地下水系统中富里酸-铁-砷的共沉淀行为

地下水系统中砷酸盐与Fe(Ⅲ)的共沉淀可以有效减少砷向水生环境的释放。有机质易参与Fe(Ⅲ)的沉淀过程,从而影响砷的固定,但目前对基于共沉淀反应的C-Fe-As耦合机制的认识还非常有限。选取富里酸(FA)为典型有机质,通过开展室内批试验,探讨不同Fe(Ⅲ)浓度和pH值条件下地下水系统中FA-Fe(Ⅲ)-As(Ⅴ)的共沉淀行为,并综合采用三维荧光光谱(3D-EEMs)、X射线衍射(XRD)、扫描电子显微镜与能谱分析(SEM-EDS)和X射线光电子能谱(XPS)等表征手段,揭示地下水系统中有机质-铁(氢)氧化物共沉淀(OFC)的固砷机理。结果表明:地下水系统中较高的Fe(Ⅲ)浓度促进水解共沉淀发生,有利于砷的固定及FA的组分分馏,FA中大分子量、强芳香性组分优先与水铁矿结合形成OFC;As(Ⅴ)通过占据OFC中类腐殖质组分与水铁矿的结合位点而被固定;地下水系统中较高的pH值抑制共沉淀发生,FA提高了Fe(Ⅲ)的溶解度,不利于砷的固定。该研究结果有助于深入理解地下水系统中砷与碳元素的地球化学循环过程,可为地下水砷污染的治理与防治提供理论基础。

水分管理模式对水稻根区砷铁磷动态变化规律的影响

采用土-砂联合培养的方法,研究了淹水-湿润-干湿交替3种不同水分管理模式对整个生育期内水稻根区介质（石英砂）中砷、铁、磷含量在不同生育期阶段和不同根区层次（距土-砂表面0-10 cm为上层,10-20cm为中层,20-30 cm为下层）动态变化的影响。结果表明：淹水管理模式下,砷的含量总体高于其它两种水分处理（P〈0.05）,而铁的含量则湿润处理总体较高（P〈0.05）,水分对不同生育期磷含量的影响未达到显著水平;根区的中层和下层砂介质中砷含量有高于上层的趋势（P〈0.05）,铁含量则是上层总体高于下层（P〈0.01）,而各层中磷含量没有显著性差异;从不同的生育阶段来看,砷和磷含量随生育期的波动不明显,但铁含量在整个生育期的变化则达到了极显著的水平（P〈0.001）。此外,在3个水分管理模式中,只有淹水条件下砷和铁的含量表现出显著正相关关系（r=0.45（n=36）,P〈0.05）。就各层而言,上层及中层,干湿交替处理下砷铁表现出一定的相关性,相关系数分别为0.65（P〈0.05）和0.84（P〈0.01）;根区的下层淹水管理模式下砷铁、砷磷均存在极显著正相关,相关系数均为0.87（P〈0.01）。

地下水环境中铁-砷运移与氧化现场模拟研究

砷在含水层中迁移、转化、释放等地球化学行为往往与地下水的氧化还原环境密切相关。本研究在山阴地区开展了为期1个月的现场模拟试验,模拟地下水环境中砷的运移,另外注入Fe(Ⅱ)溶液,同时连续曝气,以改变地下水的强氧化环境,从而达到As(Ⅲ)向As(Ⅴ)的转化并将其沉降固定的目的。试验结果表明As(Ⅲ)和As(Ⅴ)在地下水中的迁移速率是其在2mm砂质颗粒介质中的迁移速率的92.6和109.9倍,前者的速率要大于后者。在氧单独存在的情况下溶液中砷的含量变化甚小,而在加入Fe(Ⅱ)溶液以后,连续曝气的同时,Fe(Ⅱ)被氧化成Fe(Ⅲ),从而将As(Ⅲ)氧化成As(Ⅴ)并结合絮凝沉降使得砷的浓度明显降低。

Arsenic availability and transportation in soil-rice system affected by iron-modified biochar

Iron-modified biochar(FeOS)is known to be effective at immobilization of arsenic(As)in soils.A pot experiment was conducted to investigate the effects of FeOS on As availability and ttransportation in the soil-rice system at different growth stages of rice with different pollution levels.The results showed that Fe concentration decreased and As concentration increased in paddy soils with the FeOS addition,especially in 120 mg/kg As treatment,the As concentration decreased by 16.46%and 30.56%at the maturity stage with 0.5%and 1%FeOS additions,respectively.Compared with the control,the application of FeOS reduced the arsenic content in rice tissues and increased the biomass,with the root biomass increased by 12.68%and the shoot biomass was increased by 8.94%with the addition of 1%FeOS.This may be related to the promotion of iron plaque formation and the transformation of microbial community structure in FeOS treatments,in accordance with the result of gene abundance and Fe/As contents of iron plaque in the study.This study is expected to provide further support and theoretical basis for the application of FeOS in the remediation of As contaminated paddy soil.

A new mixed-valent iron arsenate black crystal

Scorodite（FeAsO4·2H2O）is the most popular phase for arsenic（As）immobilization while the reductive dissolution of Fe（Ⅲ）to Fe（Ⅱ）will promote As release.In the present study,an equilibrium between Fe（Ⅲ）and Fe（Ⅱ）was achieved in scorodite preparation system by introducing certain alcohol（methanol,ethanol,isopropanol or tert-butanol）,and thus a new mixed-valent iron arsenate black crystal formulated as Fe（Ⅱ）（5.2）Fe（Ⅲ）（8.8）（HAsO4）4（AsO4）8·H2O was prepared.In comparison with scorodite,the black crystal has higher As content（36.4%,mass fraction）and lower crystal water content（0.73%,mass fraction）.Additionally,the leaching concentration of As can be lower than the threshold value（5 mg/L）regulated by identification standards for hazardous wastes of China（GB 5080.3-2007）.Therefore,this new mixed-valent iron arsenate crystal could be classified as a non-hazardous and promising As-bearing phase in environmental applications.

Synthesis of glycerine-xanthate and its depressing mechanism in separation of marmatite from arsenopyrite

A small molecular organic depressor glycerine-xanthate was synthesized. The effect of glycerine-xanthate on the flotation of sulfide minerals was investigated based on a function of pH value and concentration of glycerine-xanthate through flotation experiments in the presence and absence of Cu^2＋. The results show that glycerinee-xanthate has a strong dressing effect on marmatite at pH〉6 and on arsenopyrite in weak acid and base conditions with butyl-xanthate as collector. In the presence of glycerine -xanthate, marmatite is activated by addition of Cu^2＋, but arsenopyrite cannot be activated and remains unfloatable. So the selective separation can be achieved for two minerals. The depression of glycerine-xanthate on sulfide minerals was discussed based on the radical electronegative calculation and the theory of HSAB. Infrared spectrum shows that there are some -OH and-CSS-in glycedne-xanthate molecule, which competes with butyl-xanthate on the mineral surface. As a result of many hydrophilic groups in glycerine-xanthate, the surfaces of marmatite and arsenopyrite become hydrophilic, thus the flotation of marmatite and arsenopyrite is depressed. The collector is adsorbed preferentially on the surface of marmatite and it shows a better floatability in the presence of Cu^2＋, whereas, the surface of arsenopyrite absorbs glycerine-xanthate and the flotation of arsenopyrite is depressed by glycerine-xanthate.

Microstructure and magnetic properties of FeAs with coarse-grain and nanocrystalline structure

The microstructure and magnetic properties of iron arsenide(FeAs) with coarse-grain and nanocrystalline structure were investigated. Coarse-grain FeAs was synthesized through high-energy ball milling and heat treatment. Nanocrystalline FeAs was obtained by ball milling of coarse-grain FeAs. The results suggest that the reduced grain size of FeAs(from >100 to 32.4 nm) is accompanied by the introduction of internal strains up to 0.568% with ball milling time from 0 to 32 h. The magnetic properties of FeAs show that the coercivity is reduced from 29.2 to 15.6 kA/m and the magnetization is increased over time of milling. The low coercivity is mainly due to the small grain size stemmed from ball milling, while the increase of magnetization is primarily caused by the change of lattice parameters of FeAs and the emergence of superparamagnetic phase at the same time.

Formation of arsenic−copper-containing particles and their sulfation decomposition mechanism in copper smelting flue gas

The heat recovery steam generator(HRSG)of copper smelting generates a large number of arsenic−coppercontaining particles,and the in-situ separation of arsenic and copper is of importance for cutting off environmental risk and realizing resource recovery.The formation of arsenic−copper-containing particles was simulated,the method of in-situ decomposition of arsenic−copper-containing particles by pyrite was proposed,and the decomposition mechanism was confirmed.It was found that particles with high arsenic content were formed in the simulated HRSG,and copper arsenate was liable for the high arsenic content.Pyrite promoted the sulfation of copper,leading to the in-situ decomposition of copper arsenate.In this process,gaseous arsenic was released,and thus the separation of arsenic and copper was realized.

Physicochemical properties of arsenic-bearing lime-ferrate sludge and its leaching behaviors

Physicochemical properties and leaching behaviors of two typical arsenic-bearing lime?ferrate sludges(ABLFS),waste acid residue(WAR)and calcium arsenate residue(CAR),are comprehensively described.The chemical composition,morphological features,phase composition and arsenic occurrence state of WAR and CAR are analyzed by ICP?AES,SEM?EDS,XRD,XPS and chemical phase analysis.The toxicity leaching test and three-stage BCR sequential extraction procedure are utilized to investigate arsenic leaching behaviors.The results show that the contents of arsenic in WAR and CAR are2.5%and21.2%and mainly present in the phases of arsenate and arsenic oxides dispersed uniformly or agglomerated in amorphous particles.The leaching concentrations of arsenic excess119and1063times of TCLP standard regulatory level with leaching rates of47.66%and50.15%for WAR and CAR,respectively.About90%of extracted arsenic is in the form of acid soluble and reducible,which is the reason of high arsenic leaching toxicity and environmental activity of ABLFS.This research provides comprehensive information on harmless disposal of ABLFS from industrial wastewater treatment of lime?ferrate process.

Interaction mechanism between arsenate and fayalite-type copper slag at high temperatures

The interaction mechanism between sodium arsenate and fayalite-type copper slag at 1200℃was investigated through XRD,XPS,HRTEM,TCLP and other technical means and methods.The results indicated that the proportions of sodium arsenate in the slag and flue gas phases were approximately 30%and 70%,respectively.The addition of sodium arsenate depolymerized the fayalite structure and changed it from a crystalline state to an amorphous state.The fayalite structural changes indicated that the[AsO_(4)]tetrahedron in sodium arsenate combined with the[SiO_(4)]tetrahedron and[FeO_(4)]tetrahedron through bridging oxygen to form a silicate glass structure.The TCLP test results of the samples before and after the high temperature reaction of fayalite and sodium arsenate showed that after high temperature reaction,fayalite could effectively reduce the leaching toxicity of sodium arsenate,reducing the leaching concentration of arsenic from 3025.52 to 12.8 mg/L before and after reaction,respectively.

Mobility of Arsenic and Heavy Metals in a Sandy-Loam Textured and Carbonated Soil

The continued effect of the pyrite-tailing oxidation on the mobility of arsenic, lead, zinc, cadmium, and copper was studied in a carbonated soil under natural conditions, with the experimental plot preserved with a layer of tailing covering the soil during three years. The experimental area is located in Southern Spain and was affected by a pyrite-mine spill. The climate in the area is typically Mediterranean, which determines the rate of soil alteration and element mobility. The intense alteration processes that occurred in the soil during three years caused important changes in its morphology and a strong degradation of the main soil properties. In this period, lead concentrated in the first 5 mm of the soil, with concentrations higher than 1500 mg kg?1, mainly associated to the neoformation of plumbojarosite. Arsenic was partially leached from the first 5 mm and mainly concentrated between 5–10 mm in the soil, with maximum values of 1239 mg kg-1; the retention of arsenates was related to the neoformation of iron hydroxysulfates (jarosite, schwertmannite) and oxyhydroxides (goethite, ferrihydrite), both with a variable degree of crystallinity. The mobility of Zn, Cd, and Cu was highly affected by pH, producing a stronger leaching in depth; their retention was related to the forms of precipitated aluminium and, in the case of Cu, also to the neoformation of hydroxysulfate.

Ultrasonic-enhanced selective sulfide precipitation of copper ions from copper smelting dust using monoclinic pyrrhotite

The sulfide passivation film produced on the surface seriously prevents further reaction in the process of using monoclinic pyrrhotite(MPr)to treat heavy metal ions in wastewater.Ultrasonic technology was introduced to assist MPr to recover the copper ions.XPS result proves that CuS products exist on the surface of MPr.XRD and SEM results show that the CuS on the particles’surface is stripped under ultrasonic condition.The kinetics results indicate that the reaction under both conventional and ultrasonic conditions conform to the Avrami model.The reaction process changes from diffusion control to chemical reaction control under the ultrasonic condition as the solid layer is stripped off.The presence of ultrasonic significantly reduces the acidity and temperature required for the reaction and enhances the utilization efficiency of MPr;by controlling the amount of MPr,the removal rates of copper and arsenic in copper smelting dust leachate exceed 99%and 95%,respectively.

Characterization of acylated homoserine lactone derivatives and their influence on biofilms of Acidithiobacillus ferrooxidans BY-3 under arsenic stress

Quorum sensing is one kind of cell-to-cell signalling system among microorganisms that works in response to their population density via autoinducers exemplified by AHL and oligopeptides. In this study, fourteen AHL derivatives were synthesised by a chemical synthesis method, and two types of AHL derivatives were measured and screened by crystal violet staining assay, which have more obvious inhibitory effects on A. ferrooxidans biofilms under arsenic environment. Their structures were verified through IR and NMR identification. The morphological changes of A. ferrooxidans under the influence of the AHL derivatives were compared. In addition, the effects of AHL derivatives(0.1 μg/mL and 1 μg/mL) on membrane formation of A. ferrooxidans under high concentration of arsenic resistance(1,600 mg/L) were explored. Solid experimental data firstly showed that a portion of logarithmic microorganisms were ruptured under the effect of high arsenic concentration. Secondly, the volume of the cell shrank and the number of extracellular polymeric substances decreased after the addition of the AHL derivatives at high concentrations. Therefore, we found here that two derivatives used at concentrations of 0.1 μg/mL and 1 μg/m L accompanied with high concentration of arsenic can both effectively restrict biofilms formation by A. ferrooxidans.

Removal and stabilization of arsenic from anode slime by forming crystal scorodite

A process was proposed for removing and stabilizing arsenic(As) from anode slime. The anode slime with high arsenic concentration was pretreated by circular alkaline leaching process. Then, the arsenic in the leaching solution can be further precipitated as a form of scorodite crystalline(FeAsO4·2H2O). In the precipitating arsenic reaction, in which ferrous ions were oxidized by air gas, the effects of acidity(p H), reaction temperature, air flow rate, initial concentration of arsenic and initial molar ratio of Fe(II) to As(V) on arsenic precipitation were investigated. The results showed that sufficiently stable crystal scorodite could be achieved under the condition of initial arsenic concentration of 10 g/L, pH 3.0-4.0, Fe/As molar ratio of 1.5, the temperature of 80-95 °C, and the air flow rate higher than 120 L/h. Under the optimal condition, more than 78% of arsenic could be precipitated as a form of scorodite crystalline. The As leaching concentration of the precipitates was less than 2.0 mg/L and the precipitates may be considered to be safe for disposal.

Effect of arsenopyrite on thiosulfate leaching of gold

Arsenopyrite was artificially added into the thiosulfate leaching solution to clarify the role of arsenopyrite on the thiosulfate leaching of gold.The effect of arsenopyrite on the thiosulfate leaching of gold was studied by the thermodynamic calculation,mineral dissolution test,leaching test and XPS analysis.The results show that the thiosulfate consumption slightly increases with increasing the concentration of arsenopyrite,but the gold dissolution is obviously hindered.This may mainly attribute to the catalytic effect of arsenopyrite on the thiosulfate decomposition and the formation of passivation layer on the gold foil surface.The passivation layer likely consists of Cu2S or Cu（S2O3）35-,element S,FeOOH and iron arsenate,which is deduced from the XPS analysis.However,the negative effect of arsenopyrite can be eliminated by adding additives.It is found that both additives of sodium carboxymethyl（CMC） and sodium phosphate（SHPP） can not only decrease the thiosulfate consumption but also improve the gold dissolution.

Effect of arsenic on spatial pattern of radial oxygen loss and iron plaque formation in rice

The effects of different arsenic （As） treatments on spatial pattern of radial oxygen loss （ROL）, iron （Fe） plaque formation and As accumulation in rice were investigated using three rice genotypes, planted under greenhouse conditions. Arsenic was applied to soil at 50 and 100 mg/kg, with untreated soil used as a control having an average As concentration of 8.5 mg/kg. It was demonstrated that the ratio of ROL in root tips to that at the root base slightly decreased with increasing As concentration, suggesting that the spatial ROL patterns in these groups may be shifted from the “tight” barrier towards the “partial” barrier form. Furthermore, increasing As concentration led to a increase in Fe plaque formation on root surfaces. In addition, root As concentrations of genotypes in 50 and 100 mg/kg As treatments were significantly higher than that of control treatment （P〈0.05）. Grain As concentration of genotype Nanyangzhan （with lower ROL） was significantly higher （P〈0.05） than that of genotype CNT87059-3 with higher ROL.

Redox behavior and chemical species of arsenic in acidic aqueous system

Arsenic(As)removal from smelting acidic wastewater is an urgent task.The most common method is oxidation of trivalent As(III)to pentavalent As(V)subsequently precipitated by ferric(Fe(III))salts.Foundations of redox behavior and chemical species are of great importance for understanding As removal.In this work,cyclic voltammetry(CV)and UV?Vis spectroscopy were used for laboratory observation;meanwhile HSC and MINTEQ software were employed for theoretical analyses.It is found that As(III)oxidation,a multiple electron transfer reaction,is diffusion-controlled.The oxidation over-potential is very high(about0.9V)in sulfuric acid solutions(pH1.0).In addition,Fe(III)?As(V)complexes are evidenced by UV?Vis spectra and chemical species analyses in series of Fe(III)?As(V)?H2SO4?H2O solutions.Therefore,the Fe(III)and As(V)species distribution against pH values are determined and a newφ?pH diagram with inclusion of Fe?As complexes is consequently compiled based on thermodynamic data predicted by other researchers.

Stabilization of ferric arsenate sludge with mechanochemically prepared FeS2/Fe composites

FeS2/Fe composites were mechanochemically prepared with iron powder and pyrite for the stabilization of ferrite arsenate sludge(FAS).The effects of preparation parameters on stabilization performance were investigated.The results show that the optimum conditions are FeS2/Fe molar ratio of 5:5,milling time of 2 h,ball-to-material mass ratio of 15:1 and milling with stainless steel ball.Then,the composites were characterized by XRD,SEM,FTIR,etc.The physicochemical properties of FeS2/Fe mixture change dramatically,which is responsible for its excellent performance.Finally,the stabilization process of FAS was optimized.When the FAS is mixed with composites at mass ratio of 4:1 and milled for 30 min,the As leaching concentration of FAS can be reduced from 639.15 to 4.74 mg/L with the stabilization ratio of 99.2%.

Galvanic effect of magnetite on electrochemical oxidation of arsenopyrite in acidic culture medium

The galvanic interaction of arsenopyrite−magnetite in acidic culture medium was investigated by electrochemical measurements,X-ray photoelectron spectroscopy characterization and leaching experiments.The results indicated that the rest potential of magnetite was 321 mV,which was more anodic than 223 mV of arsenopyrite,and the galvanic current was 7.40μA,verifying the existence of the galvanic interaction between arsenopyrite and magnetite.The galvanic potential and polarization curves suggested that the redox behaviors of arsenopyrite dominated the overall galvanic interaction.The galvanic interaction enhanced the electrochemical dissolution of arsenopyrite with the generation of more oxidation products(S^(0),SO_(3)^(2−),SO_(4)^(2−)and AsO_(3)^(3−)) on arsenopyrite and an increase in the chemical reactivity of the surface.Leaching experiments of 6 days showed that the presence of magnetite improved the arsenic release from arsenopyrite by 30 mg/L,and further confirmed the enhanced oxidation of arsenopyrite when coupled with magnetite.

Iron Activation of Natural Aluminosilicates to Remove Arsenic from Groundwater

Low-cost adsorbents constituted by Fe-modified-aluminosilicates （laminar and zeolite type minerals） were developed and characterized to be used in the arsenic removal from groundwater. Iron activation was carried out ＂in situ＂ by the synthesis and deposition of mesoporous ferrihydrite. Natural iron-rich aluminosilicate was used as reference. All samples were characterized by X-ray diffraction, Raman spectroscopy, BET N2-adsorption, SEM-EDS microscopy and ICP chemical analysis. Experimental results of arsenic sorption showed that iron-poor raw materials were not active, unlike iron activated samples. The iron loading in all activated samples was below 5% （expressed as Fe203）, whereas the removal capacity of these samples reaches between 200-700 gg of As by g of adsorbent, after reusing between 17 cycles and 70 cycles up to adsorbent saturation. Differences can be associated to mineral structure and to the surface charge modification by iron deposition, affecting the attraction of the As-oxoanion. On the basis of low-cost raw materials, the easy chemical process for activation shows that these materials are potentially attractive for As（V） removal. Likewise, the activation of clay minerals, with natural high content of iron, seems to be a good strategy to enhance the arsenic adsorption ability and consequently the useful life of the adsorbent.