Climate and soil properties regulate the vertical heterogeneity of minor and trace elements in the alpine topsoil of the Hengduan Mountains.

Soil minor and trace elements are vital regulators of ecological processes that sustain alpine ecosystem functions. In this study, the vertical pattern and driving factors of element concentrations in alpine soils of the Tibetan Plateau were investigated. Three snow mountains (Meili, Baima, and Haba) part of the Hengduan Mountain range, were selected as the study area to determine the vertical distribution of 12 typical elements (Cr, Ni, Cu, Fe, Mn, Zn, Cd, Pb, Ca, Sr, As, and Se) in topsoil with increasing and decreasing elevation, as well as the dominant driving factors of their spatial heterogeneity. Results showed that all elements, except Se, showed strong vertical heterogeneity, among which Cr, Ni, Cu, and Fe showed peak concentrations at 2700-3000 m; the highest concentrations of Mn and Zn were at 3200 m and 2700 m, with Cd and Pb at 2500 m. Ca and Sr levels gradually decreased with increasing elevation. According to the structural equation model and random forest analysis, the vertical heterogeneity of soil elements is directly regulated by the variability of climate and soil properties due to changes in elevation. A three-way PERMANOVA further quantized the contributions of climate and soil properties on vertical heterogeneity of all soil elements, which were 35.2 % and 50.5 %, respectively. This study used various statistical tools to reveal the dominant factors affecting the vertical heterogeneity of soil elements. These findings provided a scientific overview of element distribution on the Tibetan Plateau and significant references for the vertical distribution of elements in the topsoil of other snow mountains worldwide.

VFG-Chip: A high-throughput qPCR microarray for profiling virulence factor genes from the environment.

As zoonotic pathogens are threatening public health globally, the virulence factor genes (VFGs) they carry underlie latent risk in the environment. However, profiling VFGs in the environment is still in its infancy due to lack of efficient and reliable quantification tools. Here, we developed a novel high-throughput qPCR (HT-qPCR) chip, termed as VFG-Chip, to comprehensively quantify the abundances of targeted VFGs in the environment. A total of 96 VFGs from four bacterial pathogens including Klebsiella pneumoniae, Acinetobacter baumannii, Escherichia coli, and Salmonella enterica were targeted by 120 primer pairs, which were involved in encoding five types of virulence factors (VFs) like toxin, adherence, secretion system, immune evasion/invasion, and iron uptake. The specificity of VFG-Chip was both verified computationally and experimentally, with high identity of amplicon sequencing and melting curves analysis proving its robust capability. The VFG-Chip also displayed high sensitivity (by plasmid serial dilution test) and amplification efficiency averaging 97.7%. We successfully applied the VFG-Chip to profile the distribution of VFGs along a wastewater treatment system with 69 VFGs detected in total. Overall, the VFG-Chip provides a robust tool for comprehensively quantifying VFGs in the environment, and thus provides novel information in assessing the health risks of zoonotic pathogens in the environment.

Dispersal limitation and host selection drive geo-specific and plant-specific differentiation of soil bacterial communities in the Tibetan alpine ecosystem.

Soil bacteria, which are active in shrub encroachment, play key roles in regulating ecosystem structure and function. However, the differentiation characteristics and assembly process of bacterial communities in scrubbed grasslands remain unknown. Taking the Qinghai-Tibet Plateau, a hotspot of shrub encroachment, as the study area, we collected 192 soils near nine natural typical shrubs' roots on a trans-longitude transect (about 1800 km) and investigated the bacterial communities using 16S rRNA amplicon sequencing. We found that the bacterial communities exhibited plant-specific and geographic-specific differentiation. On the one hand, bacterial communities differed significantly across plant species, with widely distributed shrubs harboring high diversity communities but few plant-specific taxa, and narrowly distributed shrubs possessing low diversity communities but more plant-specific taxa. Besides, there was a significant negative correlation between bacterial community similarity and plant phylogenetic distance. On the other hand, bacterial communities differed across geographic sites, with a significant decay in bacterial community similarity with geographic distance. The bacterial alpha diversity varied in an inverted V-shape from west to east, peaking at 91°E, which could be largely driven by mean annual temperature, soil pH and soil total carbon content. Community differentiation increased with the heterogeneity degree of assembly processes, and the dominant assembly process in these two specific differentiations differed. Dominated by stochastic and deterministic forces, respectively, geography diverged bacterial communities primarily through increased dispersal limitation, whereas plants diverged bacterial communities primarily through increased variable selection. Our study provides new insight into the characteristics and mechanisms of root-surrounding soil bacteria differentiation in scrubbed grasslands, contributing to the scientific management of degraded grasslands and the prediction of bacterial community structure and ecosystem function in response to global change.

Optimal soil Eh, pH for simultaneous decrease of bioavailable Cd, As in co-contaminated paddy soil under water management strategies.

The co-contamination with cadmium (Cd) and arsenic (As) in the paddy soil is the most seriously combined pollution of toxic elements in China, and it is rather difficult to decrease bioavailable Cd and As levels in soil because of the opposite ionic forms of bioavailable Cd (cation) and As (anion). This study explored the optimal conditions of Eh and pH in different soils for simultaneous decrease of Cd and As bioavailabilities in the soil-rice system through soil culture and rice pot experiments under water management strategies. The results showed that near neutral soil pH (7.0) were eventually observed under long-term flooding conditions. Under unflooded conditions, soil pH is the dominant factor influencing bioavailabilities of Cd and As, while under flooded conditions, Eh becomes the most important factor. Pot experiments showed that flooding significantly reduced the Cd concentration in rice grains from 54.5% to 95.5%, but concomitantly increased rice As concentration substantially (214%-302%). By evaluating the trade-off value between the bioavailabilities of Cd and As in the soil, the minimal trade-off value was obtained when the soil Eh was -130 mV and the pH was 6.8.

The removal of arsenic from solution through biochar-enhanced precipitation of calcium-arsenic derivatives.

Arsenic (As) pollution remains a major threat to the quality of global soils and drinking water. The health effects of As pollution are often severe and have been largely reported across Asia and South America. This study investigated the possibility of using unmodified biochar derived from rice husk (RB) and aspen wood (WB) at 400 °C and 700 °C to enhance the precipitation of calcium/arsenic compounds for the removal of As(III) from solution. The approach was based on utilizing calcium to precipitate arsenic in solution and adding unmodified biochar to enhance the process. Using this approach, As(III) concentration in aqueous solution decreased by 58.1% when biochar was added, compared to 25.4% in the absence of biochar. Varying the pH from acidic to alkaline enabled an investigation into the pH dependent dynamics of the approach. Results indicated that significant precipitation was only possible at near neutral pH (i.e. pH = 6.5) where calcium arsenites (i.e. Ca(AsO2)2, and CaAsO2OH•½H2O) and arsenates (i.e. Ca5(AsO4)3OH) were precipitated and deposited as aggregates in the pores of biochars. Arsenite was only slightly precipitated under acidic conditions (pH = 4.5) while no arsenite was precipitated under alkaline conditions (pH = 9.5). Arsenite desorption from wood biochar was lowest at pH 6.5 indicating that wood biochar was able to retain a large quantity of the precipitates formed at pH 6.5 compared to pH 4.5 and pH 9.5. Given that the removal of As(III) from solution is often challenging and that biochar modification invites additional cost, the study demonstrated that low cost unmodified biochar can be effective in enhancing the removal of As(III) from the environment through Ca-As precipitation.

High Arsenic Levels Increase Activity Rather than Diversity or Abundance of Arsenic Metabolism Genes in Paddy Soils.

Arsenic (As) metabolism genes are generally present in soils, but their diversity, relative abundance, and transcriptional activity in response to different As concentrations remain unclear, limiting our understanding of the microbial activities that control the fate of an important environmental pollutant. To address this issue, we applied metagenomics and metatranscriptomics to paddy soils showing a gradient of As concentrations to investigate As resistance genes (ars) including arsR, acr3, arsB, arsC, arsM, arsI, arsP, and arsH as well as energy-generating As respiratory oxidation (aioA) and reduction (arrA) genes. Somewhat unexpectedly, the relative DNA abundances and diversities of ars, aioA, and arrA genes were not significantly different between low and high (∼10 versus ∼100 mg kg-1) As soils. Compared to available metagenomes from other soils, geographic distance rather than As levels drove the different compositions of microbial communities. Arsenic significantly increased ars gene abundance only when its concentration was higher than 410 mg kg-1. In contrast, metatranscriptomics revealed that relative to low-As soils, high-As soils showed a significant increase in transcription of ars and aioA genes, which are induced by arsenite, the dominant As species in paddy soils, but not arrA genes, which are induced by arsenate. These patterns appeared to be community wide as opposed to taxon specific. Collectively, our findings advance understanding of how microbes respond to high As levels and the diversity of As metabolism genes in paddy soils and indicated that future studies of As metabolism in soil or other environments should include the function (transcriptome) level. IMPORTANCE Arsenic (As) is a toxic metalloid pervasively present in the environment. Microorganisms have evolved the capacity to metabolize As, and As metabolism genes are ubiquitously present in the environment even in the absence of high concentrations of As. However, these previous studies were carried out at the DNA level; thus, the activity of the As metabolism genes detected remains essentially speculative. Here, we show that the high As levels in paddy soils increased the transcriptional activity rather than the relative DNA abundance and diversity of As metabolism genes. These findings advance our understanding of how microbes respond to and cope with high As levels and have implications for better monitoring and managing an important toxic metalloid in agricultural soils and possibly other ecosystems.

[Uptake and Accumulation of Cadmium and Zinc by Two Energy Grasses: A Field Experiment].

The remediation potential of large biomass energy grasses in cadmium-contaminated soil remains ambiguous. A field experiment was carried out in a cadmium-contaminated farmland using two energy grasses and two control plants. The two energy grasses were hybrid pennisetum (Pennisetum americanum×P. purpureum, PAP) and purple elephant grass (P. purpureum 'Purple', PPP), and the two control plants were Iris lactea var. chinensis (ILC) and a cadmium hyperaccumulator, Noccaea caerulescens (NC). The results showed that the aboveground biomass of PAP was the largest among the four plants, and 126 and 36 times that of NC and ILC, respectively, but no significant difference with that of PPP. The concentrations of cadmium and zinc in the shoots and roots of NC were significantly higher than in the other plants. Zinc concentrations in the shoots and roots of ILC were lower than in the other plants, while cadmium concentrations were significantly higher than in PAP and PPP (P<0.05). The amounts of cadmium and zinc accumulated in the shoots of PPP were the highest among the four plants, while cadmium concentrations in the shoots and roots of PPP were significantly lower than in ILC and NC (P<0.05). Cadmium amounts accumulated in PPP shoots were 7.0 and 4.1 times that of ILC and NC, respectively. Zinc amounts accumulated in PPP shoots were 41 and 11 times that of ILC and NC, respectively (P<0.05). Cadmium accumulation in the shoots of PAP was 19.4% lower than in PPP, and zinc accumulation had no significant difference with that of PPP. NC, having a bioconcentration factor of shoot (BCFS) and a translocation factor (TF) for cadmium and zinc both larger than 1, is usable for phytoextraction of soils contaminated by cadmium and zinc. ILC, having a bioconcentration factor of root (BCFR) larger than 1 and a TF lower than 1 for cadmium, is usable for the phytostabilization of soils contaminated by cadmium. PPP, having a BCFR larger than 1 and a TF lower than 1 for zinc, can be used in the phytostabilization of soils contaminated by zinc. Under field conditions, PPP and PAP showed great potential for the extraction and removal of cadmium and zinc from soil due to their large biomass and ability to produce economic benefits, have good application prospects.

A predictive model for arsenic accumulation in rice grains based on bioavailable arsenic and soil characteristics.

Arsenic (As) is a well-known human carcinogen, and rice consumption is the main way Chinese people are exposed to As. In this study, 14 kinds of paddy soils were collected from the main rice-producing areas in China. The results showed that rice roots and leaves accumulated more As than stems and grains in the following sequence: Asroot> Asleaf> Asstem> Asgrain. The accumulation of As by rice grains mainly depends on the total As and bioavailable As (0.43 mol/L HNO3 extractable As), which explained 32.2% and 22.2% of the variation in the grain As, respectively. In addition, soil pH, organic matter (OM) and clay contents were the major factors affecting grain As, explaining 13.1%, 7.9% and 5.3% of the variation, respectively. An effective prediction model was established via multiple linear regression as Asgrain= 0.024 BAs - 0.225 pH+ 0.013 OM+ 0.648 EC - 0.320 TN - 0.088 TP - 0.002 AS+ 2.157 (R2 =0.68, P < 0.01). Through the verification of the samples from both pot experiments and paddy fields, the model successfully provided accurate predictions for rice grain As.

The Great Oxidation Event expanded the genetic repertoire of arsenic metabolism and cycling.

The rise of oxygen on the early Earth about 2.4 billion years ago reorganized the redox cycle of harmful metal(loids), including that of arsenic, which doubtlessly imposed substantial barriers to the physiology and diversification of life. Evaluating the adaptive biological responses to these environmental challenges is inherently difficult because of the paucity of fossil records. Here we applied molecular clock analyses to 13 gene families participating in principal pathways of arsenic resistance and cycling, to explore the nature of early arsenic biogeocycles and decipher feedbacks associated with planetary oxygenation. Our results reveal the advent of nascent arsenic resistance systems under the anoxic environment predating the Great Oxidation Event (GOE), with the primary function of detoxifying reduced arsenic compounds that were abundant in Archean environments. To cope with the increased toxicity of oxidized arsenic species that occurred as oxygen built up in Earth's atmosphere, we found that parts of preexisting detoxification systems for trivalent arsenicals were merged with newly emerged pathways that originated via convergent evolution. Further expansion of arsenic resistance systems was made feasible by incorporation of oxygen-dependent enzymatic pathways into the detoxification network. These genetic innovations, together with adaptive responses to other redox-sensitive metals, provided organisms with novel mechanisms for adaption to changes in global biogeocycles that emerged as a consequence of the GOE.

Distribution of elements and their correlation in bran, polished rice, and whole grain.

The relationship of toxic elements (As, Cd, Cr) and trace elements (Cu, Se, Ni, Zn, Mn) in rice bran and corresponding polished rice is not well known. A total of 446 rice grains were collected from paddy fields distributed across China, and the concentrations of 8 elements in rice bran and their corresponding polished rice were measured. The levels of As, Cd, Cr, and Se have a good linear relationship between rice bran and polished rice (R 2: .79, .97, .82, .99, respectively; all p < .001). Polishing rice could effectively remove the average contents of 44.4% As, 19.8% Cd, and 15.4% Cr in the whole grain, but caused the substantial losses of more than half of Mn and Ni (57.7% and 56.9%), and nearly one-third (30.9%, 31.5%, and 29.1%) of Cu, Se, and Zn in brown rice although only about 10% of rice bran was milled. The "L" type correlation exists not only between As and Cd, but also between the nutrients Se, Mn, Ni, and the toxic elements As, Cd. These results indicated that As accumulation in rice could reduce the levels of essential mineral nutrients Mn, Ni, and Se. On the contrary, improving nutrient elements by fertilization could decrease the accumulation of some toxic elements. This provides a practical new idea for the prevention and control of rice As or Cd, and concomitantly improves the deficiency of nutrient elements in rice.

Bioavailable arsenic and amorphous iron oxides provide reliable predictions for arsenic transfer in soil-wheat system.

The application of current soil quality standards based on total arsenic (As) fails to assess the ecological risks of soil arsenic or to ensure the safety of crops and foods. In this study, bioavailable arsenic instead of total arsenic was applied to improve predictive models for arsenic transfer from soil to wheat (Triticum turgidum L.). The stepwise multiple-linear regression analysis showed that bioavailable arsenic and amorphous iron oxides (FeOX) were the two most important factors contributing to arsenic accumulation in wheat grain, with the explained percentage of variation being up to 82%. Compared with the bioavailable arsenic extracted by NH4H2PO4, bioavailable arsenic extracted by HNO3 from soils generated better predictions of the amount of arsenic in grain. The best reliable model was log[Asgrain] = 0.917 log[HNO3-As] - 0.452 log[FeOX] - 1.507 (R2 = 0.82, P <  0.001). Consistently, bioavailable arsenic and FeOX were also the key factors to predict arsenic accumulation in wheat straw, leaves and spikes. Our prediction models was successfully verified for three independent soils. Our results highlight the role of soil bioavailable heavy metals in predicting their transfer in soil-plant systems and can be used to improve existing Chinese soil quality standards.

Fate of Labile Organic Carbon in Paddy Soil Is Regulated by Microbial Ferric Iron Reduction.

Global paddy soil is the primary source of methane, a potent greenhouse gas. It is therefore highly important to understand the carbon cycling in paddy soil. Microbial reduction of iron, which is widely found in paddy soil, is likely coupled with the oxidation of dissolved organic matter (DOM) and suppresses methanogenesis. However, little is known about the biotransformation of small molecular DOM accumulated under flooded conditions and the effect of iron reduction on the biotransformation pathway. Here, we carried out anaerobic incubation experiments using field-collected samples amended with ferrihydrite and different short-chain fatty acids. Our results showed that less than 20% of short-chain fatty acids were mineralized and released to the atmosphere. Using Fourier transform ion cyclotron resonance mass spectrometry, we further found that a large number of recalcitrant molecules were produced during microbial consumption of these short-chain fatty acids. Moreover, the biotransformation efficiency of short-chain fatty acids decreased with the increasing length of carbon chains. Ferrihydrite addition promoted microbial assimilation of short-chain fatty acids as well as enhanced the activation and biotransformation of indigenous stable carbon in the soil replenished with formate. This study demonstrates the significance of ferrihydrite in the biotransformation of labile DOM and promotes a more comprehensive understanding of the coupling of iron reduction and carbon cycling in paddy soils.

Simultaneous adsorption and immobilization of As and Cd by birnessite-loaded biochar in water and soil.

A novel biochar was prepared by loading birnessite to improve its capability to simultaneously adsorb As(III), As(V), and Cd(II) in water and soil. Layer sheet-structured birnessite was successfully loaded onto the biochar surface with increased functional groups. SEM, XRD, and FTIR combining with XPS analysis were utilized to characterize birnessite-loaded biochar and its adsorption mechanisms for As and Cd(II). The saturated adsorption capabilities of the birnessite-loaded biochar (BRB) for As(III), As(V), and Cd(II) were as large as 3543, 2412, and 9068 mg/kg (calculated by Langmuir isotherm model), much higher than for the corresponding non-loaded biochar (no adsorption of As, 4335 mg/kg for Cd). Adsorption of Cd and As onto BRB was controlled by multi mechanisms; Cd(II) appeared to coordinate to vacant sites of birnessite, while As formed surface complex with functional groups. Furthermore, BRB showed higher abilities for co-adsorption of As(III) and Cd or As(V) and Cd, which may be due to the formation of Cd3(AsO4)2 surface precipitate as well as synergistic reaction between anions and cations. After conditioning to soil, BRB showed potential for Cd and As remediation under both flooded and unflooded conditions. These results suggested that BRB can be used as an effective sorbent for simultaneous immobilization of heavy metals, especially As and Cd, in environmental and agricultural systems.

Organic Carbon Amendments Affect the Chemodiversity of Soil Dissolved Organic Matter and Its Associations with Soil Microbial Communities.

The "4 per mil" initiative recognizes the pivotal role of soil in carbon resequestration. The need for evidence to substantiate the influence of agricultural practices on chemical nature of soil carbon and microbial biodiversity has become a priority. However, owing to the molecular complexity of soil dissolved organic matter (DOM), specific linkages to microbial biodiversity have eluded researchers. Here, we characterized the chemodiversity of soil DOM, assessed the variation of soil bacterial community composition (BCC), and identified specific linkages between DOM traits and BCC. Sustained organic carbon amendment significantly ( P < 0.05) increased total organic matter reservoirs, resulted in higher chemodiversity of DOM and emergence of recalcitrant moieties (H/C < 1.5). In the meantime, sustained organic carbon amendment shaped the BCC to a more eutrophic state while long-term chemical fertilization directed the BCC toward an oligotrophic state. Meanwhile, higher connectivity and complexity were observed in organic carbon amendment by DOM-BCC network analysis, indicating that soil microbes tended to have more interaction with DOM molecules after organic matter inputs. These results highlight the potential for organic carbon amendments to not only build soil carbon stocks and increase their resilience but also mediate the functional state of soil bacterial communities.

Design of High-Symmetrical Magnesium-Organic Frameworks with Acetate as Modulator and Their Fluorescence Sensing Performance.

During the formation of magnesium-organic frameworks, the coordination sphere of magnesium tends to be partially occupied by O-containing solvent molecules such as amides, which will dramatically decrease the symmetry of Mg-organic frameworks and thus lead to low stability. It is noted that up to now, most reported Mg-metal-organic frameworks (MOFs) (>80%) crystallize in the space groups whose symmetry is lower than that of a tetragonal system. In this work, we demonstrate that acetate (Ac) may act as modulator to eliminate the influence of amide solvent and improve the symmetry of Mg-organic frameworks. Two novel Mg-MOFs, namely, {[(CH3)NH3]4[Mg3(BTB)8/3(Ac)2(H2O)]} n (SNNU-35, H3BTB = 4',4'',4'''-benzene-1,3,5-tribenzoic acid) and {[(CH3)2NH2][Mg2(FDA)2(Ac)]} n (SNNU-36, H2FDA = 2,5-furandicarboxylic acid) were successfully designed, which crystallize in rhombohedral R-3 and tetragonal I4 /mmm space groups, respectively. Four independent BTB ligands link three unique Mg cations and generate superlarge [Mg21BTB17] nanocages, which interlock each other by strong π···π stacking to give a two-fold interpenetrating architecture of SNNU-35. On the other hand, carboxylate and acetate groups chelate Mg atoms to form one-dimensional chains, which are extended by FDA to produce the rod-packing framework of SNNU-36. Two microporous Mg-MOFs both exhibit notable CO2 and H2 uptakes. H3BTB and H2FDA ligands both have emission features, and Mg ions usually can enhance the fluorescent intensity, which lead to a strong solid-state luminescence emission property of SNNU-35 and -36. Importantly, two Mg-MOFs both show fast and quantative sensing performance for nitrocompounds. Among three selected models of substrate, SNNU-35 and -36 can eliminate the interference of nitromethane (NM) and exhibit high sensitivity to nitrobenzene (NB) and o-nitrotoluene (2-NT) with large k sv values (>105 M-1). Especially, the fluorescence quenching efficiency of NB (5000 ppm) and 2-NT (8000 ppm) can reach 96.3% and 89.5% and 85.0% and 83.7% for SNNU-35 and -36, respectively. This work offers not only an effective route to improve the symmetry of magnesium-organic frameworks but also two potential fluorescence sensors for nitroaromatic compounds.

[Effects of Boron Treatment on Arsenic Uptake and Efflux in Rice Seedlings].

The impacts of boron (B) root application and foliar spray on arsenic (As) uptake, translocation, and efflux by/in rice seedlings (Oryza sativa L.) were investigated in three hydroponic experiments. The addition of B to culture medium did not alter concentrations of arsenite (As[Ⅲ]), arsenate (As[Ⅴ]), and total As, nor did it alter transfer coefficients or uptake efficiency of As in rice seedlings under either As(Ⅲ) or As(Ⅴ) exposure. Foliar B supply increased shoot B concentrations 15.8-fold, and decreased root As concentrations and As uptake efficiency by 20.9% and 18.0% under As(Ⅴ) treatment, and by 12.6% and 13.8% under As(Ⅲ) treatment, respectively, yet did not significantly decrease shoot As concentrations (P>0.05). Interestingly, foliar B supply reduced root B concentrations by up to 47.1% under exposure to As(Ⅴ) but not As(Ⅲ), and corresponding root B concentrations were 85.3% higher in As(Ⅴ) treatment than in As(Ⅲ) treatment on average (P<0.05). Both total As and As(Ⅴ) concentrations were positively related to B concentration in rice roots under As(Ⅴ) treatment following foliar B supply (P<0.05). Rice seedlings extruded 105.2% more As after As(Ⅲ)-pretreatment than after As(Ⅴ)-pretreatment. Foliar B supply increased the amount of As excreted by As(Ⅲ)-pretreated rice root by 14.0%-16.9% (P>0.05), and had no effect on the As efflux of As(Ⅴ)-pretreatment seedlings. A range of 45.9%-70.7% of root As was excreted to solution during one week. These results indicate that the root application of B at four times the concentration of As can slightly decrease As accumulation by rice, whereas foliar B supply is conducive to a decline in As acquisition by rice roots. It is likely that the B channel is at least not the main pathway for As(Ⅲ) entering into rice roots, and the As(Ⅴ) distribution mechanism in rice plants may be shared with that of B.

[Mechanism of As(â ¤)Removal from Water by Lanthanum and Cerium Modified Biochars].

Loaded lanthanum or cerium biochars were prepared by one step pyrolysis of La (NO3)3-laden or Ce (NO3)3-laden rice hulls and were employed for enhancing the adsorption of As (Ⅴ) from water. In contrast with BC and Ce-BC in this study, La-BC had better adsorption capacity in the acidic condition. The maximum adsorption capacity could reach 20.1 mg ·g-1. With increased pH, the adsorption capacity of La-BC was reduced. The highest adsorption capacity reached 39.1 mg ·g-1 (pH=5) and the lowest was 17.6 mg ·g-1 (pH=9). The resulting La-BC with As (Ⅴ) adsorption was characterized by SEM-EDS, FTIR, and XPS. There were two types of active adsorption sites for As (Ⅴ), oxygen-rich functional groups and lanthanum oxide. Although Ce-BC had oxygen-rich functional groups and cerium oxide, it was unable to participate in the adsorption of As (Ⅴ) from water.

Rapid evaluation of arsenic contamination in paddy soils using field portable X-ray fluorescence spectrometry.

Arsenic (As) in paddy fields is deteriorating food security and human health through rice ingestion. Rice is the dominant food source of arsenic exposure to half of the world's population. Therefore, an in situ effective method for As risk evaluation in paddy soil is strongly needed to avoid As exposure through rice ingestion. Herein, we developed a rapid analytical methodology for determination of As in plant tissues using field portable X-ray fluorescence spectrometry (FP-XRF). This method was applied to rice roots in order to evaluate the As contamination in paddy soils. The results showed that rice roots with iron plaques were superior to rhizosphere soils for generating FP-XRF signals, especially for field sites with As concentrations lower than the soil detection limit of FP-XRF (30.0mg/kg). Moreover, the strong linear relationships of As concentrations between the rice roots and corresponding leaves and grains proved that the rice root, rather than the soil, is a better predictor of As concentrations in rice grains. The research provides an efficient As monitoring method for As contaminated paddy fields by using wetland plant roots with iron plaques and XRF-based analytical techniques.

Molecular Chemodiversity of Dissolved Organic Matter in Paddy Soils.

Organic matter (OM), and dissolved organic matter (DOM), have a major influence upon biogeochemical processes; most significantly, the carbon cycle. To date, very few studies have examined the spatial heterogeneity of DOM in paddy soils. Thus, very little is known about the DOM molecular profiles and the key environmental factors that underpin DOM molecular chemodiversity in paddy soils. Here, Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry was applied to unambiguously resolve 11 361 molecular formulas in 16 paddy soils; thereby elucidating the molecular characteristics of paddy soil DOM. Soil pH, iron complexing index (Fep/FeR) and C/N ratio were established to be key factors controlling DOM profiles. Polycyclic aromatics (derived from combustion) and polyphenols (derived from plants) increased with increasing pH, while polyphenols molecules, pyrogenic aromatics, and carboxylic compounds decreased with increasing iron complexing index. Patterns in molecular profiles indicated DOM in paddy soils to become more recalcitrant at higher soil C/N ratio and higher pH. Furthermore, plant-derived polyphenols and pyrogenic DOM were retained favorably by iron and the chemodiversity of DOM in paddy soil increased with increasing soil C/N ratios. This study provides critical information about DOM characteristics at a molecular level and will inform better global management of soil carbon in paddy soil ecosystems.

The role of sulfate-reducing prokaryotes in the coupling of element biogeochemical cycling.

Sulfate-reducing prokaryotes (SRP) represent a diverse group of heterotrophic and autotrophic microorganisms that are ubiquitous in anoxic habitats. In addition to their important role in both sulfur and carbon cycles, SRP are important biotic and abiotic regulators of a variety of sulfur-driven coupled biogeochemical cycling of elements, including: oxygen, nitrogen, chlorine, bromine, iodine and metal(loid)s. SRP gain energy form most of the coupling of element transformation. Once sulfate-reducing conditions are established, sulfide precipitation becomes the predominant abiotic mechanism of metal(loid)s transformation, followed by co-precipitation between metal(loid)s. Anthropogenic contamination, since the industrial revolution, has dramatically disturbed sulfur-driven biogeochemical cycling; making sulfur coupled elements transformation complicated and unpredictable. We hypothesise that sulfur might be detoxication agent for the organic and inorganic toxic compounds, through the metabolic activity of SRP. This review synthesizes the recent advances in the role of SRP in coupled biogeochemical cycling of diverse elements.