Sequestering of As(III) and As(V) from wastewater using a novel neem leaves/MnFe2O4 composite biosorbent

An arsenic biosorbent comprising neem leaves (NL) and MnFe₂O₄ particles was developed and its removal potential was investigated. Physicochemical analysis of the NL/MnFe₂O₄ composite (MNL) was performed for the Brunauer, Emmett and Teller surface area, Fourier transform infrared spectra (FT-IR), and scanning electron microscopy–Energy-dispersive X-ray (EDX). The following parameters were optimized: pH, biosorbent dose, contact time, temperature, and initial arsenic concentration. The optimum pH values achieved for biosorption of As(III) and As(V) were 7.0 and 4.0, respectively, when the equilibrium time was 110 minutes for both. MNL was found to be efficient with 85.217% and 88.154% biosorption efficiency at a concentration of 50 mg/L of As(III) or As(V) solution, respectively. This was also proved by the FT-IR study of arsenic-loaded biosorbent. For establishing the best suitable correlation for the equilibrium curves exploiting the procedure of the nonlinear regression for curve fitting analysis, isotherm studies were conducted for As(III) and As(V) using 30 isotherm models. The pattern of biosorption fitted well with Brouers–Sotolongo isotherm model for As(III) and Langmuir–Freundlich as well as Sips isotherm models for As(V). Dubinin–Radushkevich (D-R) isotherm studies specified that ion exchange might play a significant role. The influence of various co-existing ions at different concentrations was examined. Desorption study was performed using various concentrations of NaOH solution.     

Identification of Agrostis tenuis leaf proteins in response to As(V) and As(III) induced stress using a proteomics approach

Agrostis tenuis is known to be able to metabolise arsenate (As(V)) and arsenite (As(III)) which are toxic salts for most plants. A proteomic approach was developed to identify proteins expressed in response to treatments with these salts. A. tenuis plants were grown hydroponically in the presence of 134 and 668 μM As(V) or As(III) for 8 days at pH 7. During arsenic treatments, leaves showed chlorotic symptoms but fresh and dry leaf weights were not reduced, except in the presence of 668 μM As(III). On the contrary, a slight increase in biomass was observed with high As(V) concentrations. Thus, A. tenuis was more sensitive to As(III) than to As(V) and biomass was affected. Proteomic analysis enabled identification of a set of A. tenuis leaf proteins differentially expressed in response to arsenic exposure including a major functionally homogeneous group of enzymes such as oxygen-evolving enhancer protein, RuBisCO small and large subunits, RuBisCO activase and ATP synthase involved in the Calvin or Krebs cycle. The adaptative response to treatments resulted in partial disruption of the photosynthetic processes with prominent fragmentation of the RubisCO. Other proteins expressed differently from controls were identified and are possibly involved in the tolerance mechanisms of A. tenuis to arsenic treatments.     

INFLUENCE OF SOIL PROPERTIES AND PHOSPHATE ADDITION ON ARSENIC UPTAKE FROM POLLUTED SOILS BY VELVETGRASS (HOLCUS LANATUS)

Four kinds of soil material were used in a pot experiment with velvetgrass (Holcus lanatus). Two unpolluted soils: sand (S) and loam (L) were spiked with sodium arsenite (As III) and arsenate (As V), to obtain total arsenic (As) concentrations of 500 mg As kg^?1. Two other soils (ZS I, ZS III), containing 3320 and 5350 mg As kg^?1, were collected from Zloty Stok where gold and arsenic ores were mined and processed for several centuries. The effects of phosphate addition on plants growth and As uptake were investigated. Phosphate was applied to soils in the form of NH₄H₂PO₄ at the rate 0.2 g P/kg. Average concentrations of arsenic in the shoots of velvetgrass grown in spiked soils S and L without P amendment were in the range 18–210 mg As kg^?1 d.wt., whereas those in plants grown on ZS I and ZS II soils were considerably lower, and varied in the range 11–52 mg As kg^?1 d.wt. The addition of phosphate caused a significant increase in plant biomass and therefore the total amounts of As taken up by plants, however, the differences in As concentrations in the shoots of velvetgrass amended and non-amended with phosphate were not statistically significant.     

The Role of Low-Molecular-Weight Organic Carbons in Facilitating the Mobilization and Biotransformation of As(V)/Fe(III) from a Realgar Tailing Mine Soil

Several low-molecular-weight organic carbon (LMWOC) compounds (acetate, propionate, butyrate, lactate, and glucose) were added to flooded arsenic-rich tailing mine soil to investigate their effect to the mobilization of As/Fe and potential shift of microbial community. A promoting effect to the mobilization and biotransformation of As(V)/Fe(III) in the soils resulting from the supplementation with LMWOCs substrate was indicated compared to the biotic microcosm amended with deionized water alone. During 38-day biotic incubation, more than 2100 μg/L of As(III) and 4.2 mg/L of Fe(II) levels were released from the soils amended with LMWOCs substrates, compared to the levels of As(III) and Fe(II) (less 35 μg/L and 1.82 mg/L) derived from the biotic supplementation with deionized water alone. PCR-DGGE indicated that several LMWOCs-responded bacteria were mostly related to Firmicutes and Proteobacteria. Moreover, a negligible impact on the abundance of Fe(III)-reducing family Geobacteraceae was indicated in the LMWOCs-amended soils. However, an increased abundance of sulfate-reducing bacteria but a decreased abundance of arsenate-respiring bacteria were indicated upon the soils supplemented with acetate alone, compared with other LMWOC amendments. DNA-stable isotope probing analysis demonstrated that the dual roles of acetate was not only served as an electron donor for biotransformation of As(V)/Fe(III) in soil, but also assimilated as a powerful energy source to promote the growth of sulfate-reducing bacteria. The findings suggest that there are specific bacteria that preferentially respond to the additions of LMWOC for controlling the biochemical cycle process of As/Fe in soils.     

Arsenic Resistance and Bioaccumulation of an Indigenous Bacterium Isolated from Aquifer Sediments of Datong Basin,Northern China

To obtain bacteria with arsenic accumulation potential that can be used to remove arsenic from contaminated waters, experiments were made to investigate the tolerance and accumulation to arsenic of an indigenous bacterium XZM002 isolated from aquifer sediments of Datong Basin, northern China. The results showed that strain XZM002 belongs to the genus Bacillus and has evolved defense mechanisms to reduce arsenic injury: the change of cellular shape from initial rod to oval and then to round with increment of arsenic toxicity. The effect of arsenate or arsenite on the bacterial growth was also investigated. Results showed that growth of the strain was inhibited under As(III) and high concentration As(V) (over 1200 μg l^?1) conditions in the first 2 days and promoted under low concentration As(V) (under 400 μg l^?1) condition. Its arsenic bioaccumulation potential was surveyed by monitoring the concentration changes of total arsenic and arsenic speciation in the medium and in the cytoplasm, and those of total arsenic on the membrane. Methylated arsenic species were not detected throughout the experiment. The results indicated that 11.5% of arsenic was removed from liquid medium into the bacterial cells and 9.22% of As(V) in the medium was transformed gradually to As(III) during 4 d of incubation. Approximately 80% of the total accumulated arsenic was adsorbed onto the membrane instead of into cytoplasm; and the arsenic accumulation almost approached saturation after incubation for 72 h.     

Exceptions in patterns of arsenic compounds in urine of acute promyelocytic leukaemia patients treated with As<Subscript>2</Subscript>O<Subscript>3</Subscript>

Arsenic trioxide (As(III) in solution) has been shown to be the most active single agent in combating acute promyelocytic leukemia (APL). It is metabolized and excreted via urine as monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and As(V), along with excess As(III). In our study eight APL patients were treated (intravenously) with 0.15 mg As₂O₃/kg/day. During the therapy As(III) and its metabolites were followed in pre- and post-infusion urine using HPLC for separation followed by on-line detection using hydride generation-atomic fluorescence spectrometry. Five patients had a normal excretion pattern of residual arsenic compounds in morning pre-infusion urine, with 15–25 % of As(III), 35–55 % of DMA, 25–30 % of MMA and 1–5 % of As(V), while three patients showed unexpected exceptions from typical excretion patterns of arsenic compounds (i) a high DMA/MMA ratio (factor 5.3), (ii) severe As(III) oxidation (10.2 % As(III) converted to As(V)) or (iii) the presence of an excessive amount of As(III) (average 30.4 % of total arsenic). Intriguing was the occurrence of post-infusion oxidation of As(III) to As(V) observed in almost all patients and being especially high (>40 %) in patient with increased residual As(V). Results indicate that arsenic metabolites patterns can be unpredictable. Observed high levels of un-metabolised As(III) are a warning signal for side effects and for routine determination of arsenic metabolites during first days of treatment. High or low percentages of MMA or DMA did not show any observable effect on treatment results, while clear presence of post-infusion As(V) supports theoretical claims of in vivo oxidation (detoxification) of As(III) to As(V) associated with various metabolic processes.     

Extraction of hydrocarbons from freshwater green microalgae (Botryococcus sp.) biomass after phycoremediation of domestic wastewater

This study was undertaken to analyze the efficiency of Botryococcus sp. in the phycoremediation of domestic wastewater and to determine the variety of hydrocarbons derived from microalgal oil after phycoremediation. The study showed a significant (p < 0.05) reduction of pollutant loads of up to 93.9% chemical oxygen demand, 69.1% biochemical oxygen demand, 59.9% total nitrogen, 54.5% total organic carbon, and 36.8% phosphate. The average dry weight biomass produce was 0.1 g/L of wastewater. In addition, the dry weight biomass of Botryococcus sp. was found to contain 72.5% of crude oil. The composition analysis using Gas Chromatogram - Mass Spectrometry (GC-MS) found that phthalic acid, 2-ethylhexyltridecyl ester (C₂₉H₄₈O₄), contributed the highest percentage (71.6%) of the total hydrocarbon compounds to the extracted algae oil. The result of the study suggests that Botryococcus sp. can be used for effective phycoremediation, as well as to provide a sustainable hydrocarbon source as a value-added chemical for the bio-based plastic industry.     

Effect of Fluoride on Arsenic Uptake from Arsenic-Contaminated Groundwater using Pteris vittata L.

High-arsenic groundwater in inland basins usually contains high concentrations of fluoride. In the present study, the effects of fluoride on arsenic uptake by Pteris vittata and on arsenic transformation in growth media were investigated under greenhouse conditions. After P. vittata was hydroponically exposed to 66.8 μM As (V) in the presence of 1.05 mM F^? in the form of NaF, KF, or NaF+KF for 10 d, no visible toxicity symptoms were observed, and there were not significant differences in the dry biomass among the four treatments. The results showed that P. vittata tolerated F^? concentrations as high as 1.05 mM but did not accumulate fluoride in their own tissues. Arsenic uptake was inhibited in the presence of 1.05 mM F^?. However, in hydroponic batches with 60 μM As (III) or 65 μM As (V), it was found that 210.6 and 316.0 μM F^? promoted arsenic uptake. As(III) was oxidized to As(V) in the growth media in the presence and absence of plants, and F^? had no effect on the rate of As(III) transformation. These experiments demonstrated that P. vittata was a good candidate to remediate arsenic-contaminated groundwater in the presence of fluoride. Our results can be used to develop strategies to remediate As-F-contaminated water using P. vittata.     

A subgroup of plant aquaporins facilitate the bi-directional diffusion of As(OH)<Subscript>3</Subscript> and Sb(OH)<Subscript>3</Subscript>across membranes

Background  

Arsenic is a toxic and highly abundant metalloid that endangers human health through drinking water and the food chain. The most common forms of arsenic in the environment are arsenate (As(V)) and arsenite (As(III)). As(V) is a non-functional phosphate analog that enters the food chain via plant phosphate transporters. Inside cells, As(V) becomes reduced to As(III) for subsequent extrusion or compartmentation. Although much is known about As(III) transport and handling in microbes and mammals, the transport systems for As(III) have not yet been characterized in plants.     

Phycoremediation of phenol-polluted petro-industrial effluents and its techno-economic values as a win-win process for a green environment,sustainable energy and bioproducts

The discharge of the toxic phenol-polluted petro-industrial effluents (PPPIE) has severe environmental negative impacts, thus it is mandatory to be treated before its discharge. The objective of this review was to discuss the sustainable application of microalgae in phenols degradation, with a special emphasis on the enzymes involved in this bioprocess and the factors affecting the success of PPPIE phycoremediation. Moreover, it confers the microalgae bioenergetic strategies to degrade different forms of phenols in PPPIE. It also points out the advantages of the latest application of bacteria, fungi and microalgae as microbial consortia in phenols biodegradation. Briefly, phycoremediation of PPPIE consumes carbon dioxide emitted from petro-industries for; valorization of the polluted water to be reused and production of algal biomass which can act as a source of energy for such integrated bioprocess. Besides, the harvested algal biomass can feasibly produce; third-generation biofuels, biorefineries, bioplastics, fish and animal feed, food supplements, natural dyes, antioxidants and many other valuable products. Consequently, this review precisely confirms that the phycoremediation of PPPIE is a win-win process for a green environment and a sustainable future. Thus, to achieve the three pillars of sustainability; social, environmental and economic; it is recommendable to integrate PPPIE treatment with algal cultivation. This integrated process would overcome the problem of greenhouse gas emissions, global warming and climate change, solve the problem of water-scarce, and protect the environment from the harmful negative impacts of PPPIE.     

The removal of As(III) and As(V) from aqueous solutions by waste materials

The use of different waste materials such as Atlantic Cod fish scale, chicken fat, coconut fibre and charcoal in removing arsenic [As(III) and As(V)] from aqueous solutions was investigated. Initial experimental runs, conducted for both As(III) and As(V) with the aforementioned materials, demonstrated the potential of using Atlantic Cod fish scale in removing both species of arsenic from aqueous streams. Therefore, the biosorbent fish scale was selected for further investigations and various parameters such as residence time, adsorbent dose, initial concentration of adsorbate, grain size of the adsorbent and pH of the bulk phase were studied to establish optimum conditions. The maximum adsorption capacity was observed at pH value 4.0. The equilibrium adsorption data were interpreted by using both Freundlich and Langmuir models. Rapid small-scale column tests (RSSCT) were also performed to determine the breakthrough characteristics of the arsenic species with respect to packed biosorbent columns.     

The ArsD As(III) metallochaperone

Arsenic, a toxic metalloid widely existing in the environment, causes a variety of health problems. The ars operon encoded by Escherichia coli plasmid R773 has arsD and arsA genes, where ArsA is an ATPase that is the catalytic subunit of the ArsAB As(III) extrusion pump, and ArsD is an arsenic chaperone for ArsA. ArsD transfers As(III) to ArsA and increases the affinity of ArsA for As(III), allowing resistance to environmental concentrations of arsenic. Cys12, Cys13 and Cys18 in ArsD form a three sulfur-coordinated As(III) binding site that is essential for metallochaperone activity. ATP hydrolysis by ArsA is required for transfer of As(III) from ArsD to ArsA, suggesting that transfer occurs with a conformation of ArsA that transiently forms during the catalytic cycle. The 1.4 Å x-ray crystal structure of ArsD shows a core of four ??-strands flanked by four ??-helices in a thioredoxin fold. Docking of ArsD with ArsA was modeled in silico. Independently ArsD mutants exhibiting either weaker or stronger interaction with ArsA were selected. The locations of the mutations mapped on the surface of ArsD are consistent with the docking model. The results suggest that the interface with ArsA involves one surface of ??1 helix and metalloid binding site of ArsD.     

Use of X-ray absorption spectroscopy and biochemical techniques to characterize arsenic uptake and reduction in pea (Pisum sativum) plants.

Arsenite (As(III)) and arsenate (As(V)) uptake by peas was investigated using inductively coupled plasma/optical emission spectroscopy (ICP-OES) at pH below 4 and at pH 5.8. Additionally, total amylolitic activity and alpha-amylase (1,4-alpha-d-glucan glucanohydrolase; EC 3.2.1.1) activity was assayed in plants exposed to arsenic treatments. At pH below 4, the uptake for As(III) and As(V) in roots was 137 and 124 mg As kg(-1) dry weight (d wt), respectively. Translocation of arsenic to the aerial part was relatively low ( approximately 5mg As kg(-1) d wt). The uptake for As(III) and As(V) in roots at pH 5.8 was about 43 and 30 mg As kg(-1) d wt, respectively, and translocation of As to the aerial part was not detectable. None of the arsenic treatments affected the total amylolitic activity in roots; however, the shoots from all treatments showed an increase in the total amylolitic activity. Alpha-amylase activity in the pea leaves was not significantly affected by arsenic treatments. X-ray absorption spectroscopy (XAS) studies showed a reduction of As(V) to As(III) in the roots. From linear combination X-ray absorption near edge structure (LC-XANES) fittings, it was determined that arsenic was present as a mixture of As(III) oxide and sulfide in pea roots.     

The role of selected tree species in industrial sewage sludge/flotation tailing management

The aim of the study was to estimate the ability of ten tree and bush species to tolerate and accumulate Cd, Cu, Pb, Zn, and As species [As(III), As(V), and total organic arsenic] in industrial sewage sludge extremely contaminated with arsenic (almost 27.5 g kg^?1) in a pot experiment. The premise being that it will then be possible to select the most promising tree/bush species, able to grow in the vicinity of dams where sewage sludge/flotation tailings are used as landfill. Six of the ten tested tree species were able to grow on the sludge. The highest content of total As was observed in Betula pendula roots (30.0 ± 1.3 mg kg^?1 DW), where the dominant As species was the toxic As(V). The highest biomass of Quercus Q1 robur (77.3 § 2.6 g) and Acer platanoides (76.0 § 4.9 g) was observed. A proper planting of selected tree species that are able to thrive on sewage sludge/flotation tailings could be an interesting and promising way to protect dams. By utilizing differences in their root systems and water needs, we will be able to reduce the risk of fatal environmental disasters.     

Arsenic-resistant <Emphasis Type="BoldItalic">Pseudomonas</Emphasis> spp. and <Emphasis Type="BoldItalic">Bacillus</Emphasis> sp. bacterial strains reducing As(V) to As(III), isolated from Alps soils,Italy

Five arsenic-resistant bacterial strains (designated MP1400, MP1400a, MP1400d, APSLA3, and BPSLA3) were isolated from soils collected at the Alps region (Italy), which showed no contamination by arsenic. Phylogenetic analysis of the 16S rRNA gene sequences assigned them to the genera Pseudomonas and Bacillus. Bacillus sp. strain 1400d and Pseudomonas spp. strains APSLA3 and MP1400 showed higher tolerance to As(III), as indicated by minimum inhibitory concentrations of 10 mmol/L. Pseudomonas sp. strain MP1400 exhibited higher tolerance to As(V) (minimum inhibitory concentration of 135 mmol/L). The isolated arsenic-resistant strains were able to reduce As(V) to As(III), especially Pseudomonas sp. strain MP1400 reducing 2 mmol/L of As(V) to As(III) within 24 h. The results suggest that the isolated bacterial strains play a role in the arsenic biogeochemical cycle of arsenic-poor soils in the Alps mount area.     

Toxicity of arsenic (III) and (V) on plant growth, element uptake, and total amylolytic activity of mesquite (Prosopis juliflora x P. velutina)

The effects of arsenite [As(III)] and arsenate [As(V)] on the growth of roots, stems, and leaves and the uptake of arsenic (As), micro- and macronutrients, and total amylolytic activity were investigated to elucidate the phytotoxicity of As to the mesquite plant (Prosopis juliflora x P. velutina). The plant growth was evaluated by measuring the root and shoot length, and the element uptake was determined using inductively coupled plasma optical emission spectroscopy. The root and leaf elongation decreased significantly with increasing As(III) and As(V) concentrations; whereas, stem elongation remained unchanged. The As uptake increased with increasing As(III) or As(V) concentrations in the medium. Plants treated with 50 mg/L As(III) accumulated up to 920 mg/kg dry weight (d wt) in roots and 522 mg/kg d wt in leaves, while plants exposed to 50 mg/L As(V) accumulated 1980 and 210 mg/kg d wt in roots and leaves, respectively. Increasing the As(V) concentration up to 20 mg/L resulted in a decrease in the total amylolytic activity. On the contrary, total amylolytic activity in As(III)-treated plants increased with increasing As concentration up to 20 mg/L. The macro- and micronutrient concentrations changed in As-treated plants. In shoots, Mo and K were reduced but Ca was increased, while in roots Fe and Ca were increased but K was reduced. These changes reduced the size of the plants, mainly in the As(III)-treated plants; however, there were no visible sign of As toxicity.     

Inhibition of iron(II) oxidation by arsenic(III,V) in Thiobacillus ferrooxidans: Effects on arsenopyrite bioleaching

Summary The more complex inhibitory effect of As(III) than that of As(V) on Fe(II) oxidation in a non-growing Thiobacillus ferrooxidans suspension was demonstrated. The yield of arsenic bioextraction from a chalcopyrite concentrate was not affected by arsenic inhibition due to the low sensitivity of the strain to arsenic ions, supported by a spontaneous conversion of As(III) to As(V).     

Integration Process for Protein Extraction from Microalgae Using Liquid Biphasic Electric Flotation (LBEF) System

Microalgae are the most promising sources of protein, which have high potential due to their high-value protein content. Conventional methods of protein harnessing required multiple steps, and they are generally complex, time consuming, and expensive. Currently, the study of integration methods for microalgae cell disruption and protein recovery process as a single-step process is attracting considerable interest. This study aims to investigate the novel approach of integration method of electrolysis and liquid biphasic flotation for protein extraction from wet biomass of Chlorella sorokiniana CY-1 and obtaining the optimal operating conditions for the protein extraction. The optimized conditions were found at 60% (v/v) of 1-propanol as top phase, 250 g/L of dipotassium hydrogen phosphate as bottom phase, crude microalgae loading of 0.1 g, air flowrate of 150 cc/min, flotation time of 10 min, voltage of 20 V and electrode’s tip touching the top phase of LBEF. The protein recovery and separation efficiency after optimization were 23.4106?±?1.2514% and 173.0870?±?4.4752%, respectively. Comparison for LBEF with and without the aid of electric supply was also conducted, and it was found that with the aid of electrolysis, the protein recovery and separation efficiency increased compared to the LBEF without electrolysis. This novel approach minimizes the steps for overall protein recovery from microalgae, time consumption, and cost of operation, which is beneficial in bioprocessing industry.     

微生物氧化As(III)和Sb(III)的研究进展

砷(Arsenic,As)和锑(Antimony,Sb)属于同族元素,具有相似的化学性质,是公认的有毒类金属(metalloid),广泛存在于自然界中。随着人类的发展,环境中砷和锑的污染日益严重,类金属污染环境的修复已经刻不容缓。现已表明,自然界中的微生物在砷和锑的生物地球化学循环中发挥着重要的作用,尤其是微生物的氧化作用,可以将毒性较强的亚砷酸盐[Arsenite,As(III)]和亚锑酸盐[Antimonite,Sb(III)]氧化为毒性较低的砷酸盐[Arsenate,As(V)]和锑酸盐[Antimonate,Sb(V)],被认为是一种潜在的类金属污染环境修复方法。本文就国内外对As(III)氧化菌和Sb(III)氧化菌的多样性、As(III)和Sb(III)微生物氧化调控机制和应用的研究进展进行总结,旨在为深入了解和探索微生物介导的砷和锑生物地球化学循环及污染环境的微生物修复提供参考。     

Potential of diatom consortium developed by nutrient enrichment for biodiesel production and simultaneous nutrient removal from waste water

Because of the decreasing fossil fuel supply and increasing greenhouse gas (GHG) emissions, microalgae have been identified as a viable and sustainable feedstock for biofuel production. The major effect of the release of wastewater rich in organic compounds has led to the eutrophication of freshwater ecosystems. A combined approach of freshwater diatom cultivation with urban sewage water treatment is a promising solution for nutrient removal and biofuel production. In this study, urban wastewater from eutrophic Hussain Sagar Lake was used to cultivate a diatom algae consortium, and the effects of silica and trace metal enrichment on growth, nutrient removal, and lipid production were evaluated. The nano-silica-based micronutrient mixture Nualgi containing Si, Fe, and metal ions was used to optimize diatom growth. Respectively, N and P reductions of 95.1% and 88.9%, COD and BOD reductions of 91% and 51% with a biomass yield of 122.5 mg L^?1 day^?1 and lipid productivity of 37 mg L^?1 day^?1 were observed for cultures grown in waste water using Nualgi. Fatty acid profiles revealed 13 different fatty acids with slight differences in their percentage of dry cell weight (DCW) depending on enrichment level. These results demonstrate the potential of diatom algae grown in wastewater to produce feedstock for renewable biodiesel production. Enhanced carbon and excess nutrient utilization makes diatoms ideal candidates for co-processes such as CO₂ sequestration, biodiesel production, and wastewater phycoremediation.