Nitrogen-fixing cyanobacteria enhance microbial carbon utilization by modulating the microbial community composition in paddy soils of the Mollisols region.

Nitrogen-fixing cyanobacteria (NFC) are photosynthetic prokaryotic microorganisms capable of nitrogen fixation. They can be used as biofertilizers in paddy fields, thereby improving the rice tillering capacity and yield. To reveal the microbiological mechanisms by which nitrogen-fixing cyanobacteria alter soil carbon storage, we conducted a field experiment using NFC as a partial substitute for nitrogen fertilizer in paddy fields in the Sanjiang Plain of Northeast China's Mollisols region. Using metagenomic sequencing technology and Biolog Ecoplate™ carbon matrix metabolism measurements, we explored the changes in the soil microbial community structure and carbon utilization in paddy fields. The results indicated that the replacement of nitrogen fertilizer with NFC predisposed the soil microbial community to host a great number of copiotrophic bacterial taxa, and Proteobacteria and Actinobacteria were closely associated with the metabolism of soil carbon sources. Moreover, through co-occurrence network analysis, we found that copiotrophic bacteria clustered in modules that were positively correlated with the metabolic level of carbon sources. The addition of NFC promoted the growth of copiotrophic bacteria, which increased the carbon utilization level of soil microorganisms, improved the diversity of the microbial communities, and had a potential impact on the soil carbon stock. The findings of this study are helpful for assessing the impact of NFC on the ecological function of soil microbial communities in paddy fields in the black soil area of Northeast China, which is highly important for promoting sustainable agricultural development and providing scientific reference for promoting the use of algal-derived nitrogen fertilizers.

Enhancing the bioreduction and interaction of arsenic and iron by thiosulfate in groundwater.

Thiosulfate influences the bioreduction and migration transformation of arsenic (As) and iron (Fe) in groundwater environments. The aim of this study was to investigate the impact of microbially-mediated sulfur cycling on the bioreduction and interaction of As and Fe. Microcosm experiments were conducted, including bioreduction of thiosulfate, As(V), and Fe(III) by Citrobacter sp. JH012-1, as well as the influence of thiosulfate input at different initial arsenate concentrations on the bioreduction of As(V) and Fe(III). The results demonstrate that Citrobacter sp. JH012-1 exhibited strong reduction capabilities for thiosulfate, As(V), and Fe(III). Improving thiosulfate level promoted the bioreduction of Fe(III) and As(V). When 0, 0.1, 0.5, and 1 mM thiosulfate were added, Fe(III) was completely reduced within 9 days, 3 days, 1 day, and 0.5 days, simultaneously, 72.8%, 82.2%, 85.5%, and 90.0% of As(V) were reduced, respectively. The products of As(III) binding with sulfide are controlled by the ratio of As-S. When the initial arsenate concentration was 0.025 mM, the addition of thiosulfate resulted in the accumulation of soluble thioarsenite. However, when the initial arsenate level increased to 1 mM, precipitates of orpiment or realgar were formed. In the presence of both arsenic and iron, As(V) significantly inhibits the bioreduction of Fe(III). Under the concentrations of 0, 0.025, and 1 mM As(V), the reduction rates of Fe(III) were 100%, 91%, and 83%, respectively. In this scenario, the sulfide produced by thiosulfate reduction tends to bind with Fe(II) rather than As(III). Therefore, the competition of arsenic-iron and thiosulfate concentration should be considered to study the impact of thiosulfate on arsenic and iron migration and transformation in groundwater.

Nitrite-dependent anaerobic methane oxidation (N-DAMO) in global aquatic environments: A review.

The vast majority of processes in the carbon and nitrogen cycles are driven by microorganisms. The nitrite-dependent anaerobic oxidation of methane (N-DAMO) process links carbon and nitrogen cycles, offering a novel approach for the simultaneous reduction of methane emissions and nitrite pollution. However, there is currently no comprehensive summary of the current status of the N-DAMO process in natural aquatic environments. Therefore, our study aims to fill this knowledge gap by conducting a comprehensive review of the global research trends in N-DAMO processes in various aquatic environments (excluding artificial bioreactors). Our review mainly focused on molecular identification, global study sites, and their interactions with other elemental cycling processes. Furthermore, we performed a data integration analysis to unveil the effects of key environmental factors on the abundance of N-DAMO bacteria and the rate of N-DAMO process. By combining the findings from the literature review and data integration analysis, we proposed future research perspectives on N-DAMO processes in global aquatic environments. Our overarching goal is to advance the understanding of the N-DAMO process and its role in synergistically reducing carbon emissions and removing nitrogen. By doing so, we aim to make a significant contribution to the timely achievement of China's carbon peak and carbon neutrality targets.

Application of coconut shell activated carbon filter in vertical subsurface flow constructed wetland for enhanced multi-metal bioremediation and antioxidant response of Salvinia cucullate.

Coconut shell activated carbon (CNSAC) was applied as a filter layer in hybrid vertical subsurface flow constructed wetland (H-VSSF-CW), in order to enhance the multi-metal removal efficiency of the constructed wetland (CW) and to reduce heavy metal accumulation on Salvinia cucullata. Treatment P + AC, (having CNSAC filter layer), showed 32, 21 and 34% more Cd, Cr, and Pb removal efficiency than treatment P (without CNSAC layer). CNSAC activated carbon adsorbed Cd and Pb and Cr by functional groups -NH, -NO2, -C-O, -OH and -CO, and significantly reduced Cd and Pb exposure to S. cucullate. Chromium adsorption by CNSAC filter layer was half (just 25% of total input) of the Cd and Pb. In treatment P, due to high Cd, Pb and Cr accumulation in S. cucullate, the antioxidant defense mechanism of the plant was collapsed and cell death was observed, which in turn has resulted reduced biomass gain (5% reduction). On the other hand, in treatment P + AC, an antioxidant defense mechanism was active in the form significantly (p ≤ 0.05) increased of SOD, CAT and proline content while reduced MDA, EL, %EB and soluble sugar. So, the application of CNSAC increased the heavy metal removal efficiency of H-VSSF-CW by adsorption of a considerable share of heavy metal and hence, reduced the heavy metal load/exposure to S. cucullate.

Manganese promotes stability of natural arsenic sinks in a groundwater system with arsenic-immobilization minerals: Natural remediation mechanism and environmental implications.

Arsenic (As)-immobilizing iron (Fe)-manganese (Mn) minerals (AFMM) represent potential As sinks in As-enriched groundwater environments. The process and mechanisms governing As bio-leaching from AFMM through interaction with reducing bacteria, however, remain poorly delineated. This study examined the transformation and release of As from AFMM with varying Mn/Fe molar ratios (0:1, 1:5, 1:3, and 1:1) in the presence of As(V)-reducing bacteria specifically Shewanella putrefaciens CN32. Notably, strain CN32 significantly facilitated the bio-reduction of As(V), Fe(III), and Mn(IV) in AFMM. In systems with Mn/Fe molar ratios of 1:5, 1:3, and 1:1, As bio-reduction decreased by 28%, 34%, and 47%, respectively, compared to the system with a 0:1 ratio. This Mn-induced inhibition of Fe/As bio-reduction was linked to several concurrent factors: preferential Mn bio-reduction, reoxidation of resultant Fe(II)/As(III) due to Mn components, and As adsorption onto emergent Fe precipitates. Both the reductive dissolution of AFMM and the bio-reduction of As(V) predominantly controlled As bio-release. Structural equation models indicated that reducing bacteria destabilize natural As sinks more through As reduction than through Mn(II) release, Fe reduction, or Fe(II) release. Systems with Mn/Fe molar ratios of 1:5, 1:3, and 1:1 showed a decrease in As bio-release by 24%, 41%, and 59%, respectively, relative to the 0:1 system. The observed suppression of As bioleaching was ascribed to both the inhibition of As/Fe bio-reduction by Mn components and the immobilization of As by freshly generated Fe precipitates. These insights into the constraining effect of Mn on the biotransformation and bioleaching of As from AFMM are crucial for grasping the long-term stability of natural As sinks in groundwater, and enhance strategies for in-situ As stabilization in As-afflicted aquifers through Nature-Based Solutions.

Leptolyngbya sp. XZMQ and Bacillus XZM co-inoculation reduced sunflower arsenic toxicity by regulating rhizosphere microbial structure and enzyme activity.

Microorganisms are of great significance for arsenic (As) toxicity amelioration in plants as soil fertility is directly affected by microbes. In this study, we innovatively explored the effects of indigenous cyanobacteria (Leptolyngbya sp. XZMQ) and plant growth-promoting bacteria (PGPB) (Bacillus XZM) on the growth and As absorption of sunflower plants from As-contaminated soil. Results showed that single inoculation and co-inoculation stimulated the growth of sunflower plants (Helianthus annuus L.), enhanced enzyme activities, and reduced As contents. In comparison to the control group, single innoculation of microalgae and bacteria in the rhizosphere increased extracellular polymeric substances (EPS) by 21.99% and 14.36%, respectively, whereas co-inoculation increased them by 35%. Compared with the non-inoculated group, As concentration in the roots, stems and leaves of sunflower plants decreased by 38%, 70% and 41%, respectively, under co-inoculation conditions. Inoculation of Leptolyngbya sp. XZMQ significantly increased the abundance of nifH in soil, while co-inoculation of cyanobacteria and Bacillus XZM significantly increased the abundance of cbbL, indicating that the coupling of Leptolyngbya sp. XZMQ and Bacillus XZM could stimulate the activity of nitrogen-fixing and carbon-fixing microorganisms and increased soil fertility. Moreover, this co-inoculation increased the enzyme activities (catalase, sucrase, urease) in the rhizosphere soil of sunflower and reduced the toxic effect of As on plant. Among these, the activities of catalase, peroxidase, and superoxide dismutase decreased. Meanwhile, co-inoculation enables cyanobacteria and bacteria to attach and entangle in the root area of the plant and develop as symbiotic association, which reduced As toxicity. Co-inoculation increased the abundance of aioA, arrA, arsC, and arsM genes in soil, especially the abundance of microorganisms with aioA and arsM, which reduced the mobility and bioavailability of As in soil, hence, reduced the absorption of As by plants. This study provides a theoretical basis for soil microbial remediation in mining areas.

Red light alleviates Cd toxicity in Egeria densa by modifying carbon-nitrogen metabolism and boosting energy metabolism.

Among the various pollutants detected in aquatic ecosystems, cadmium (Cd) is considered as one of the most hazardous. Freshwater macrophytes have been recognized as possible candidates for eliminating Cd from environment. Nevertheless, the impact of light quality on their ability to tolerate Cd toxicity remains unclear, and the underlying mechanisms have yet to be fully elucidated. In this study, we utilized physiological testing and metabolomics to explore the potential mechanisms by which light quality influences the ability of Egeria densa, a significant Cd hyperaccumulator, to withstand Cd toxicity. The study demonstrated that following Cd treatment, E. densa grown under red light exhibited superior photosynthetic efficiency compared to those grown under blue light, as evidenced by significantly increased photosynthetic rate, higher starch content, and greater activity of photosynthetic enzymes. Moreover, metabolomic analyses revealed that under Cd stress, E. densa grown under red light exhibited an enhanced glycolysis for increased energy production. Sucrose metabolism was also improved to generate sufficient sugar including glucose, fructose and mannose for osmotic adjustment. Moreover, under red light, the heightened production of α-ketoglutarate via tricarboxylic acid (TCA) cycle redirected nitrogen flow towards the synthesis of resilient substances such as γ-Aminobutyric Acid (GABA) and methionine. The production of these substances was ∼2.0 and 1.3 times greater than that of treatment with Cd under blue light, thereby improving E. densa's capacity to withstand Cd stress. This study represents the initial investigation into the possible mechanisms by which light quality influences the ability of E. densa to withstand Cd toxicity through regulating CN metabolism. Furthermore, these findings have the potential to improve phytoremediation strategies aimed at reducing Cd pollution.

Native microalgae and Bacillus XZM remediate arsenic-contaminated soil by forming biological soil crusts.

Biological soil crusts (BSCs) are a useful tool for immobilization of metal(loid)s in mining areas. Yet, the typical functional microorganisms involved in promoting the fast development of BSCs and their impacts on arsenic(As) contaminated soil remain unverified. In this study, As-contaminated soil was inoculated with indigenous Chlorella thermophila SM01 (C. thermophila SM01), Leptolyngbya sp. XZMQ, isolated from BSCs in high As-contaminated areas and plant growth-promoting (PGP) bacteria (Bacillus XZM) to construct BSCs in different manners. After 45 days of ex-situ culture experiment, Leptolyngbya sp. XZMQ and bacteria could form obvious BSCs. Compared to single-inoculated microalgae, the co-inoculation of Leptolyngbya sp. XZMQ and Bacillus XZM increased soil pH and water content by 10% and 26%, respectively, while decreasing soil EC and density by 19% and 14%, respectively. The soil catalase, alkaline phosphatase, sucrase, and urease activities were also increased by 30.53%, 96.24%, 154.19%, and 272.17%, respectively. The co-inoculation of Leptolyngbya sp. XZMQ and Bacillus XZM drove the formation of BSCs by producing large amounts of extracellular polymeric substances (EPS). The three-dimensional fluorescence spectroscopy (3D-EEM) analysis showed that induced BSCs increased As immobilization by enhancing the contents of tryptophan and tyrosine substances, fulvic acid, and humic acid in EPS. The presence of the -NH2 and -COOH functional groups in tryptophan residues were determined using Fourier Transform Infrared Spectroscopy (FTIR). X-Ray Diffraction (XRD) analysis showed that there were iron (hydrogen) oxides in BSCs, which could form ternary complexes with humic acid and As, thereby increasing the adsorption of As. Therefore, BSCs formed by co-inoculation of Leptolyngbya sp. XZMQ and Bacillus XZM increased the immobilization of As, thereby reducing the content of soluble As in the environment. In summary, our findings innovatively provided a new method for the remediation of As-contaminated soil in mining areas.

Blue Light Enhances Cadmium Tolerance of the Aquatic Macrophyte Potamogeton crispus.

Cadmium (Cd) is highly toxic and widely distributed in aquatic systems due to its high solubility and mobility in water, which can severely inhibit the survival of aquatic macrophytes. The phytotoxicity of Cd depends on environmental factors; however, it remains unclear whether and how light quality affects its toxicity on aquatic macrophytes. In this study, we investigated the effects of Cd on aquatic macrophytes Potamogeton crispus under different light qualities (white, blue, and red light). We evaluated morphological and photo-physiological traits, as well as the cellular antioxidant defense system. Our findings indicate that P. crispus under Cd stress showed notable damage in leaf morphology, decreased photosynthetic efficiency, inhibited HCO3- uptake, and reduced antioxidant enzyme activities, as well as oxidative damage indicated by MDA accumulation and superoxide (O2-) overproduction. However, compared with white or red light under Cd stress, blue light reduced structural damage and oxidative stress caused by Cd while increasing pigment synthesis and photosynthetic efficiency, as well as increasing ascorbate peroxidase (APX) activity. In conclusion, the changes induced by blue light in P. crispus's photosynthesis and antioxidant system strengthen its tolerance to Cd. Further research on signal transmission in relation to light quality in Cd-exposed aquatic plants is still needed.

Phosphate removal mechanism of a novel magnesium slag-modified coal gasification coarse slag adsorbent.

We used magnesium slag (MS) as a calcium source for modifying coal gasification coarse slag (CGCS) in the presence of NaOH to prepare a novel phosphate adsorbent (MS-CGCS). Ca2SiO4 in MS reacts with NaOH during the high-temperature synthesis process, with sodium displacing a part of the calcium content in Ca2SiO4 and entering the mineral lattice to form Na2CaSiO4. Hydroxide ions reacted with calcium in Ca2SiO4 to generate Ca(OH)2 and decomposed into CaO at a high temperature. The two newly formed species participated in the phosphate removal. The MS-CGCS adsorbent showed good phosphate removal performance over a wide pH range, with a maximum phosphate adsorption capacity of 50.14 mg/g, which was significantly higher than that of other reported adsorbents. The Langmuir and pseudo-second-order models described the adsorption process well, indicating it being a monolayer and chemisorption process. The main mechanisms of phosphate removal are as follows: electrostatic interaction between the positively charged MS-CGCS and negatively charged phosphate ions; the inner-sphere complexation of oxides of metal, such as magnesium, aluminum, and calcium, with phosphate ions; and the precipitation of phosphate ions with calcium ions. Precipitation contributes to ~ 32% of the phosphate removal. This study provides a new method for the development of phosphate adsorbents while recycling CGCS and MS.

Application of BCXZM Composite for Arsenic Removal: EPS Production, Biotransformation and Immobilization of Bacillus XZM on Corn Cobs Biochar.

This study determined the effect of Bacillus XZM extracellular polymeric substances (EPS) production on the arsenic adsorption capacity of the Biochar-Bacillus XZM (BCXZM) composite. The Bacillus XZM was immobilized on corn cobs multifunction biochar to generate the BCXZM composite. The arsenic adsorption capacity of BCXZM composite was optimized at different pHs and As(V) concentrations using a central composite design (CCD)22 and maximum adsorption capacity (42.3 mg/g) was attained at pH 6.9 and 48.9 mg/L As(V) dose. The BCXZM composite showed a higher arsenic adsorption than biochar alone, which was further confirmed through scanning electron microscopy (SEM) micrographs, EXD graph and elemental overlay as well. The bacterial EPS production was sensitive to the pH, which caused a major shift in the -NH, -OH, -CH, -C=O, -C-N, -SH, -COO and aromatic/-NO2 peaks of FTIR spectra. Regarding the techno economic analysis, it was revealed that USD 6.24 are required to prepare the BCXZM composite to treat 1000 gallons of drinking water (with 50 µg/L of arsenic). Our findings provide insights (such as adsorbent dose, optimum operating temperature and reaction time, and pollution load) for the potential application of the BCXZM composite as bedding material in fixed-bed bioreactors for the bioremediation of arsenic-contaminated water in future.

Role of Al substitution in the reduction of ferrihydrite by Shewanella oneidensis MR-1.

Substitution of aluminum under natural environmental conditions has been proven to inhibit the transformation of weakly crystalline iron (oxyhydr)-oxides towards well crystalline iron oxides, thereby enhancing their long-term stability. However, exploration on the role of aluminum substitution in bacteria-mediated iron oxides transformation is relatively lacking, especially in the anaerobic underground condition where iron (oxyhydr)-oxides are easy to reduced. In this study, we selected four different levels of substitution aluminum prevalent in iron oxides under natural conditions, which are 0 mol%, 10 mol%, 20 mol%, and 30 mol% (mol Al/mol (Al + Fe)) respectively. With the presence of Shewanella oneidensis MR-1, we conducted a 15-day anaerobic microcosm experiment in simulated groundwater conditions. The experiment data suggested that aluminum substitution result in a decrease in bio-reduction rate constants of ferrihydrite from 0.24 in 0 mol% Al to 0.17 in 30 mol% Al. Besides, when containing substituted aluminum, secondary minerals produced by biological reduction of ferrihydrite changed from magnetite to akaganeite. These results were attributed to the surface coverage of Al during the reduction process, which affects the contact between S. oneidensis MR-1 and the unexposed Fe(III), thus inhibiting the further reduction of ferrihydrite. Since iron (oxyhydr)-oxides exhibit a strong affinity on multiple kinds of pollutants, results in this study may contribute to predicting the migration and preservation of contaminants in groundwater systems.

Thiosulfate driving bio-reduction mechanisms of scorodite in groundwater environment.

Reductive dissolution of scorodite results in the release and migration of arsenic (As) in groundwater. The purpose of this study was to explore the possible abiotic and biotic reduction of scorodite in groundwater environment and the effect of microbial-mediated sulfur cycling on the bio-reduction of scorodite. Microcosm experiments consisting of scorodite with bacterium Citrobacter sp. JH012-1 or free sulfide were carried out to determine the effects of thiosulfate on the mobilization of As/Fe. The results show arsenic release is positively correlated with iron reduction. The arsenate [As(V)] released can agglomerate with Fe(II) on the surface of scorodite to form crystalline parasymplesite, while no parasymplesite was detected in the abiotic reduction of scorodite by sulfide. The reduction of scorodite and As(V) was affected by thiosulfate. When 0.5 mM thiosulfate was added, the Fe(III) reduction rate increased from 32% to 82%, and the As(V) reduction rate rose from 54% to 64%. When the addition of thiosulfate was increased from 0.5 mM to 2 mM and 5 mM, Fe(III) reduction rate added 4% and 8%, and As(V) reduction rate increased 11% and 16%, respectively. In addition, the presence of thiosulfate promoted the scorodite almost completely converting to parasymplesite. Therefore, the effect of microbial-mediated sulfur cycling should be considered in arsenic migration and reduction from scorodite.

Occurrence, distribution, and ecological risk of organophosphorus flame retardants and their degradation products in water and upper sediment of two urban rivers in Shenzhen, China.

Organophosphorus flame retardants (OPFRs) are widely used in various industrial manufacturing processes; thus, their environmental impact in agglomerated industrial areas is of great concern. In this study, seventeen kinds of OPFRs and five kinds of organophosphate diesters (Di-OPs) in water and upper sediment samples from two urban rivers in the agglomerated industrial area of Shenzhen city, China, were investigated. The results showed that the total concentrations of detectable OPFRs ranged from 3438.83 to 12,838.87 ng/L with an average of 6494.94 ng/L in water samples and from 47.16 to 524.46 ng/g (dry weight, dw) with an average of 181.48 ng/g dw in sediment. The values were higher than those in other rivers worldwide. Tris(2-chloroethyl) phosphate (TCEP) is the predominant OPFRs in water and upper sediment, up to 10,664.23 ng/L in water and 414.12 ng/g dw in sediment. The total concentration of OPFRs of sediment samples in the Maozhou River was around twice as high as in the Guanlan River. The results indicated that the level of OPFRs was associated with the industrial activity intensity. Di-OPs exhibited lower concentrations than their parent compounds, and can be attributed to the degradation/metabolism of their parent compounds in the river. The sediment-water partition of OPFRs is significantly correlated with their log Kow values. Risk assessment revealed moderate ecological risks posed by OPFRs in water to aquatic organisms. The present study revealed the pollution status of OPFRs in rivers from agglomerated industrial and residential areas.

Indigenous cyanobacteria enhances remediation of arsenic-contaminated soils by regulating physicochemical properties, microbial community structure and function in soil microenvironment.

Biocrust was widely used for the immobilization and removal of arsenic (As) in drainage systems of rice fields and mining areas. In this study, the role of an indigenous cyanobacteria (Leptolyngbya sp. XZMQ) was explored in the bioremediation of As-contaminated farmland and tailing soil. After 80 d of inoculation with cyanobacteria, total As (As(T)) accumulated in the cyanobacterial crust of farmland and tailing soil was 279.89 mg kg-1 and 269.57 mg kg-1, respectively, and non-EDTA exchangeable fraction was the major fraction of it. The As(T) in farmland and tailing soil of micro-environment decreased by 10.76% and 12.73%, respectively. Meanwhile, the available As (As(a)) decreased by 21.25% and 27.65%, respectively. The XRD results showed that hematite and SiO2 existed in cyanobacterial crust of farmland and tailing soil. FTIR spectra indicated that the adsorption of As in cyanobacterial crust was mediated by OH and CO. After inoculation of Leptolyngbya sp. XZMQ, in subcrust soil, As biotransformation gene aioA was the most abundant, followed by arsM. The dominant phyla of soil biota were Proteobacteria, Cyanobacteria, Actinobacteria, and Bacteroiota, which could play critical roles in shaping aioA and arsM harboring microbe communities in soil. Redundancy analysis (RDA) showed that soil organic carbon (OC), pH, and chlorophyll a (Chl a) were the most important environmental factors in altering soil bacterial communities. Correlation analysis showed the Leptolyngbya had a positive correlation with Chl a, effective nitrogen (N(a)), electrical conductivity (EC), OC, pH in the soil, respectively, while it had a significant negative correlation with As(a), As(III) and As(T). These results emphasized on the significance of cyanobacteria in the behavior of As in mine soils and offered a promising strategy for bioremediation of As-contaminated soil in the mining area.

Coupling and environmental implications of in situ formed biogenic Fe-Mn minerals induced by indigenous bacteria and oxygen perturbations for As(III) immobilization in groundwater.

Iron (Fe)-manganese (Mn) minerals formed in situ can be used for the natural remediation of the primary poor-quality groundwater with coexistence of arsenite [As(III)], Mn(II), and Fe(II) (PGAMF). However, the underlying mechanisms of immobilization and coupling of As, Mn, and Fe during in-situ formation of Fe-Mn minerals in PGAMF remains unclear. The simultaneous immobilization and coupling of arsenic (As), Mn, and Fe in PGAMF during in-situ formation of biogenic Fe-Mn minerals induced by O2 perturbations and indigenous bacteria (Comamonas sp. RM6) were investigated at the different molar ratios of Fe(II):Mn(II) (1:1, 2:1, and 3:1). Compared with systems without Fe(II) in the presence of Mn(II), the coexisted Fe(II) significantly enhanced Mn(II) bio-oxidation and mineral precipitation, resulting in As immobilization increased by 5, 7, and 7 times at initial Fe(II) concentration of 0.3, 0.6, and 0.9 mM, respectively. Moreover, the As(III) immobilization efficiencies in Mn(II) and Fe(II) mixed system at initial Fe(II) concentration of 0.3, 0.6, and 0.9 mM were 73%, 91%, and 92%, respectively, that were significantly higher than those of single Fe(II) system (30%, 59%, and 74%) and those of single Mn(II) system (12%), indicating that Fe(II) and Mn(II) oxidation synergically enhanced As(III) immobilization. This was mainly attributed to the formation and As adsorption capacity of biogenic Fe-Mn minerals (BFMM). The formed BFMM significantly facilitated simultaneous immobilization of Fe, Mn, and As in PGAMF by oxidation, adsorption, and precipitation/coprecipitation, a coupling of biological, physical, and chemical processes. Fe component was mainly responsible for As fixation, and Mn component dominated As(III) oxidation. Based on the results from this work, biostimulation and bioaugmentation techniques can be developed for in-situ purification and remediation of PGAMF. This work provides insights into the simultaneous immobilization of pollutants in PGAMF, as well as promising strategies for in-situ purification and remediation of PGAMF.

Effects of Sulfide Input on Arsenate Bioreduction and Its Reduction Product Formation in Sulfidic Groundwater.

Microbes have important impacts on the mobilization of arsenic in groundwater. To study the effects of sulfide on As(V) bioreduction in sulfidic groundwater, Citrobacter sp. JH012-1 isolated from sediments in the Jianghan Plain was used in a microcosm experiment. The results showed that sulfide significantly enhanced As(V) bioreduction as an additional electron donor. The reduction rates of As(V) were 21.8%, 34.5%, 73.6% and 85.9% under 0, 15, 75 and 150 µM sulfide inputting, respectively. The main products of As(V) bioreduction were thioarsenite and orpiment and the concentration of thioarsenite reached to 5.5 and 7.1 µM in the solution with the initial 75 and 150 µM sulfide, respectively. However, under 0 and 15 µM sulfide inputting, the dominant product was arsenite with no thioarsenite accumulation. The decrease in pH enhanced the bioreduction of As(V) and promoted the formation of thioarsenite and orpiment. In addition, the percentage of thioarsenite in total arsenic decreased with the decrease in the ratio of sulfur to arsenic, indicating that the formation of thioarsenite was limited by the concentration of initial sulfide. Therefore, the presence of sulfide had a significant effect on the transformation of arsenic in groundwater. This study provides new insights into the bioreduction of As(V) and the formation of thioarsenite in sulfidic groundwater.

Study on adsorption of phosphate from aqueous solution by zirconium modified coal gasification coarse slag.

Zr-modified materials have an adsorption affinity for phosphate ions, but because of the cost of carrier materials, they are difficult to apply on a large scale. Herein, coal gasification coarse slag (CGCS) was used as a carrier material and modified with Zr, and its dephosphorization performance was studied. A series of adsorbents with different CGCS/ZrOCl2·8H2O mass ratios were prepared, from which the adsorbent with a CGCS/ZrOCl2·8H2O mass ratio of 5 : 4 (denoted as CGCS-Zr4) was identified as the most promising for phosphate adsorption. The specific surface area of CGCS-Zr4 was much greater than that of raw CGCS (100.12 vs. 12.43 m2 g-1). CGCS-Zr4 showed good adsorption selectivity towards phosphate when competitive anions co-existed, and exhibited good reusability; the adsorption capacity in the fourth adsorption-desorption cycle remained above 11.98 mg g-1. The adsorbent was also suitable for the continuous treatment of up to 830 and 743 bed volumes of synthesised and actual wastewater, respectively. The results of Fourier-transform infrared and X-ray photoelectron spectroscopy indicated that CGCS not only plays the role of a carrier, but also that Ca and Al in CGCS play an important role in phosphate adsorption. Compared with other carrier materials such as biochar and synthetic zeolite, CGCS has the advantages of a large stockpile, low cost, and easy availability. In addition, the preparation of CGCS-Zr4 is simpler and more energy-saving. Zr-modified CGCS is a promising dephosphorization material.

Effects of Calcium on Arsenate Adsorption and Arsenate/Iron Bioreduction of Ferrihydrite in Stimulated Groundwater.

The reduction and transformation of arsenic-bearing ferrihydrite by arsenate-iron reducing bacteria is one of the main sources of arsenic enrichment in groundwater. During this process the coexistence cations may have a considerable effect. However, the ionic radius of calcium is larger than that of iron and shows a low affinity for ferrihydrite, and the effect of coexisting calcium on the migration and release of arsenic in arsenic-bearing ferrihydrite remains unclear. This study mainly explored the influence of adsorbed Ca2+ on strain JH012-1-mediated migration and release of arsenate in a simulated groundwater environment, in which 3 mM ferrihydrite and pH 7.5. Ca2+ were pre-absorbed on As(V)-containing ferrihydrite with a As:Fe ratio of 0.2. Solid samples were analyzed by X-ray diffraction (XRD), scanning electron microscopic (SEM), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The results show that calcium and arsenate can synergistically adsorb on ferrihydrite due to the electrostatic interactions, and the adsorbed Ca2+ mainly exists on the surface through the outer-sphere complex. Adsorbed Ca2+ entering the stimulated groundwater was easily disturbed and led to an extra release of 3.5 mg/L arsenic in the early stage. Moreover, adsorbed Ca2+ inhibited biogenic ferrous ions from accumulating on ferrihydrite. As a result, only 12.30% Fe(II) existed in the solid phase, whereas 29.35% existed without Ca2+ adsorption. Thus, the generation of parasymplesite was inhibited, which is not conducive to the immobilization of arsenic in groundwater.

Human Exposure to Chlorinated Organophosphate Ester Flame Retardants and Plasticizers in an Industrial Area of Shenzhen, China.

Human exposure to organophosphate esters (OPEs) is more pervasive in industrial areas manufacturing OPE-related products. OPE exposure is of great concern due to its associations with adverse health effects, while studies on OPE exposure in industrial districts are scarce. This study aimed to assess human exposure to OPEs in a typical industrial area producing large amounts of OPE-related products in Shenzhen, China. Tris (2-chloroethyl)-phosphate (TCEP), tris (2-chloroisopropyl) phosphate (TCPP) and other common OPEs were analyzed in urine (n = 30) and plasma (n = 21) samples. Moreover, we measured five OPE metabolites (mOPEs) in plasma samples (n = 21). The results show that TCPP and TCEP are dominant compounds, with moderate to high levels compared with those reported in urine and plasma samples from other regions. In addition, di-n-butyl phosphate (DnBP) and diethyl phosphite (DEP) were frequently detected in plasma samples and could be considered as biomarkers. Risk assessment revealed a moderate to high potential health risk from TCEP exposure. Our results provide basic data for human exposure to OPEs in industrial areas and call for the prevention and mitigation of industrial chlorinated OPE pollution.