Improvement of biotic nitrate reduction in constructed photoautotrophic biofilm-soil microbial fuel cells.

The biotic nitrate reduction rate in freshwater ecosystems is typically constrained by the scarcity of carbon sources. In this study, 'two-chambers' - 'two-electrodes' photoautotrophic biofilm-soil microbial fuel cells (P-SMFC) was developed to accelerate nitrate reduction by activating in situ electron donors that originated from the soil organic carbon (SOC). The nitrate reduction rate of P-SMFC (0.1341 d-1) improved by âˆ¼ 1.6 times on the 28th day compared to the control photoautotrophic biofilm. The relative abundance of electroactive bacterium increased in the P-SMFC and this bacterium contributed to obtain electrons from SOC. Biochar amendment decreased the resistivity of P-SMFC, increased the electron transferring efficiency, and mitigated anodic acidification, which continuously facilitated the thriving of putative electroactive bacterium and promoted current generation. The results from physiological and ecological tests revealed that the cathodic photoautotrophic biofilm produced more extracellular protein, increased the relative abundance of Lachnospiraceae, Magnetospirillaceae, Pseudomonadaceae, and Sphingomonadaceae, and improved the activity of nitrate reductase and ATPase. Correspondingly, P-SMFC in the presence of biochar achieved the highest reaction rate constant for nitrate reduction (kobs) (0.2092 d-1) which was 2.4 times higher than the control photoautotrophic biofilm. This study provided a new strategy to vitalize in situ carbon sources in paddy soil for nitrate reduction by the construction of P-SMFC.

The interplay of hematite and photic biofilm triggers the acceleration of biotic nitrate removal.

The soil-water interface is replete with photic biofilm and iron minerals; however, the potential of how iron minerals promote biotic nitrate removal is still unknown. This study investigates the physiological and ecological responses of photic biofilm to hematite (Fe2O3), in order to explore a practically feasible approach for in-situ nitrate removal. The nitrate removal by photic biofilm was significantly higher in the presence of Fe2O3 (92.5%) compared to the control (82.8%). Results show that the presence of Fe2O3 changed the microbial community composition of the photic biofilm, facilitates the thriving of Magnetospirillum and Pseudomonas, and promotes the growth of photic biofilm represented by the extracellular polymeric substance (EPS) and the content of chlorophyll. The presence of Fe2O3 also induces oxidative stress (•O2-) in the photic biofilm, which was demonstrated by electron spin resonance spectrometry. However, the photic biofilm could improve the EPS productivity to prevent the entrance of Fe2O3 to cells in the biofilm matrix and mitigate oxidative stress. The Fe2O3 then promoted the relative abundance of Magnetospirillum and Pseudomonas and the activity of nitrate reductase, which accelerates nitrate reduction by the photic biofilm. This study provides an insight into the interaction between iron minerals and photic biofilm and demonstrates the possibility of combining biotic and abiotic methods to improve the in-situ nitrate removal rate.

Influence of crop residue-induced Fe-DOC complexation on nitrate reduction in paddy soil.

Although complexation between dissolved organic matter (DOM) and ubiquitous Fe is known to have a major influence on electron transferring ability in redoximorphic soil, it was unclear whether and how this complexation affected nitrate reduction and N2O productivity. The nitrate reduction of paddy soil in the presence of crop residues returning under flooding conditions was explored in this study. The rate of nitrate reduction in control soil was 0.0677 d-1, while it improved 1.99 times in treatment soil with Chinese milk vetch (CMV) straw returning. During a 28-day incubation period, N2O productivity decreased 0.08-0.91 ppb in CMV soil and 0.43-0.50 ppb in rice straw soil compared with control. The presence of crop residue increased DOC content and Fe (III) reduction rate, which aided in the formation of Fe (II)-DOC complexation. Meanwhile, the addition of CMV increased the content of DOC by 5.14-78.77 mg/kg and HCl extractable Fe (II) by 35.12-1221.03 mg/kg. Crop residues returning to soil increased the relative abundance of iron reductive and electroactive genera, as well as denitrifying genera with more copies of denitrification genes (Archangiaceae, Gemmatimonadaceae, and Burkholderiaceae). The synergistic effect of Fe-DOC complexation, electroactive genera, and denitrifying genera contributed to up-regulated expression of napA and narG (5.84 × 106 and 3.39 × 107 copies increased in the CMV soil compared to the control) numbers and equally accelerated reduction of nitrate to nitrite, while further nitrite reduction was primarily attributed to the abiotic reaction by Fe (II). From a bio-electrochemical point of view, this work provided new insight into the nitrate reduction of paddy soil impacted by Fe-DOC complexation.

Reduced arsenic availability in paddy soil through Fe-organic ligand complexation mediated by bamboo biochar.

The reuse of arsenic (As)-contaminated paddy fields is a global challenge because long-term flooding would result in As release due to the reductive dissolution of iron minerals. Biochar amendment is a common and effective remediation technique for As-contaminated paddy soil. However, the literature is still lacking in systematic research on the function of biochar in controlling the complexation of released dissolved organic matter (DOM) and iron oxides and its synergistic impact on the availability of As in flooded paddy soil. In the present study, bamboo biochar was prepared at different pyrolysis temperatures (300, 450 and 600 °C), as BB300, BB450 and BB600. Four paddy soil treatments including BB300, BB450, BB600 applications (1% ratio, m/m, respectively) and control (CK, no biochar application) were set and incubated for 60 d in flooding condition. The results showed that As availability represented by adsorbed As species (A-As) was mitigated by BB450 amendment compared with CK. The amendment of BB450 in paddy soil facilitated the complexation of HCl extractable Fe(III)/(II) and DOM and formation of amorphous iron oxides (e.g. complexed Fe species). Moreover, the abundance of Geobacteraceae and Xanthomonadaceae, as common electroactive bacteria, was promoted in the BB450 treated paddy soil in comparison to CK, which assisted to form amorphous iron oxides. The formed amorphous iron oxides then facilitated the formation of ternary complex (As-Fe-DOM) with highly stability, which could be considered as a mechanism for As immobilization after biochar was applied to the flooding paddy soil. Thus, the synergistic effect between amorphous iron oxides and electroactive stains could make main contribution to the passivation of released As in paddy soil under long-term flooding condition. This study provided a new insight for As immobilization via regulating iron-organic ligand complexation amendment with biochar in flooding paddy soil.

Susceptibility of Cd availability in microplastics contaminated paddy soil: Influence of ferric minerals and sulfate reduction.

The combined contamination of cadmium (Cd) and microplastics (MPs) in paddy soil always occurred, while its influence on Cd availability remained unclear. This study investigated the Cd availability in Cd-MPs co-contaminated paddy soil in consideration of both ferric minerals and sulfate reduction under flooding conditions. The presence of MPs resulted in a higher Cd releasing risk, as represented by the increase in the available Cd and decrease in Fe-Mn oxide-bound Cd contents, especially on the 7th and 14th days based on the sequential extraction results. MPs facilitated the formation of Fe-organic ligands, which accelerated the reductive dissolution of iron minerals but decreased the amounts of amorphous iron minerals due to the release of dissolved organic substances into pore water. Furthermore, MPs promoted the relative abundance of sulfate-reducing bacteria (such as Streptomyces and Desulfovibrio genera), thus increasing the contents of reductive S species, which was advantageous to the co-precipitation of Fe, S, and Cd on the surface of MPs based on our experimental and statistical results. Taken together, both iron and sulfate reduction under anaerobic conditions played a critical role in Cd mobilization in Cd-MPs co-contaminated paddy fields.

Co-exposure of polystyrene microplastics influence cadmium trophic transfer along the "lettuce-snail" food chain: Focus on leaf age and the chemical fractionations of Cd in lettuce.

Cadmium (Cd) and polystyrene microplastics (PS) co-contamination always occurs in environment; however, the trophic transfer of Cd and PS is still poorly understood. A hydroponic experiment was conducted to investigate the behavior of Cd in lettuce, together with the root or foliar exposure of different sized PS. Accumulation and chemical form distributions of Cd in leaves were distinguished into young and mature leaves. Subsequently, a 14-day snail feeding experiment was performed. Data showed that Cd accumulation in roots, rather than in leaves, are significantly affected by PS coexistence. However, mature leaves had a higher Cd content than young leaves under the root exposure of PS, while a reverse effect was observed in the foliar exposure. There existed a positive correlation between the food-chain transfer associated Cd (CdFi+Fii+Fiii) in mature leaves and Cd content in snail soft tissue (r = 0.705, p < 0.001), but not in young leaves. Though no bio-amplification of Cd in food chain was observed, an increase of Cd transfer factor (TF) from lettuce to snail was noted in the root exposure of 5 µm PS and the foliar exposure of 0.2 µm PS. Moreover, we observed a highest increase rate of 36.8 % in TF values from lettuce to snail viscera, and a chronic inflammatory response in snail stomach tissue. Therefore, more attentions should be paid to study the ecological risks of heavy metals and microplastics co-contamination in environment.

A review of clay based photocatalysts: Role of phyllosilicate mineral in interfacial assembly, microstructure control and performance regulation.

Over the past decades, inspired by the outstanding properties of clay minerals such as abundance, low-cost, environmental benignity, high stability, and regularly arranged silica-alumina framework, researchers put much efforts on the interface assembly and surface modification of natural minerals with bare photocatalysts, i.e. TiO2, g-C3N4, ZnO, MoS2, etc. The clay-based hybrid photocatalysts have resulted in a rich database for their tailor-designed microstructures, characterizations, and environmental-related applications. Therefore, in this study, we took a brief introduction of three representative minerals, i.e. kaolinite, montmorillonite and rectorite, and discussed their basic merits in photocatalysis applications. After that, we summarized the recent advances in construction of stable visible-light driven photocatalysts based on these minerals. The structure-activity relationships between the properties of clay types, pore structure, distribution/dispersion and light absorption, carrier separation efficiency as well as redox performance were illustrated in detail. Such representative information would provide theoretical basis and scientific support for the application of clay based photocatalysts. Finally, we pointed out the major challenges and future directions at the end of this review. Undoubtedly, control and preparation of novel photocatalysts based on clays will continue to witness many breakthroughs in the arena of solar-driven technologies.

Clinoptilolite mediated activation of peroxymonosulfate through spherical dispersion and oriented array of NiFe2O4: Upgrading synergy and performance.

Inspired by the features of both transition metal oxide and natural clinoptilolite (flaky structure with suitable pore diameter and open skeleton structure), we adopted a robust strategy by immobilization of nickel ferrite nanoparticles (NiFe2O4) on the clinoptilolite surface via typical citric acid combustion method. The hybrid catalyst exhibited enhanced peroxymonosulfate (PMS) activation efficiency and bisphenol A (BPA) degradation performance. Calculated by effective equivalent of NiFe2O4, it is found that the reaction rate constant (k) of NiFe2O4/clinoptilolite/PMS system (0.1859 min-1) was 11.9 times higher than that of bare NiFe2O4/PMS system (0.0156 min-1), which demonstrated that catalyst would be conjugated to PMS or contaminant efficiently and renders the rapid degradation and mineralization in the presence of clinoptilolite. After comprehensive characterization analysis and DFT simulations, natural mineral carrier effect (i.e. decreased crystalline size, increased oxygen vacancy content, etc.), abundant surface-bonded and structural hydroxyl groups as well as effective bonding with iron or nickel ions charged for the potential activation mechanism of PMS by NiFe2O4/clinoptilolite composite. And it is indicated that not only •OH and SO4•-, but also 1O2 was involved into series reactions. Overall, this study put forward a green and promising technology for high-toxic wastewater treatment.

Dam Construction as an Important Anthropogenic Activity Disturbing Soil Organic Carbon in Affected Watersheds.

To explore whether and how anthropogenic activities related to surface water regulation (i.e., dam construction) disturb soil ecosystems in the surrounding uplands, a long-term monitoring program was conducted from 1998 to 2017 in the Three Gorges Reservoir Region, China. The Three Gorges Dam (TGD) is the largest hydraulic engineering project in the world. We present a direct, ecosystem-scale demonstration of changes in the soil organic carbon (SOC) content in the TGD watershed before and after the surface water was reshaped. The average SOC content decreased from 12.9 to 9.5 g/kg between 2004 and 2012 and then recovered to 13.8 g/kg in 2017. Dynamics of SOC were partly attributed to shifts in the composition of soil microbial communities responsible for carbon biogeochemistry. The shifts in microbial taxa were associated with the changed microclimate affected by the TGD as well as global and regional climate variability. The microclimate, soil microorganisms, and plant organic carbon input explained 40.2% of the variation in the SOC content. This study revealed that dam construction was an important and indirect driver for the SOC turnover, and the subsequent effects on the upland soil ecosystem must be considered when large-scale disturbance activities (such as dam construction) are conducted in the future.

UV365 induced elimination of contaminants of emerging concern in the presence of residual nitrite: Roles of reactive nitrogen species.

The presence of nitrite (NO2-) is inevitable with concentrations of several mg L-1 in some typical water bodies. In this study, UV at wavelength of 365 nm was investigated to degrade contaminants of emerging concern (CECs) in the presence of NO2- at environmentally relevant concentrations (0.1-5.0 mg L-1). Six selected CECs with different structures were efficiently removed because of the generation of reactive nitrogen species (RNS) and hydroxyl radical (HO•) from photolysis of NO2-. Contributions of UV365 photolysis, RNS, and HO• to CEC degradation in UV365/NO2- system were calculated, and RNS were found to be the predominant species that are responsible for CEC degradation. The second major contributor is HO• for the degradation of selected CECs except for the case of sulfadiazine. Impacts of water matrix components (including dissolved oxygen, solution pH, and natural organic matter) on CEC degradation in UV365/NO2- system were evaluated. Furthermore, evolution profiles of CECs and NO2- in UV365/NO2- system were tracked when actual water samples were used as background, and a simultaneous removal of CECs and NO2- was observed. Transformation products of bisphenol A and carbamazepine were proposed according to the results of HPLC/MS and quantum chemistry calculations. Nitration induced by RNS and hydroxylation induced by HO• are main reactions occurred during CEC degradation in UV365/NO2- system. Overall, UV365 is a potential technology to remove CECs and NO2- in aquatic environment when residual NO2- is present. Our present study also provides possibility for the application of sunlight to remediate water co-polluted by CECs and NO2-.

Dual benefits of long-term ecological agricultural engineering: Mitigation of nutrient losses and improvement of soil quality.

Soil erosion of sloped farmland in the Three Gorges Reservoir area (TGRA) has led to the serious loss of nutrients, soil quality degradation and the downstream water quality being threatened. Thus, a series of ecological agricultural engineering measures was established in 2011, as a field experiment using citrus (navel orange) plants to reduce soil erosion, which was monitored from 2011 to 2018. These ecological agricultural engineering measures included three treatments: 1) citrus intercropped with white clover (WC), 2) citrus orchard land mulched with straw (SM) and 3) citrus intercropped with hemerocallis (Hemerocallis flava) contour hedgerows (CH). The conventional citrus orchard management was regarded as control (CK). The results show, that compared with CK, nutrient loss from the experiments were reduced by the following amounts: for nitrogen - WC (35.5%), SM (44.0%) and CH (52.0%); for phosphorus - WC (40.0%), SM (51.7%) and CH (58.3%). Therefore, the ecological agricultural engineering measures effectively mitigate the nutrient loss loads of the navel orange citrus gardens. The citrus intercropped with the hemerocallis hedgerows is the most effective measure for the control of nutrient loss. After 8 years of experiment, the soil quality represented by average soil quality index (SQI) in these three treatments, are significantly higher than that of the CK (and the beginning of the experiment). This is because the application of these measures prevented the loss of: soil organic matter, bulk density and total phosphorus. It is predicted that the soil qualities of these three treatments will remain in the range of soil grade II and I for the next 5 years but the soil quality of CK will decrease to soil quality grade II and III. These results show that ecological agricultural engineering measures are a long-term promising and feasible method to reduce soil erosion and enhance soil quality.

Bismuth impregnated biochar for efficient estrone degradation: The synergistic effect between biochar and Bi/Bi2O3 for a high photocatalytic performance.

An innovative advanced oxidation process was successfully developed to photocatalytic-degradation of estrone through the synergistic effect of biochar and Bi/Bi2O3 in bismuth-containing photocatalytic biochar (BiPB). The highest reaction rate constant (kobs) of estrone degradation by BiPB was 0.045 min-1 under the conditions of initial concentration of estrone =10.4 µmol L-1, [BiPB] =1 g L-1, pH = 7.0. The kobs was almost tenfold and more than 20 times than that of biochar without bismuth impregnation and pristine Bi/Bi2O3, respectively. The best photocatalytic performance of BiPB composites for the degradation of estrone was primarily attributed to generation of OH radicals. Impregnation of bismuth helped control the concentration of persistent free radicals (PFRs) and develop a hierarchical porous structure of biochar. The presence of biochar facilitated pre-concentration estrone on BiPB and improved the separation and transfer efficiency of charge carriers. The synergistic effect between biochar and Bi/Bi2O3 contributed to the generation of OH radicals for estrone degradation under neutral pH conditions. The transformation pathway of estrone was also proposed based on the measured transformation products in the presence of BiPB. The high efficiency of BiPB composites indicated that this easily-obtained material was promising for estrone-wastewater treatment applications as a low-cost composite photocatalyst.

The unexpected concentration-dependent response of periphytic biofilm during indole acetic acid removal.

Due to its extensive application in agriculture as a germinating agent and growth promoter, indole acetic acid (IAA) is present in a variety of aquatic ecosystems. To explore the response of microbial aggregates to exogenous IAA in aquatic ecosystems, periphytic biofilm, a typical microbial aggregate, was exposed to IAA at different concentrations. Results reveal an unexpected concentration-dependent effect of IAA on periphytic biofilm. Concentrations of IAA less than 10 mg/L inhibit periphytic growth, but stimulate growth when the IAA concentration exceeds 50 mg/L. Periphytic biofilm adapts to different IAA concentrations by antioxidant enzyme activation, community structure optimization and carbon-metabolism pattern change, and promotes bioremediation of IAA contaminated water in the process. The removal rates of IAA reached up to 95%-100%. This study reveals the capacity of periphytic biofilm for IAA removal in practice.

Susceptibility of atrazine photo-degradation in the presence of nitrate: Impact of wavelengths and significant role of reactive nitrogen species.

The role of reactive nitrogen species (RNS) formed from nitrate photolysis has aroused interests in transformation of contaminants of emerging concern. This study investigated the influence of UV wavelengths (255, 285 and 365 nm) on photolysis of nitrate for degradation of atrazine (ATZ). The UV285/nitrate system showed the fastest rate constant for degradation of ATZ with kobs of 0.0022 cm2 mJ-1. UV photolysis, RNS, and hydroxyl radical (HO) were identified as main contributors to ATZ degradation in UV/nitrate system. Among the contributors, RNS made the major contribution to degradation of ATZ in UV285/nitrate system, while HO is the predominant specie in UV255/nitrate system. Variance decomposition analysis showed that degradation of ATZ was slightly impacted by natural organic matter and carbonate/bicarbonate in UV285/nitrate system but was dramatically affected in UV255/nitrate system. Main transformation products of ATZ in UV285/nitrate system were identified and possible pathways were proposed. RNS were confirmed to be favorable for acceleration of ATZ photolysis through further reaction of RNS with hydroxyatrazine (with electron-rich moieties). Our study provides deep insights on the influence of UV wavelength on nitrate photolysis and ATZ degradation, and provides a novel method for remediation of water co-contaminated by nitrate and organic contaminants.

Protection Mechanisms of Periphytic Biofilm to Photocatalytic Nanoparticle Exposure.

Researchers are devoting great effort to combine photocatalytic nanoparticles (PNPs) with biological processes to create efficient environmental purification technologies (i.e., intimately coupled photobiocatalysis). However, little information is available to illuminate the responses of multispecies microbial aggregates against PNP exposure. Periphytic biofilm, as a model multispecies microbial aggregate, was exposed to three different PNPs (CdS, TiO2, and Fe2O3) under xenon lamp irradiation. There were no obvious toxic effects of PNP exposure on periphytic biofilm as biomass, chlorophyll content, and ATPase activity were not negatively impacted. Enhanced production of extracellular polymetric substances (EPS) is the most important protection mechanism of periphytic biofilm against PNPs exposure. Although PNP exposure produced extracellular superoxide radicals and caused intracellular reactive oxygen species (ROS) accumulation in periphytic biofilm, the interaction between EPS and PNPs could mitigate production of ROS while superoxide dismutase could alleviate biotic ROS accumulation in periphytic biofilm. The periphytic biofilms changed their community composition in the presence of PNPs by increasing the relative abundance of phototrophic and high nutrient metabolic microorganisms (families Chlamydomonadaceae, Cyanobacteriacea, Sphingobacteriales, and Xanthomonadaceae). This study provides insight into the protection mechanisms of microbial aggregates against simultaneous photogenerated and nanoparticle toxicity from PNPs.

Augmenting nitrogen removal by periphytic biofilm strengthened via upconversion phosphors (UCPs).

The application of periphytic biofilm in removing nitrogen from water is limited by the fluctuating nitrogen concentration. Here, we delineate a novel approach to enhance periphytic biofilm performance in nitrogen removal via upconversion luminescence of upconversion phosphors (UCPs). Nitrogen removal rates (14 d) in high nitrogen wastewater (26 mg/L) were significantly improved to 58.6% and 61.4% by UCPs doped with Pr3+ and Li+ and UCPs doped with Pr3+, respectively, and to 95.1% and 95.9% in low nitrogen surface water (2 mg/L), respectively. The stimulation of UCPs optimized the microbial community structure in the periphytic biofilms, and also resulted in good acclimation to use different carbon sources. The enhanced synergic action of cyanobacterial biomass, ratio of Gram +ve to Gram -ve bacteria and carbon source metabolic capacity contributed to the improved nitrogen removal. This novel approach is promising in nitrogen removal from wastewater and surface water with fluctuating initial nitrogen concentration.

Arsenic immobilization through regulated ferrolysis in paddy field amendment with bismuth impregnated biochar.

Iron minerals are important for arsenic immobilization in paddy fields; however, intensive ferrolysis causes arsenic (As) release. Bismuth-impregnated biochar derived from wheat straw (BiBC) was synthesized to immobilize arsenic by regulating the ferrolysis process in a paddy field. Further X-ray based analysis (XRD and XPS) results demonstrated that crystal particles of bismuth oxide and bismuth oxychloride were loaded on the biochar surface, helped create additional micropores and improved its specific surface area. The bioavailability of As, as determined via (non)specifically adsorbed As, decreased as the amended dosage of BiBC increased, while wheat straw biochar (WBC) resulted in arsenic release. The presence of biochar caused a faster reduction rate of iron oxides; however, BiBC promoted the sequential co-precipitation of iron and arsenic ions. Adsorption kinetic experiments indicated that ferrous ions facilitated precipitation of As on the surface of BiBC. The XRD analysis of soil samples showed BiBC facilitated the formation/stability of FeOOH. Thus, amendment with BiBC regulated ferrolysis to buffer iron leaching, which contributed to arsenic immobilization under flooding conditions. This study demonstrated the feasibility of As immobilization by metal-impregnated biochar in paddy soils.

A New Concept of Promoting Nitrate Reduction in Surface Waters: Simultaneous Supplement of Denitrifiers, Electron Donor Pool, and Electron Mediators.

The efficiency of biological nitrate reduction depends on the community composition of microorganisms, the electron donor pool, and the electron mediators participating in the biological reduction process. This study aims at creating an in situ system comprising of denitrifiers, electron donors, and electron mediators to reduce nitrate in surface waters. The ubiquitous periphytic biofilm in waters was employed to promote in situ nitrate reduction in the presence of titanium dioxide (TiO2) nanoparticles (NPs). The nitrate removal rate in the periphytic biofilm and TiO2 NPs system was significantly higher than the control (only periphytic biofilm or TiO2 NPs). TiO2 NPs optimized the community composition of periphytic biofilm for nitrate reduction by increasing the relative abundance of four dominant denitrifying bacteria. Periphytic biofilm showed a substantial increase in extracellular polymeric substance, especially the humic acid and protein content, due to the presence of TiO2 NPs. The synergistic action of humic acid, protein, denitrifying bacteria of the periphytic biofilm, and TiO2 NPs contributed to 80% of the nitrate reduction. The protein and humic acid, acting as electron mediators, facilitated the transfer of exogenous electrons from photoexcited TiO2 NPs to periphytic biofilm containing denitrifiers, which enhanced nitrate reduction in surface waters.

Synthesis of mesoporous bismuth-impregnated aluminum oxide for arsenic removal: Adsorption mechanism study and application to a lab-scale column.

High mobility and toxicity of arsenic [As (III)] limit its removal from an aquatic environment and pose a threat to human health. In this work, batch adsorption experiments were conducted to investigate the adsorption capacity of bismuth-impregnated aluminum oxide (BiAl). Continuous application of As (III) removal was achieved via a lab-scale column reactor. Bismuth impregnation decreased the specific surface area of aluminum oxide and affected its pore size distribution. However, because of its abundant and well-proportioned mesoporous character, it also enhanced its adsorption capacity through the surface complexation of As (III). Batch adsorption experiments demonstrated a suitable Freundlich model and a fitted pseudo-second-kinetic model for As (III) adsorption. The main mechanism was chemisorption with both bismuth and aluminum atoms; however, physisorption also contributed to arsenic adsorption at the initial stage of the reaction. The Adams-Bohart model better described the breakthrough curves than the Thomas model. BiAl exhibited efficient As (III) adsorption over a wide pH range and could be applied to As (III) removal from wastewater. A high As (III) removal efficiency (91.6%) was obtained at an initial As (III) concentration of 5 mg L-1 at a flow rate of 1 mL min-1. This study indicates the potential for the practical application of BiAl in As (III) removal.

Arsenic removal by periphytic biofilm and its application combined with biochar.

A biochar and periphyton-based system (BPS) comprising of a biochar column and a periphyton bioreactor was designed to avoid the toxicity issue associated with removing As(III) from wastewater. Results showed that the periphyton can grow when As(III) is less than 5.0mgL-1. The BPS obtained a high As(III) removal rate (∼90.2-95.4%) at flow rate=1.0mLmin-1 and initial concentration of As(III)=2.0mgL-1. About 60% of the As(III) was pre-treated (adsorbed) in the biochar column and the removal of the remaining As(III) was attributed to the periphyton bioreactor. The As(III) removal process by periphytic biofilm in the initial stage fits a pseudo-second-kinetic model. The calcite in the periphytic biofilm surfaces and the OH and CO groups were responsible for the As(III) removal. This study indicates the feasibility of the BPS for As(III) removal in practice.