases, cough, and rheumatism. Polysaccharides are an important bioactive component of mushrooms. In nature, sulfated polysaccharides have never been reported in mushrooms. Furthermore, there is no information on differences in physicochemical properties and anti-breast cancer activities between polysaccharides (PS) and sulfated polysaccharides (SPS) of L. sulphureus. AIM OF THE STUDY: This study aimed to investigate the physicochemical properties of PS and SPS isolated from fruiting bodies of L. sulphureus and examine their anti-proliferative effects and mechanism(s) of action on MDA-MB-231 breast cancer cells. METHODS: Polysaccharides (PS) were isolated using hot water and ethanol precipitation methods. Sulfated polysaccharides (SPS) were isolated by the papain-assisted hydrolysis method. Physicochemical properties comprising sugar, protein, uronic acid, and sulfate contents, and molecular weight, monosaccharide composition, and structural conformation were analyzed on PS and SPS. In the anti-cancer study, a triple-negative breast cancer cell line (MDA-MB-231) and a normal human mammary epithelial cell line (H184B5F5/M10) were used to evaluate the anti-proliferative activity of PS and SPS, and their mechanism(s) of action. RESULTS: The results showed that SPS, which had higher sulfate and protein contents and diversified monosaccharide composition, exhibited more potent anti-proliferative activity against MDA-MB-231 cells than PS. Furthermore, it had a selective cytotoxic effect on breast cancer cells but not the normal cells. SPS induced cell cycle arrest at G0/G1 phase via down-regulating CDK4 and cyclin D1 and up-regulating p21 protein expression. Breast cancer cell apoptosis was not observed until 72 h after SPS treatment. In addition, SPS also markedly inhibited breast cancer cell migration. CONCLUSION: This study demonstrates that SPS exhibited selective cytotoxicity and was more potent than PS in inhibiting MDA-MB-231 cell proliferation. The contents of sulfate and protein, and monosaccharide composition could be the main factors affecting the anti-breast cancer activity of L. sulphureus SPS.

Sulphate-based electrochemical processes as an alternative for the remediation of a beauty salon effluent‡.

Beauty salons (BS) are places that deal with a wide range of cosmetics with potentially hazardous chemicals, and their effluent should be properly treated before going to the sewage system, once it represents characteristics of industrial wastewater. This work provides an extensive characterization of a BS effluent and its respective electrochemical treatment by comparing NaCl, Na2SO4, and Na2S2O8 as supporting electrolytes with a boron-doped diamond (BDD) as anode, applying 10 or 30 mA cm-2 of current density (j). The inclusion of UVC irradiation was also performed but the improvements achieved in removing the organic matter were null or lower. The analysis of chemical oxygen demand (COD) removal, energy consumption, and total current efficiency (TCE) was required to prove the efficacy of the processes and the comparative study of the performance of different technologies. Precipitate analysis was also done due to the high turbidity of the raw effluent and the appearance of a precipitate before and during the electrolysis, mainly with Na2S2O8. The precipitate confirmed the presence of silicates and small amounts of heavy metals. The results clearly showed that 6 h of treatment with Na2SO4 achieved 58% of COD removal with an energy consumption of about 0.52 kWh m-3, being the best electrolyte option for treating BS effluent by applying 10 mA cm-2. Under these experimental conditions, the final wastewater can be directly discharged into the sewage system with a lower amount of visible precipitate, and with 73% less turbidity. The treatment here proposed can be used as an alternative to decision-makers and governments once it can be a step further in the implementation of better and advanced politics of water sanitation.

Major ions in Central European precipitation - Insight into changes in NO3-/SO42-, NH4+/NO3- and NH4+/SO42- ratios over the last four decades.

Knowledge of precipitation composition is important, among other things, to reveal changes in atmospheric chemistry. Here we present the long-term time trends in ratios of major ions in precipitation, namely nitrate to sulphate (NO3-/SO42-), ammonium to sulphate (NH4+/SO42-) and ammonium to nitrate (NH4+/NO3-). For this we explore the long-term time series recorded by the Czech Hydrometeorological Institute at eight monitoring sites situated in urban, rural and mountain regions of the Czech Republic between 1980 and 2020. To that end, we use innovative Bayesian inference with the Integrated Nested Laplace Approximation (INLA) computational method appropriate for investigating complicated large-scale data. Our results indicated: (i) increasing NO3-/SO42- ratio in precipitation over time and distinct seasonal behaviour with higher values in winter and lower values in summer, (ii) increasing NH4+/SO42- ratio in precipitation and distinct seasonal behaviour with higher values in summer and lower values in winter and (iii) relatively stable NH4+/NO3- ratio in precipitation with a mild recent increase and distinct seasonal behaviour with higher values in summer and lower values in winter. This behaviour pattern holds true for all the sites analysed, irrespective of their geographical position, altitude or environment. Though explored in detail rarely, the ion ratios are important to study as they reflect changes in atmospheric chemistry, mirroring changes in emissions and meteorology and suggesting changing impacts on ecosystems and the environment.