Sources and transformations of riverine nitrogen across a coastal-plain river network of eastern China: New insights from multiple stable isotopes.

Riverine nitrogen pollution is ubiquitous and attracts considerable global attention. Nitrate is commonly the dominant total nitrogen (TN) constituent in surface and ground waters; thus, stable isotopes of nitrate (δ15N/δ18O-NO3-) are widely used to differentiate nitrate sources. However, δ15N/δ18O-NO3- approach fails to present a holistic perspective of nitrogen pollution for many coastal-plain river networks because diverse nitrogen species contribute to high TN loads. In this study, multiple isotopes, namely, δ15N/δ18O-NO3-, δ18O-H2O, δ15N-NH4+, δ15N-PN, and δ15Nbulk/δ18O/SP-N2O in the Wen-Rui Tang River, a typical coastal-plain river network of Eastern China, were investigated to identify transformation processes and sources of nitrogen. Then, a stable isotope analysis in R (SIAR) model-TN source apportionment method was developed to quantify the contributions of different nitrogen sources to riverine TN loads. Results showed that nitrogen pollution in the river network was serious with TN concentrations ranging from 1.71 to 8.09 mg/L (mean ± SD: 3.77 ± 1.39 mg/L). Ammonium, nitrate, and suspended particulate nitrogen were the most prominent nitrogen components during the study period, constituting 45.4 %, 28.9 %, and 19.9 % of TN, respectively. Multiple hydrochemical and isotopic analysis identified nitrification as the dominant N cycling process. Biological assimilation and denitrification were minor N cycling processes, whereas ammonia volatilization was deemed negligible. Isotopic evidence and SIAR modeling revealed municipal sewage was the dominant contributor to nitrogen pollution. Based on quantitative estimates from the SIAR model, nitrogen source contributions to the Wen-Rui Tang River watershed followed: municipal sewage (40.6 %) ≈ soil nitrogen (39.5 %) > nitrogen fertilizer (9.7 %) > atmospheric deposition (2.8 %) during wet season; and municipal sewage (59.1 %) > soil nitrogen (30.4 %) > nitrogen fertilizer (4.1 %) > atmospheric deposition (1.0 %) during dry season. This study provides a deeper understanding of nitrogen dynamics in eutrophic coastal-plain river networks, which informs strategies for efficient control and remediation of riverine nitrogen pollution.

Riverine nitrate source identification combining δ15N/δ18O-NO3- with Δ17O-NO3- and a nitrification 15N-enrichment factor in a drinking water source region.

Dual nitrate isotopes (δ15N/δ18O-NO3-) are an effective tool for tracing nitrate sources in freshwater systems worldwide. However, the initial δ15N/δ18O values of different nitrate sources might be altered by isotopic fractionation during nitrification, thereby limiting the efficiency of source apportionment results. This study integrated hydrochemical parameters, site-specific isotopic compositions of potential nitrate sources, multiple stable isotopes (δD/δ18O-H2O, δ15N/δ18O-NO3- and Δ17O-NO3-), soil incubation experiments assessing the nitrification 15N-enrichment factor (εN), and a Bayesian mixing model (MixSIAR) to reduce/eliminate the influence of 15N/18O-fractionations on nitrate source apportionment. Surface water samples from a typical drinking water source region were collected quarterly (June 2021 to March 2022). Nitrate concentrations ranged from 0.35 to 3.06 mg/L (mean = 0.78 ± 0.46 mg/L), constituting ∼70 % of total nitrogen. A MixSIAR model was developed based on δ15N/δ18O-NO3- values of surface waters and the incorporation of a nitrification εN (-6.9 ± 1.8 ‰). Model source apportionment followed: manure/sewage (46.2 ± 10.7 %) > soil organic nitrogen (32.3 ± 18.5 %) > nitrogen fertilizer (19.7 ± 13.1 %) > atmospheric deposition (1.8 ± 1.6 %). An additional MixSIAR model coupling δ15N/δ18O-NO3- with Δ17O-NO3- and εN was constructed to estimate the potential nitrate source contributions for the June 2021 water samples. Results revealed similar nitrate source contributions (manure/sewage = 43.4 ± 14.1 %, soil organic nitrogen = 29.3 ± 19.4 %, nitrogen fertilizer = 19.8 ± 13.8 %, atmospheric deposition = 7.5 ± 1.6 %) to the original MixSIAR model based on εN and δ15N/δ18O-NO3-. Finally, an uncertainty analysis indicated the MixSIAR model coupling δ15N/δ18O-NO3- with Δ17O-NO3- and εN performed better as it generated lower uncertainties with uncertainty index (UI90) of 0.435 compared with the MixSIAR model based on δ15N/δ18O-NO3- (UI90 = 0.522) and the MixSIAR model based on δ15N/δ18O-NO3- and εN (UI90 = 0.442).

Micro- and nano-plastics in the atmosphere: A review of occurrence, properties and human health risks.

The ubiquitous occurrence of micro/nano plastics (MNPs) poses potential threats to ecosystem and human health that have attracted broad concerns in recent decades. Detection of MNPs in several remote regions has implicated atmospheric transport as an important pathway for global dissemination of MNPs and hence as a global health risk. In this review, the latest research progress on (1) sampling and detection; (2) origin and characteristics; and (3) transport and fate of atmospheric MNPs was summarized. Further, the current status of exposure risks and toxicological effects from inhaled atmospheric MNPs on human health is examined. Due to limitations in sampling and identification methodologies, the study of atmospheric nanoplastics is very limited today. The large spatial variation of atmospheric MNP concentrations reported worldwide makes it difficult to compare the overall indoor and outdoor exposure risks. Several in vitro, in vivo, and epidemiological studies demonstrate adverse effects of immune response, apoptosis and oxidative stress caused by MNP inhalation that may induce cardiovascular diseases and reproductive and developmental abnormalities. Given the emerging importance of atmospheric MNPs, the establishment of standardized sampling-pretreatment-detection protocols and comprehensive toxicological studies are critical to advance environmental and health risk assessments of atmospheric MNPs.

Airborne microplastics in urban, rural and wildland environments on the Tibetan Plateau.

The concentration of airborne microplastics is largely unknown in the remote high mountain area of the Tibetan Plateau. Here we report airborne microplastic concentrations of 2.5-58.8 n/m3 in urban, rural and wildland areas across the Tibetan Plateau, with smaller (∼89% <100 µm) fragments (>80%) dominating. Polyethylene terephthalate, polyethylene, polyamide and polystyrene were the dominant polymers of airborne microplastics on the Tibetan Plateau. Distribution of airborne microplastics was positively correlated with anthropogenic activity indices, such as population density and nighttime light intensity. Although the contribution of long-range atmospheric transport is valid, dispersed villages also appear to be a source of airborne microplastics for wildland areas across the Tibetan Plateau.

Rapid determination of triglyceride and glucose levels in Drosophila melanogaster induced by high-sugar or high-fat diets based on near-infrared spectroscopy.

Triglyceride and glucose levels are important indicators for determining metabolic syndrome, one of the leading public-health burdens worldwide. Drosophila melanogaster is an ideal model for investigating metabolic diseases because it has 70% homology to human genes and its regulatory mechanism of energy metabolism homeostasis is highly similar to that of mammals. However, traditional analytical methods of triglyceride and glucose are time-consuming, laborious, and costly. In this study, a simple, practical, and reliable near-infrared (NIR) spectroscopic analysis method was developed for the rapid determination of glucose and triglyceride levels in an in vivo model of metabolic disorders using Drosophila induced by high-sugar or high-fat diets. The partial least squares (PLS) model was constructed and optimized using different spectral regions and spectral pretreatment methods. The overall results had satisfactory prediction performance. For Drosophila induced by high-sugar diets, the correlation coefficient (RP) and root mean square error of prediction (RMSEP) were 0.919 and 0.228 mmoL gprot-1 for triglyceride and 0.913 and 0.143 mmoL gprot-1 for glucose respectively; for Drosophila induced by high-fat diets, the RP and RMSEP were 0.871 and 0.097 mmoL gprot-1 for triglyceride and 0.853 and 0.154 mmoL gprot-1 for glucose, respectively. This study demonstrated the potential of using NIR spectroscopy combined with PLS in the determination of triglyceride and glucose levels in Drosophila, providing a rapid and effective method for monitoring metabolite levels during disease development and a possibility for evaluating metabolic diseases in humans in clinical practice.

Microplastic pollution characteristics and its future perspectives in the Tibetan Plateau.

Microplastics are an emerging and persistent pollutant due to their threat to global ecological systems and human health. Recent studies showed that microplastics have infiltrated the remote Third Pole - the Tibetan Plateau. Here, we summarize the current evidence for microplastic pollution in the different environments (rivers/lakes, sediment, soil, ice/snow and atmosphere) of the Tibetan Plateau. We assess the spatial distribution, source, fate, and potential ecological effects of microplastics in this broad plateau. The integrated results show that microplastics were pervasive in biotic and abiotic components of the Tibetan Plateau, even at the global highest-altitude, Mt. Everest. Although the concentration of microplastics in the Tibetan Plateau was far below that found in the densely populated lowlands, it showed a higher concentration than that in the ocean system. Tourist populations are identified as a substantial source of anthropogenic plastic input rather than local residents due to the rapid development of the tourism industry. In the sparsely inhabited remote area of the Tibetan Plateau, long-range atmospheric transport facilitates allochthonous microplastic diffusion. Robust solar radiation in the Tibetan Plateau might enhanced production of secondary microplastics by weathering (UV-photooxidation) of abandoned plastic waste. A rough estimation showed that the microplastic export flux from melting glaciers was higher than that measured in most of the world's largest rivers, which affects local and downstream areas. Since the Tibetan Plateau is vital for Asian water supply and numerous endangered wildlife, the potential human and ecological risk of microplastics to these fragile ecosystems needs to be fully evaluated within the context of climate-change impacts.

Toward Enhanced Aerosol Particle Adsorption in Never-Bursting Bubble via Acoustic Levitation and Controlled Liquid Compensation.

Bubbles in air are ephemeral because of gravity-induced drainage and liquid evaporation, which severely limits their applications, especially as intriguing bio/chemical reactors. In this work, a new approach using acoustic levitation combined with controlled liquid compensation to stabilize bubbles is proposed. Due to the suppression of drainage by sound field and prevention of capillary waves by liquid compensation, the bubbles can remain stable and intact permanently. It has been found that the acoustically levitated bubble shows a significantly enhanced particle adsorption ability because of the oscillation of the bubble and the presence of internal acoustic streaming. The results shed light on the development of novel air-purification techniques without consuming any solid filters.

Expedient Synthesis of Dihaloalkenynes via Pd-Catalyzed Haloalkynylation Reaction.

Herein, the PdII -catalyzed construction of functionalized dihaloalkenynes from haloalkynes via a self-haloalkynylation reaction, without specialized ligands or oxidizing additives, is reported. The method tolerates a diverse range of haloalkynes, including electron-donating and electron-withdrawing functional groups, such as macrocyclic alkynols, spiro-oxy ring alkynols, and even carbazole-containing, pyrrolidine-2,5-dione-containing and silyl-protected bromoalkynes. Using an opposite lithium halide (LiX) to the haloalkyne starting material, remarkably high regio- and stereoselectivity of the haloalkynylation reaction is possible, yielding 1-bromo-2-chloroalkenyne or 2-bromo-1-chloroalkenyne products as desired.

Continuous air purification by aqueous interface filtration and absorption.

The adverse impact of particulate air pollution on human health1,2 has prompted the development of purification systems that filter particulates out of air3-5. To maintain performance, the filter units must inevitably be replaced at some point, which requires maintenance, involves costs and generates solid waste6,7. Here we show that an ion-doped conjugated polymer-coated matrix infiltrated with a selected functional liquid enables efficient, continuous and maintenance-free air purification. As the air to be purified moves through the system in the form of bubbles, the functional fluid provides interfaces for filtration and for removal of particulate matter and pollutant molecules from air. Theoretical modelling and experimental results demonstrate that the system exhibits high efficiency and robustness: its one-time air purification efficiency can reach 99.6%, and its dust-holding capacity can reach 950 g m-2. The system is durable and resistant to fouling and corrosion, and the liquid acting as filter can be reused and adjusted to also enable removal of bacteria or odours. We anticipate that our purification approach will be useful for the development of specialist air purifiers that might prove useful in a settings such as hospitals, factories and mines.

Nitrate pollution source apportionment, uncertainty and sensitivity analysis across a rural-urban river network based on δ15N/δ18O-NO3- isotopes and SIAR modeling.

Nitrate pollution is of considerable global concern as a threat to human health and aquatic ecosystems. Nowadays, δ15N/δ18O-NO3- combined with a Bayesian-based SIAR model are widely used to identify riverine nitrate sources. However, little is known regarding the effect of variations in pollution source isotopic composition on nitrate source contributions. Herein, we used δ15N/δ18O-NO3-, SIAR modeling, probability statistical analysis and a perturbing method to quantify the contributions and uncertainties of riverine nitrate sources in the Wen-Rui Tang River of China and to further investigate the model sensitivity of each nitrate source. The SIAR model confirmed municipal sewage (MS) as the major nitrate source (58.5-75.7%). Nitrogen fertilizer (NF, 8.6-20.9%) and soil nitrogen (SN, 7.8-20.1%) were also identified as secondary nitrate sources, while atmospheric deposition (AD, <0.1-7.9%) was a minor source. Uncertainties associated with NF (UI90 = 0.32) and SN (UI90 = 0.30) were high, whereas those associated with MS (UI90 = 0.14) were moderate and AD low (UI90 = 0.0087). A sensitivity analysis was performed for the SIAR modeling and indicated that the isotopic composition of the predominant source (i.e., MS in this study) had the strongest effect on the overall riverine nitrate source apportionment results.

Integrated effects of polymer type, size and shape on the sinking dynamics of biofouled microplastics.

Sinking of microplastics (MPs) after biofouling is considered an important mechanisms responsible for the downward transport/sedimentation of MPs in the ocean and freshwaters. Previous studies demonstrated MP sinking caused by an increase in the composite density of MPs after biofouling, while MPs with smaller size or shapes with higher surface area to volume ratios (SA:V), such as films, are speculated to sink faster. In this study, we designed an in situ microcosm to simulate the ambient environmental conditions experienced by floating MPs to elucidate the biofouling and sinking of polyethylene (PE), polypropylene (PP), and expanded-polystyrene (EPS) MPs of various sizes and shapes. Our results showed smaller PE and PP MP granules sank faster than large ones. Even EPS granules of 100 µm diameter, having a much lower density (0.02 mg/mm3) than water, started to sink after 2 weeks of biofouling. Moreover, PE film and fiber MPs with higher SA:V did not sink faster than PE MP granules of the same mass, implying that mechanisms other than SA:V, such as fouling contact area and drag coefficient, play a role in the regulation of biofouling and sinking of MPs.

Palladium-Catalyzed Cross Haloalkynylation of Haloalkynes.

Herein, we have developed a robust Pd-catalyzed haloalkynylation of haloalkynes for the synthesis of dihaloalkenyne derivatives. This cross-haloalkynylation reaction proceeds in a highly chemo- and regioselective manner under mild conditions in the presence of two slightly structurally different haloalkynes and shows strong functional group tolerance under ligand- and base-free conditions.

Comprehensive evaluation of Dendrobium officinale from different geographical origins using near-infrared spectroscopy and chemometrics.

Dendrobium officinale, often used as a kind of tea for daily drinks, has drawn increasing attention for its beneficial effects. Quality evaluation of D. officinale is of great significance to ensure its health care value and safeguard consumers' interest. Given that traditional analytical methods for assessing D. officinale quality are generally time-consuming and laborious, this study developed a comprehensive strategy, with the advantages of being rapid and efficient, enabling the quality evaluation of D. officinale from different geographical origins using near-infrared (NIR) spectroscopy and chemometrics. As the quality indicators, polysaccharides, polyphenols, total flavonoids, and total alkaloids were quantified. Three types of wavelength selection methods were used for model optimization and these were synergy interval (SI), genetic algorithm (GA), and competitive adaptive reweighted sampling (CARS). From the qualitative perspective, the geographical origins of D. officinale were differentiated by NIR spectroscopy combined with partial least squares-discriminant analysis (PLS-DA) and support vector classification (SVC). The PLS models constructed based on the wavelengths selected by CARS yielded the best performance for prediction of the contents of quality indicators in D. officinale. The root mean square error (RMSEP) and coefficient of determination (Rp2) in the independent test sets were 12.7768 g kg-1 and 0.9586, 1.1346 g kg-1 and 0.9670, 0.3938 g kg-1 and 0.8803, 0.0825 and 0.7031 and for polysaccharides, polyphenols, total flavonoids, and total alkaloids, respectively. As for the origin identification, the nonlinear SVC was superior to the linear PLS-DA, with the correct recognition rates in calibration and prediction sets up to 100% and 100%, respectively. The overall results demonstrated the potential of NIR spectroscopy and chemometrics in the rapid determination of quality parameters and geographical origin. This study could provide a valuable reference for quality evaluation of D. officinale in a more rapid and comprehensive manner.

Microplastic ingestion from atmospheric deposition during dining/drinking activities.

Human-health risks from microplastics have attracted considerable attention, but little is known about human-exposure pathways and intensities. Recent studies posited that inhalation of atmospheric microplastics was the dominant human-exposure pathway. Herein, our study identified that atmospheric microplastics ingested from deposition during routine dining/drinking activities represent another important exposure pathway. We measured abundances of atmospheric-deposited microplastics of up to 105 items m-2 d-1 in dining/drinking venues, with 90% smaller than 100 µm and a dominance of amorphous fragments rather than fibers. Typical work-life scenarios projected an annual ingestion of 1.9 × 105 to 1.3 × 106 microplastics through atmospheric deposition on diet, with higher exposure rates for indoor versus outdoor dining/drinking settings. Ingestion of atmospheric-deposited microplastics through diet was similar in magnitude to presumed inhalation exposure, but 2-3 orders of magnitude greater than direct ingestion from food sources. Simple mitigation strategies (e.g., covering and rinsing dishware) can substantially reduce the exposure of atmospheric deposition microplastics through diet.

Modular configurations of living biomaterials incorporating nano-based artificial mediators and synthetic biology to improve bioelectrocatalytic performance: A review.

Currently, the industrial application of bioelectrochemical systems (BESs) that are incubated with natural electrochemically active microbes (EABs) is limited due to inefficient extracellular electron transfer (EET) by natural EABs. Notably, recent studies have identified several novel living biomaterials comprising highly efficient electron transfer systems allowing unparalleled proficiency of energy conversion. Introduction of these biomaterials into BESs could fundamentally increase their utilization for a wide range of applications. This review provides a comprehensive assessment of recent advancements in the design of living biomaterials that can be exploited to enhance bioelectrocatalytic performance. Further, modular configurations of abiotic and biotic components promise a powerful enhancement through integration of nano-based artificial mediators and synthetic biology. Herein, recent advancements in BESs are synthesized and assessed, including heterojunctions between conductive nanomaterials and EABs, in-situ hybrid self-assembly of EABs and nano-sized semiconductors, cytoprotection in biohybrids, synthetic biological modifications of EABs and electroactive biofilms. Since living biomaterials comprise a broad range of disciplines, such as molecular biology, electrochemistry and material sciences, full integration of technological advances applied in an interdisciplinary framework will greatly enhance/advance the utility and novelty of BESs. Overall, emerging fundamental knowledge concerning living biomaterials provides a powerful opportunity to markedly boost EET efficiency and facilitate the industrial application of BESs to meet global sustainability challenges/goals.

Synthesis of Substituted Thiophenes through Dehydration and Heterocyclization of Alkynols.

A protocol was described for obtaining a variety of substituted thiophenes with functional potential via metal-free dehydration and sulfur cyclization of alkynols with elemental sulfur (S8) or EtOCS2K in moderate-to-good yields. The method provides the base-free generation of a trisulfur radical anion (S3•-) and its addition to alkynes as an initiator. This research broadens the applications of S3•- in the synthesis of sulfur-containing heterocycles.

Synthesis of Deuterated (E)-Alkene through Xanthate-Mediated Hydrogen-Deuterium Exchange Reactions.

Herein we have developed a reversible hydrogen-deuterium exchange reaction of nonactivated olefins. By using EtOCS2K as a mediator, the H/D exchange reaction was realized through repeated addition and elimination reactions, demonstrating reversible H/D exchange between ordinary olefins and deuterated olefins. Using the lowest cost D2O without precious metal catalysts and ligands, a broad spectrum of compatibility of functional groups was achieved.

Airborne microplastics in indoor and outdoor environments of a coastal city in Eastern China.

Microplastics (MPs) in marine and terrestrial environments have been intensively studied, but the dynamics of airborne MPs remains limited. Existing studies on atmospheric MPs are mostly derived from collection of atmospheric deposition, whereas direct measurements of airborne MPs are scarce. However, the abundance of airborne MPs is more relevant for evaluating human inhalation exposure risk. Herein, airborne MPs in indoor and outdoor environments from urban and rural areas of a coastal city in eastern China were investigated. MP concentrations (mean±SD) in indoor air (1583 ± 1180 n/m3) were an order of magnitude higher than outdoor air (189 ± 85 n/m3), and airborne MP concentrations in urban areas (224 ± 70 n/m3) were higher than rural areas (101 ± 47 n/m3). MPs smaller than 100 µm dominated airborne MPs, and the predominant shape of airborne MPs was fragments, as opposed to fibers. The larger MP size fractions contained a higher proportion of fibers, whereas the smaller size fractions were nearly exclusively composed of fragments. The health risk caused by ubiquitous airborne MPs should not be discounted as the maximum annual outdoor exposure of airborne MPs can reach 1 million/year, while indoor exposure may be even higher due to higher indoor airborne MP concentrations.

A support vector regression model to predict nitrate-nitrogen isotopic composition using hydro-chemical variables.

Nitrate is a prominent pollutant in surface and groundwater bodies worldwide. Isotopes in nitrate provide a powerful approach for tracing nitrate sources and transformations in waters. Given that analytical techniques for determining isotopic compositions are generally time-consuming, laborious and expensive, alternative methods are warranted to supplement and enhance existing approaches. Hence, we developed a support vector regression (SVR) model and explored its feasibility to predict nitrogen isotopic composition of nitrate (δ15N-NO3-) in a rural-urban river system in Southeastern China. A total of 16 easily obtained hydro-chemical variables were measured in the wet season (September 2019) and dry season (January 2020) and used to develop the SVR prediction model. The grading method utilized ~75% (35) of the samples for model building while the remaining 11 samples assessed model performance. Principal component analysis (PCA) extracted 7 principal components for SVR model inputs as PCA reduces superfluous variables. We optimized tuning parameters in the SVR model using a grid search technique coupled with V-fold cross-validation. The optimized SVR model provided accurate δ15N-NO3- predictions with a determination coefficient (R2) of 0.88, Nash-Sutcliffe (NS) of 0.87, and mean square error (MSE) of 0.53‰ in the testing step, and performed much better than the corresponding multivariate linear regression model (R2 = 0.60, NS = 0.58 and MSE = 1.76‰) and general regression neural network model (R2 = 0.66, NS = 0.65 and MSE = 1.45‰). Overall, the SVR model provides a potential indirect method to predict environmental isotope values for water quality management that will complement and enhance the interpretation of direct measurements of δ15N-NO3-.

Role of MnO2 in controlling iron and arsenic mobilization from illuminated flooded arsenic-enriched soils.

This study examined the role of intermittent illumination/dark conditions coupled with MnO2-ammendments to regulate the mobility of As and Fe in flooded arsenic-enriched soils. Addition of MnO2 particles with intermittent illumination led to a pronounced increase in the reductive-dissolution of Fe(III) and As(V) from flooded soils compared to a corresponding dark treatments. A higher MnO2 dosage (0.10 vs 0.02 g) demonstrated a greater effect. Over a 49-day incubation, maximum Fe concentrations mobilized from the flooded soils amended with 0.10 and 0.02 g MnO2 particles were 2.39 and 1.85-fold higher than for non-amended soils under dark conditions. The corresponding maximum amounts of mobilized As were at least 92 % and 65 % higher than for non-amended soils under dark conditions, respectively. Scavenging of excited holes by soil humic/fulvic compounds increased mineral photoelectron production and boosted Fe(III)/As(V) reduction in MnO2-amended, illuminated soils. Additionally, MnO2 amendments shifted soil microbial community structure by enriching metal-reducing bacteria (e.g., Anaeromyxobacter, Bacillus and Geobacter) and increasing c-type cytochrome production. This microbial diversity response to MnO2 amendment facilitated direct contact extracellular electron transfer processes, which further enhanced Fe/As reduction. Subsequently, the mobility of released Fe(II) and As(III) was partially attenuated by adsorption, oxidation, complexation and/or coprecipitation on active sites generated on MnO2 surfaces during MnO2 dissolution. These results illustrated the impact of a semiconducting MnO2 mineral in regulating the biogeochemical cycles of As/Fe in soil and demonstrated the potential for MnO2-based bioremediation strategies for arsenic-polluted soils.