Bioaccessibility of lead and cadmium in soils around typical lead-acid power plants and their effect on gut microorganisms.

Potentially toxic elements (Pb and Cd) contamination of soil can adversely affect human health. Moreover, these metal ions interact with the gut microbiota after entering the human digestive system. Based on the physiologically based extraction test and the simulator of human intestinal microbial ecosystem, the bioaccessibility of Pb and Cd in soils contaminated with lead-acid power plants was assessed. The gastric stage exhibited the greatest average bioaccessibility of lead and cadmium (63.39% and 57.22%), followed by the small intestinal stage (6.86% and 36.29%); due to gut microorganisms, the bioaccessibility of lead and cadmium was further reduced in the colon stage (1.86% and 4.22%). Furthermore, to investigate soil contamination's effects on gut microbes, 16S rRNA high-throughput sequencing was used to identify the gut microbial species after the colon period. Due to Pb and Cd exposure, the relative abundance of Firmicutes and unidentified_Bacteria decreased, while the relative abundance of Proteobacteria, Synergistota, and Bacteroidota increased. The relationship between environmental factors and the number of microbial species in the gut was also examined using Spearman correlation analysis. Pb and Cd exposure has been found to affect the composition and structure of the gut microbiota.

Contrasting effects of a novel biochar-microalgae complex on arsenic and mercury removal.

Biochar and algae were commonly used as environmental-friendly adsorbents to treat wastewater contaminated with heavy metals. In the study, we used a biochar-microalgae complex of Coconut shell activated carbon (Csac) and Chlorella to evaluate and compare the adsorption ability of arsenic and mercury. The adsorption kinetic study showed that the adsorption efficiency of the biochar-microalgae complex for mercury was better remarkably than arsenic (about 74.84% higher in initial 1 min and 71.62% higher at adsorption equilibrium), which could be interpreted as the complex had excellent adsorption capacity for mercury. The new biochar-microalgae complex adsorbed up to 46.8 µg·g-1 of mercury at 100 µg·L-1 concentration. FTIR and XPS indicated that the surface of biochar-microalgae complex adsorbent had abundant oxygen-containing functional groups that could provide active sites during the adsorption process, i.e., -COOH, -OH and C-O-C et al. Compared with arsenic, the adsorption peaks of mercury moved or changed significantly, suggesting that the complex strongly adsorbed mercury and the main adsorption mechanisms were the ion exchange and complexation between functional groups and mercury ion. What must be emphasized was arsenic mainly existed as negative ions (AsO2-, AsO23-) in water, which was the reason for the weak adsorption capacity of the biochar-microalgae complex for arsenic. In short, the adsorption efficiency and performance of the biochar-microalgae complex was significantly higher than that of arsenic (p < 0.01), and the adsorption of mercury by biochar-microalgae was chemisorption based on the single molecular layer theory.

Mercury Reduction, Uptake, and Species Transformation by Freshwater Alga Chlorella vulgaris under Sunlit and Dark Conditions.

As a major entry point of mercury (Hg) to aquatic food webs, algae play an important role in taking up and transforming Hg species in aquatic ecosystems. However, little is known how and to what extent Hg reduction, uptake, and species transformations are mediated by algal cells and their exudates, algal organic matter (AOM), under either sunlit or dark conditions. Here, using Chlorella vulgaris (CV) as one of the most prevalent freshwater model algal species, we show that solar irradiation could enhance the reduction of mercuric Hg(II) to elemental Hg(0) by both CV cells and AOM. AOM reduced more Hg(II) than algal cells themselves due to cell surface adsorption and uptake of Hg(II) inside the cells under solar irradiation. Synchrotron radiation X-ray absorption near-edge spectroscopy (SR-XANES) analyses indicate that sunlight facilitated the transformation of Hg to less bioavailable species, such as ß-HgS and Hg-phytochelatins, compared to Hg(Cysteine)2-like species formed in algal cells in the dark. These findings highlight important functional roles and potential mechanisms of algae in Hg reduction and immobilization under varying lighting conditions and how these processes may modulate Hg cycling and bioavailability in the aquatic environment.

Synergistic Effects of a Chalkophore, Methanobactin, on Microbial Methylation of Mercury.

Microbial production of the neurotoxin methylmercury (MeHg) is a significant health and environmental concern, as it can bioaccumulate and biomagnify in the food web. A chalkophore or a copper-binding compound, termed methanobactin (MB), has been shown to form strong complexes with mercury [as Hg(II)] and also enables some methanotrophs to degrade MeHg. It is unknown, however, if Hg(II) binding with MB can also impede Hg(II) methylation by other microbes. Contrary to expectations, MB produced by the methanotroph Methylosinus trichosporium OB3b (OB3b-MB) enhanced the rate and efficiency of Hg(II) methylation more than that observed with thiol compounds (such as cysteine) by the mercury-methylating bacteria Desulfovibrio desulfuricans ND132 and Geobacter sulfurreducens PCA. Compared to no-MB controls, OB3b-MB decreased the rates of Hg(II) sorption and internalization, but increased methylation by 5- to 7-fold, suggesting that Hg(II) complexation with OB3b-MB facilitated exchange and internal transfer of Hg(II) to the HgcAB proteins required for methylation. Conversely, addition of excess amounts of OB3b-MB or a different form of MB from Methylocystis strain SB2 (SB2-MB) inhibited Hg(II) methylation, likely due to greater binding of Hg(II). Collectively, our results underscore the complex roles of microbial exogenous metal-scavenging compounds in controlling net production and bioaccumulation of MeHg in the environment.IMPORTANCE Some anaerobic microorganisms convert inorganic mercury (Hg) into the neurotoxin methylmercury, which can bioaccumulate and biomagnify in the food web. While the genetic basis of microbial mercury methylation is known, factors that control net methylmercury production in the environment are still poorly understood. Here, it is shown that mercury methylation can be substantially enhanced by one form of an exogenous copper-binding compound (methanobactin) produced by some methanotrophs, but not by another. This novel finding illustrates that complex interactions exist between microbes and that these interactions can potentially affect the net production of methylmercury in situ.

Arsenic accumulation, distribution and source analysis of rice in a typical growing area in north China.

Rice (Oryza sativa) is believed to be a major source of arsenic (As) exposure in humans, especially in Asia. In this study, As accumulation, distribution and source analysis of rice are investigated in five sites (SZ, QH, XZ, WS and JX) in the Nansi Lake area, an important rice-growing region in north China. Findings show that total As average concentrations were 6.3-13.6 mg kg-1 and 5.5-9.9 µg L-1 in paddy soil and irrigation water, respectively. Inorganic arsenic As(III) and dimethylarsinic acid DMAs(V) were the major speciation in polished rice, with a small proportion of As(V) evident. Notably, the percentage of As(III) increased by 63.9-68.5%. Based on survey data, the addition of total As to farm soil due to fertilizer application was 31.5-11,580 mg per hectare per year. According to the results of Spearman's rank correlation analysis and Principal Component Analysis (PCA), As levels in soil and irrigation water may be important factors influencing As concentration in rice.

Characterization of Arsenic Biotransformation by a Typical Bryophyte Physcomitrella patens.

Arsenic (As) is a ubiquitous environmental toxin that has created catastrophic human health and environmental problems around world. Physcomitrella patens is a potential model plant for the study of environmental monitoring, which exists in all kinds of ecosystems. In this study, arsenic metabolism was investigated by this moss. When supplied with different levels of arsenate (50, 100, 200 µmol/L) for a 4-week period, the total arsenic concentrations were up to 231.4-565.4 mg/kg DW in this moss. Arsenite concentration increased with increasing external arsenate concentrations, the proportion was up to 25.1-36.8% of the total As. An arsenate reductase, PpACR2, was identified and functionally characterized. Heterologous expression of PpACR2 in an As(V)-sensitive strain WC3110 (ΔarsC) of Escherichia coli conferred As(V) resistance. Purified PpACR2 protein exhibited the arsenate reductase activity. Given its powerful As accumulation ability, the bryophyte could be exploited in bioremediation of As-contaminated environments.

Study on arsenic speciation, bioaccessibility, and gut microbiota in realgar-containing medicines by DGT technique and artificial gastrointestinal extraction (PBET) combine with simulated human intestinal microbial ecosystem (SHIME).

It is well-known that several Chinese patent medicines use realgar as a specific component. People are more aware of the health dangers associated with realgar since it includes arsenic. Previous research overstated the arsenic toxicity of realgar-containing Chinese prescription medications because little thought was given to the influence of arsenic bioaccessibility by gut microbiota. In light of this, this study examined the total content, bioaccessibility and speciation of targeted medications while also examining intestinal epithelial transit utilizing the diffusive gradients in thin-films (DGT). All samples contained arsenic, and the bioaccessibilities of the colon, intestine and gastric regions ranged from 0.19% to 1.73%, 0.25-1.88% and 0.21-1.70% respectively. The range of DGT-bioaccessibility is 0.01-0.0018%. Three steps of analysis were conducted on inorganic As(III) and As(V). In health risk assessment, the ADDs and HQs of DGT-bioaccessibility were below the threshold levels when compared to computing average daily intake dose (ADD) and hazard quotient (HQ) by bioaccessibility of gastric, intestinal and colon. Additionally, Proteobacteria and Firmicutes were discovered to be the two predominant kinds of gut microbes in this study. Under arsenic exposure, the abundance of Christensenellaceae, Desulfovibrionaceae and Akkermansiaceae increased, but the quantity of Rikenellaceae decreased. These findings revealed that alterations in gut microbiota had an impact on host metabolism.

Biotransformation and volatilization of arsenic by three photosynthetic cyanobacteria.

Arsenic (As) is a pervasive and ubiquitous environmental toxin that has created worldwide human health problems. However, there are few studies about how organisms detoxify As. Cyanobacteria are capable of both photolithotrophic growth in the light and heterotrophic growth in the dark and are ubiquitous in soils, aquatic systems, and wetlands. In this study, we investigated As biotransformation in three cyanobacterial species (Microcystis sp. PCC7806, Nostoc sp. PCC7120, and Synechocystis sp. PCC6803). Each accumulated large amounts of As, up to 0.39 g kg(-1) dry weight, 0.45 g kg(-1) dry weight, and 0.38 g kg(-1) dry weight when treated with 100 µM sodium arsenite for 14 d, respectively. Inorganic arsenate and arsenite were the predominant species, with arsenate making up >80% of total As; methylated arsenicals were detected following exposure to higher As concentrations. When treated with arsenate for 6 weeks, cells of each cyanobacterium produced volatile arsenicals. The genes encoding the As(III) S-adenosylmethionine methyltransferase (ArsM) were cloned from these three cyanobacteria. When expressed in an As-hypersensitive strain of Escherichia coli, each conferred resistance to arsenite. Two of the ArsM homologs (SsArsM from Synechocystis sp. PCC6803 and NsArsM from Nostoc sp. PCC7120) were purified and were shown to methylate arsenite in vitro with trimethylarsine as the end product. Given that ArsM homologs are widespread in cyanobacteria, we propose that they play an important role in As biogeochemistry.

Study on the mechanism of biochar loaded typical microalgae Chlorella removal of cadmium.

Coconut shell activated carbon (Csac) is one of the most widely used materials to remove cadmium (Cd) from contaminated water. A large diversity of microorganisms exists in various aquatic systems and may aid Cd removal by Csac. In this study, we explored the reactions of Csac with microalgae (Chlorella) in Cd-containing media. The results of scanning electron microscope (SEM) imaging, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), superconducting pulse-Fourier transform nuclear magnetic resonance (pulse-FT NMR) and X-ray photoelectron spectroscopy (XPS) indicated that Chlorella could adhere in the micropores of Csac formed Csac@Chlorella composite adsorbent loading Chlorella. Furthermore, the composite adsorbent surface had abundant functional groups such -COOH, -OH and C-O-C, which served as active sites during the adsorption process. Compared with Csac, Csac@Chlorella had an enhanced Cd adsorption capacity evidently. The results showed that pH 8, 0.2 g Csac, OD680 of 0.1 for Chlorella were optimal conditions for maximum Cd adsorption capacity within one hour contact time. Furthermore, the Cd adsorption process was well described by the pseudo-second-order and Langmuir adsorption isotherm models. The models revealed that the adsorption process was mainly based on chemical adsorption of a single molecular layer, accompanied by electrostatic attraction, complexation and intracellular adsorption, amongst other parameters. Collectively, the findings illustrate that the microalgae (Chlorella)-Csac-Cd interaction is complex and will thus have immense interest to a broad range of biological, environmental, and geoscience communities.

Contrary effects of phytoplankton Chlorella vulgaris and its exudates on mercury methylation by iron- and sulfate-reducing bacteria.

Mercury (Hg) is a pervasive environmental pollutant and poses serious health concerns as inorganic Hg(II) can be converted to the neurotoxin methylmercury (MeHg), which bioaccumulates and biomagnifies in food webs. Phytoplankton, representing the base of aquatic food webs, can take up Hg(II) and influence MeHg production, but currently little is known about how and to what extent phytoplankton may impact Hg(II) methylation by itself or by methylating bacteria it harbors. This study investigated whether some species of phytoplankton could produce MeHg and how the live or dead phytoplankton cells and excreted algal organic matter (AOM) impact Hg(II) methylation by several known methylators, including iron-reducing bacteria (FeRB), Geobacter anodireducens SD-1 and Geobacter sulfurreducens PCA, and the sulfate-reducing bacterium (SRB) Desulfovibrio desulfuricans ND132 (or Pseudodesulfovibrio mercurii). Our results indicate that, among the 4 phytoplankton species studied, none were capable of methylating Hg(II). However, the presence of phytoplankton cells (either live or dead) from Chlorella vulgaris (CV) generally inhibited Hg(II) methylation by FeRB but substantially enhanced methylation by SRB D. desulfuricans ND132. Enhanced methylation was attributed in part to CV-excreted AOM, which increased Hg(II) complexation and methylation by ND132 cells. In contrast, inhibition of methylation by FeRB was attributed to these bacteria incapable of competing with phytoplankton for Hg(II) binding and uptake. These observations suggest that phytoplankton could play different roles in affecting Hg(II) methylation by the two groups of anaerobic bacteria, FeRB and SRB, and thus shed additional light on how phytoplankton blooms may modulate MeHg production and bioaccumulation in the aquatic environment.

Characterization of arsenate transformation and identification of arsenate reductase in a green alga Chlamydomonas reinhardtii.

Arsenic (As) is a pervasive and ubiquitous environmental toxin that has created catastrophic human health problems world-wide. Chlamydomonas reinhardtii is a unicellular green alga, which exists ubiquitously in freshwater aquatic systems. Arsenic metabolism processes of this alga through arsenate reduction and sequent store and efflux were investigated. When supplied with 10 micromol/L arsenate, arsenic speciation analysis showed that arsenite concentration increased from 5.7 to 15.7 mg/kg dry weight during a 7-day period, accounting for 18%-24% of the total As in alga. When treated with different levels of arsenate (10, 20, 30, 40, 50 micromol/L) for 7 days, the arsenite concentration increased with increasing external arsenate concentrations, the proportion of arsenite was up to 23%-28% of the total As in alga. In efflux experiments, both arsenate and arsenite could be found in the efflux solutions. Additionally, the efflux of arsenate was more than that of arsenite. Furthermore, two arsenate reductase genes of C. reinhardtii (CrACR2s) were cloned and expressed in Escherichia coli strain WC3110 (deltaarsC) for the first time. The abilities of both CrACR2s genes to complement the arsenate-sensitive strain were examined. CrACR2.1 restored arsenate resistance at 0.8 mmol/L. However, CrACR2.2 showed much less ability to complement. The gene products were demonstrated to reduce arsenate to arsenite in vivo. In agreement with the complementation results, CrACR2.1 showed higher reduction ability than CrACR2.2, when treated with 0.4 mmol/L arsenate for 16 hr incubation.

In vitro oral bioaccessibility investigation and human health risk assessment of heavy metals in wheat grains grown near the mines in North China.

There is limited research on the effects of gut microbiota on bioaccessibility of heavy metals in wheat grains. In this study, bioaccessibility of heavy metals (Cu, Cd, Pb, and Zn) in wheat was determined to elucidate transfer characteristics in the soil-grain-human systems near two large-scale mining areas in Shandong Province, North China using the physiologically-based extraction test (PBET) in combination with a simulator of human intestinal microbial ecosystems (SHIME). The results showed the bioconcentration factors (BCFs) of Cu, Cd, Pb, and Zn were 0.123-0.327, 0.188-0.478, 0.019-0.099, and 0.262-0.825, respectively. Significant and positive correlations were observed between heavy metals in soils and wheat grains. In the simulated colon phase, bioaccessibility of Cd and Zn significantly decreased to 7.81% and 8.81%, respectively, being 53% and 64% of that in the simulated small intestinal phase. However, bioaccessibility of Pb showed an obvious escalating trend, being 2.4 times higher than that of intestinal incubation. Based on the estimated daily intakes and contribution, the relative high contribution of Cu to the benchmark dose in both phases, Cu metabolism by human gut microbiota should be considered in human health risk assessment regarding wheat consumption.

Ambient air pollution, smog episodes and mortality in Jinan, China.

We aimed to assess the acute effects of ambient air pollution and weather conditions on mortality in the context of Chinese smog episodes. A total of 209,321 deaths were recorded in Jinan, a large city in eastern China, during 2011-15. The mean concentrations of daily particulate matter ≤10 µm (PM10), fine particulate matter (PM2.5), sulfur dioxide (SO2) and nitrogen dioxide (NO2) were 169 µg/m3, 100 µg/m3, 77 µg/m3, and 54 µg/m3, respectively. Increases of 10 µg/m3 in PM10, PM2.5, SO2 and NO2 were associated with 1.11% (95% CI 0.96-1.26%), 0.71% (95% CI 0.60-0.82%), 1.69% (95% CI 1.56-1.83%), and 3.12% (95% CI 2.72-3.53%) increases in daily non-accidental mortality rates, respectively. Moreover, the risk estimates for these 4 pollutants were higher in association with respiratory and cardiovascular mortality. The effects of all the evaluated pollutants on mortality were greater in winter than in summer. Smog episodes were associated with a 5.87% (95% CI 0.16-11.58%) increase in the rate of overall mortality. This study highlights the effect of exposure to air pollution on the rate of mortality in China.

Biomethylation and Volatilization of Arsenic by Model Protozoan Tetrahymena pyriformis under Different Phosphate Regimes.

Tetrahymena pyriformis, a freshwater protozoan, is common in aquatic systems. Arsenic detoxification through biotransformation by T. pyriformis is important but poorly understood. Arsenic metabolic pathways (including cellular accumulation, effluxion, biomethylation, and volatilization) of T. pyriformis were investigated at various phosphate concentrations. The total intracellular As concentration increased markedly as the external phosphate concentration decreased. The highest concentration was 168.8 mg·kg-1 dry weight, after exposure to As(V) for 20 h. Inorganic As was dominant at low phosphate concentrations (3, 6, and 15 mg·L-1), but the concentration was much lower at 30 mg·L-1 phosphate, and As(V) contributed only ~7% of total cellular As. Methylated As contributed 84% of total As at 30 mg·L-1 phosphate, and dimethylarsenate (DMAs(V)) was dominant, contributing up to 48% of total As. Cellular As effluxion was detected, including inorganic As(III), methylarsenate (MAs(V)) and DMAs(V). Volatile As was determined at various phosphate concentrations in the medium. All methylated As concentrations (intracellular, extracellular, and volatilized) had significant linear positive relationships with the initial phosphate concentration. To the best of our knowledge, this is the first study of As biotransformation by protozoa at different phosphate concentrations.

Efficient Photocatalytic Disinfection of Escherichia coli O157:H7 using C70-TiO2 Hybrid under Visible Light Irradiation.

Efficient photocatalytic disinfection of Escherichia coli O157:H7 was achieved by using a C70 modified TiO2 (C70-TiO2) hybrid as a photocatalyst under visible light (λ > 420 nm) irradiation. Disinfection experiments showed that 73% of E. coli O157:H7 died within 2 h with a disinfection rate constant of k = 0.01 min(-1), which is three times that measured for TiO2. The mechanism of cell death was investigated by using several scavengers combined with a partition system. The results revealed that diffusing hydroxyl radicals play an important role in the photocatalytically initiated bacterial death, and direct contact between C70-TiO2 hybrid and bacteria is not indispensable in the photocatalytic disinfection process. Extracellular polymeric substances (EPS) of bacteria have little effect on the disinfection efficiency. Analyses of the inhibitory effect of C70-TiO2 thin films on E. coli O157:H7 showed a decrease of the bacterial concentration from 3 × 10(8) to 38 cfu mL(-1) in the solution with C70-TiO2 thin film in the first 2 h of irradiation and a complete inhibition of the growth of E. coli O157:H7 in the later 24 h irradiation.

Biomethylation and volatilization of arsenic by the marine microalgae Ostreococcus tauri.

Ostreococcus tauri is a marine green microalga, recognized as a model organism of the marine phytoplankton assemblage and widely distributed from coastal to oligotrophic waters. This study showed it could tolerate both arsenite and arsenate concentrations of up to 100µM, and cellular As concentration increased significantly (P<0.01) with increasing concentration of As(V) in the medium (0-50µM). It was revealed that As biotransformations were mediated by algal cells. Volatilized As was detected and the ability of As biovolatilization by O. tauri was demonstrated. The reduction of As(V) to As(III) might be the limiting step for As methylation and volatilization from seawater since the treatment with As(III) yielded five times more volatile As as compared to that with As(V). Arsenic biogeochemical cycle in the marine environment might play an important role based on the huge surface area of ocean (71%) and the massive number of marine phytoplankton.

Arsenate toxicity and stress responses in the freshwater ciliate Tetrahymena pyriformis.

The arsenic metabolism in different biological organisms has been studied extensively. However, little is known about protozoa. Herein, we investigated the cell stress responses of the freshwater ciliate Tetrahymena pyriformis to arsenate toxicity. An acute toxicity assay revealed an 18-h EC(50) arsenate concentration of ca. 40 µM, which caused significant changes in the cell shape, growth and organism mobility. Whereas, under exposure to 30 µM arsenate, T. pyriformis could grow reasonably well, indicating a certain resistance of this organism. Arsenic speciation analysis revealed that 94-98% of the total arsenate in cells of T. pyriformis could be transformed to monomethylarsonic acid, dimethylarsinic acid and a small proportion of arsenite after 18 h of arsenate exposure, thus indicating the major detoxification pathway by arsenic oxidation/reduction and biomethylation. Finally, comparative proteomic analysis unveiled significant changes in the expression of multiple proteins involved in anti-oxidation, sugar and energy metabolism, proteolysis, and signal transduction. Our results revealed multiple pathways of arsenate detoxification in T. pyriformis, and indicated that protozoa may play important roles in the biogeochemical cycles of arsenic.

Rapid biotransformation of arsenic by a model protozoan Tetrahymena pyriformis GL-C. [corrected].

Arsenic biomethylation and biovolatilization are thought to be two important metabolic pathways in aquatic and soil environments. Tetrahymena thermophila is a genus of free-living ciliated protozoan that is widely distributed in freshwater environments around the world. In this study, we studied arsenic accumulation, speciation, efflux, methylation and volatilization in this unicellular eukaryote exposed to various concentrations of arsenate. Our results show that T. thermophila accumulated 187 mg.kg⁻¹ dry weight of arsenic when exposed to 40 µM for 48 h, with MMAs(V) (monomethylarsenate) and DMAs(V) (dimethylarsenate) as the dominant species, accounting for 66% of the total arsenic. Meanwhile, arsenate, arsenite, MMAs(V) and DMAs(V) were detected in the culture medium; the last three were released by the cells. The production of volatile arsenic increased with increasing external As(V) concentrations and exposure time. To our knowledge, this is the first study on arsenic metabolism, particularly biomethylation and biovolatilization, in protozoa.