Simultaneous oxidation of Mn(II) and As(III) on cupric oxide (CuO) promotes As(III) removal at circumneutral pH

Oxidation of Mn(II) or As(III) by molecular oxygen is slow at pH < 9, while they can be catalytically oxidized in the presence of oxide minerals and then removed from contaminated water. However, the reaction mechanisms on simultaneous oxidation of Mn(II) and As(III) on oxide mineral surface and their accompanied removal efficiency remain unclear. This study compared Mn(II) oxidation on four common metal oxides (γ-Al₂O₃, CuO, α-Fe₂O₃ and ZnO) and investigated the simultaneous oxidation and removal of Mn(II) and As(III) through batch experiments and spectroscopic analyses. Among the tested oxides, CuO and α-Fe₂O₃ possess greater catalytic activity toward Mn(II) oxidation. Oxidation and removal kinetics of Mn(II) and As(III) on CuO indicate that O₂ is the terminal electron acceptor for Mn(II) and As(III) oxidation on CuO, and Mn(II) acts as an electron shuttle to promote As(III) oxidation and removal. The main oxidized product of Mn(II) on CuO is high-valent MnO_x species. This newly formed Mn(III) or Mn(IV) phases promote As(III) oxidation on CuO at circumneutral pH 8 and is reduced to Mn(II), which may be then released into solution. This study provides new insights into metal oxide-catalyzed oxidation of pollutants Mn(II) and As(III) and suggests that CuO should be considered as an efficient material to remediate Mn(II) and As(III) contamination.     

Effect of ionic strength on adsorption of As（Ⅲ） and As（Ⅴ） on variable charge soils

The study was to investigate the adsorption behavior of arsenite (As(Ⅲ)) and arsenate (As(Ⅴ)) on two variable charge soils, i.e., Haplic Acrisol and Rhodic Ferralsol at different ionic strengths and pH with batch methods. Results indicated that the amount of As(Ⅲ) adsorbed by these two soils increased with increasing solution pH, whereas it decreased with increasing ionic strength under the acidic condition. This suggested that As(Ⅲ) was mainly adsorbed on soil positive charge sites through electrostatic attraction under the acidic condition. Moreover, intersects of As(Ⅴ) adsorption-pH curves at different ionic strengths (a characteristic pH) are obtained for both soils. It was noted that above this pH, the adsorption of As(Ⅴ) was increased with increasing ionic strength, whereas below it the reverse trend was true. Precisely the intersect pH was 3.6 for Haplic Acrisol and 4.5 for Rhodic Ferralsol, which was near the values of PZSE (soil point of zero salt effect) of these soils. The effects of ionic strength and pH on arsenate adsorption by these soils were interpreted by the adsorption model. The results of zeta potential suggested that the potential in adsorption plane becomes less negative with increasing ionic strength above soil PZSE and decreases with increasing ionic strength below soil PZSE. These results further supported the hypothesis of the adsorption model that the potential in the adsorption plane changes with ionic strength with an opposite trend to surface charge of the soils. Therefore, the change of the potential in the adsorption plane was mainly responsible for the change of arsenate adsorption induced by ionic strength on variable charge soils.     

纳米零价铁颗粒去除As(III)和As(V)的动力学过程及性能研究

本研究系统分析了不同初始砷浓度和不同nZVI投加量等条件下,nZVI去除As（III）和As（V）的动力学过程和除砷性能.结果表明,nZVI可快速有效地去除As（III）和As（V）,除砷过程均符合准二级动力学模型,且As（III）的去除速率明显快于As（V）.在砷浓度为5 mg·L^-1时,As（III）去除速率常数达最大值0.30 g·mg^-1·min^-1,为As（V）去除速率（0.034 g·mg^-1·min^-1）的8.8倍.Weber-Morris粒子内扩散模型拟合结果表明,nZVI除砷速率是由外扩散和颗粒内扩散共同控制的.分析反应平衡时砷浓度测定结果,发现不同砷浓度条件下nZVI对As（III）的去除量为As（V）的1.5~2.6倍,nZVI对砷的去除量随初始砷浓度增加而降低,随nZVI投加量增加而增加.砷浓度为50.0 mg·L^-1时,As（III）和As（V）去除量达到最高,分别为152.14 mg·g^-1和62.02 mg·g^-1,均高于传统（羟基）氧化铁对As（III）和As（V）的去除量.因此,nZVI可高效去除水中As（III）和As（V）,且用于修复以As（III）污染为主的地下水更具有优势.     

草酸盐介导下含As(V)黄钾铁矾的相转化过程与As(V)的再分配行为

黄钾铁矾能够通过吸附和共沉淀作用固定酸性矿山废水（AMD）中的重（类）金属（如砷）,降低其迁移性和生物可利用性.草酸盐广泛存在于天然水环境中,其具有的羧酸官能团能改变铁矿物的稳定性,进而影响吸持的重（类）金属的再分配行为.利用水热法合成含As（V）黄钾铁矾,探究其在不同草酸盐浓度与pH条件下的溶解、重结晶和共沉淀As（V）的行为.研究结果表明,草酸盐与含As（V）黄钾铁矾表面Fe（III）活性位点配位形成的可溶性强络合物是促进矿物溶解的第一步和关键;在pH 2.5时,含As（V）黄钾铁矾的溶解速率随草酸盐浓度增加而增加,伴随大量As（V）释放到溶液,反应过程中只有少量As（V）重新吸附到固相上,这是由于草酸盐与As（V）竞争矿物表面的同一活性位点;在pH 6.5条件下,草酸盐促进含As（V）黄钾铁矾的重结晶,经X射线衍射分析表明针铁矿和纤铁矿为主要产物,能有效地吸附释放的As（V）.研究结果有助于揭示在AMD环境下黄钾铁矾沉积物与含羧酸官能团有机酸共存时对As（V）的释放和固定机理,对AMD环境中As（V）污染控制有重要意义.     

Oxidation of As（Ⅲ） by potassium permanganate

The oxidation of As（Ⅲ） with potassium permanganate was studied under conditions including pH, initial As（Ⅲ） concentration and dosage of Mn（Ⅶ）. The results have shown that potassium permanganate was an effective agent for oxidation of As（Ⅲ） in a wide pH range. The pH value of tested water was not a significant factor affecting the oxidation of As（Ⅲ） by Mn（Ⅲ）. Although theoretical redox analyses suggest that Mn（Ⅶ） should have better performance in oxidization of As（Ⅲ） within lower pH ranges, the experimental results show that the oxidation efficiencies of As（Ⅲ） under basic and acidic conditions were similar, which may be due to the adsorption of As（Ⅲ） on the Mn（OH）2 and MnO2 resulting from the oxidation of As（Ⅲ）.     

半连续活性污泥法对污水中五价砷的去除

采用控制污泥浓度ＭＬＳＳ为２０００ｍｇ／Ｌ的半动态试验，我们研究了活性污泥对不同浓度砷、同一浓度但有机负荷不同时的去除能力。结果表明：活性污泥对砷的吸附在１－２小时左右达到平衡状态；含２０ｐｐｍ、１００ｐｐｍ，Ａｓ（Ⅴ）和污泥作用１２小时后，其去除率分别为５５．８％和４６．３％；只有极少量Ａｓ（Ⅴ）转化成Ａｓ（Ⅳ）；污水的有机负荷（ＣＯＤ）高，污泥对砷的去除率也上升。     

利用天然磁黄铁矿去除水中As (V)的研究

考察了时间、pH、温度、吸附剂投加量、无机阴离子等因素对磁黄铁矿去除As(V)过程的影响.同时,对去除过程的动力学和等温线进行分析,并探究了动态去除的效果.结果显示:磁黄铁矿对As(V)的去除在24 h达到平衡;在pH值3~9范围内去除率都达到80%以上;温度升高和吸附剂用量增加都对As(V)去除具有促进作用;PO_4~(3-)、SiO_3~(2-)、CO_3~(2-)对吸附有较强的抑制作用;在As(V)初始浓度为2 mg·L~(-1)时动态吸附出水浓度在150个吸附床体积(BV)内能达到国家饮用水标准;吸附去除过程符合拟二级动力学方程和Langmuir等温方程.能谱仪和X射线电子能谱分析表明,去除过程是一个自发吸热的配位离子交换反应.本实验表明,天然磁黄铁矿是一种有潜力的除砷吸附剂.     

复合稳定剂对砷污染土壤的稳定研究

重金属污染土壤均含有多种元素,使用一种药剂对土壤进行稳定的效果不佳且处理费用较高.本研究采集富含砷(As)、镉(Cd)、锌(Zn)的重金属污染土壤,选用无机和有机稳定剂对土壤进行快速化学稳定化实验研究,利用酸浸提程序(TCLP法)评价土壤中重金属的浸出毒性,结果表明,含钙物质、含硫物质以及含铁物质对于降低金属流动性非常有效,6种试剂中稳定效率排序为:氧化钙>硫化钠>有机硫>壳聚糖>硫酸亚铁>二乙基二硫代氨基甲酸钠.根据不同试剂稳定重金属的靶向特性对两种类型稳定剂进行组合,对复合稳定剂的稳定效果进行评价,分析结果显示复配试剂的综合稳定效率更高:铁钙复配(3%硫酸亚铁+5%氧化钙)对土壤中3种金属的稳定率为81.7%、97.2%、68.2%,而有机硫氧化钙复配试剂(3%氧化钙+5%有机硫)对3种金属的稳定率达到76.6%、95.7%、93.8%.重金属形态测试的结果认为重金属从可交换态转变为还原态(无机类试剂)或氧化态(有机类试剂)是重金属稳定的主要原因,且形态转变程度决定了土壤的稳定程度.     

Shewanella oneidensis MR-1异化还原Fe(III)介导的As(III)氧化转化

在实验室模拟条件下,研究了Shewanella oneidensis MR-1作用下Fe(III)还原和As(III)氧化动力学及其影响因素.结果表明,Fe(III)被还原为Fe(II)的同时伴随着As(III)氧化为As(V);S. oneidensis MR-1 在含低浓度As(III)培养基上生长良好,在高浓度培养基上生长被抑制;As(III)通过制约菌体的生长与活性来抑制Fe(III)异化还原.同样,适量浓度的Fe(III)含量对As(III)氧化转化有很强的促进作用,但是过高浓度的Fe(III)浓度使得溶液中产生过多的Fe(II),从而对As(III)氧化转化有一定程度的抑制作用.此外,弱碱环境更有利于As(III)氧化转化.     

载铁(β-FeOOH)球形棉纤维素吸附剂去除地下水As(Ⅴ)的研究

制备了一种载铁(β- FeOOH)球形棉纤维素吸附剂,球珠孔隙度大,强度好,活性成分铁的载入量可高达360mg/mL ,(质量分数达50%) ,活性好.研究表明,当铁含量为220mg/mL时,该吸附剂对As(V)的最大吸附量为15.6mg/mL(33.2mg/g) ,Langmuir和Freundlich方程能很好地描述吸附等温线.吸附速度较快,10h可达到吸附平衡,吸附动力学符合Lagergren二级方程.SiO₃^2- ,SO₄^2-,Cl^-干扰离子均不影响砷的去除.柱吸附实验表明,空床停留时间为5.9min ,进水As(V)浓度为500μg/L时,As(V)的穿透体积为5000BV .吸附剂可以用1.5mol·L^-1 NaOH再生,洗脱和再生效率可达90%以上.活性成分β-FeOOH形态稳定,柱操作和再生时铁无溶出.吸附剂制备方法简单,新颖,对地下水和饮用水砷去除具有较好的应用前景.     

黄浦江表层沉积物中吸附态As(V)的释放研究

通过实验室模拟释放实验,研究了黄浦江表层沉积物对吸附态A(sV)的释放规律。结果表明,在静置条件下,淀峰和吴淞口处沉积物中A(sV)的释放量随时间的增加逐渐增大,在第1～16天时A(sV)释放量分别由3.33μg/L和6.73μg/L达到12.54μg/L和15.34μg/L,然后渐渐趋于稳定;扰动条件有利于A(sV)的释放,As(V)的释放量随扰动档速的提高急剧上升;在5～45℃温度试验范围,温度升高有利于A(sV)的释放;在pH由2～11范围内,A(sV)的释放量随pH的变化呈现"V"字形变化,在pH 5附近A(sV)释放最低,淀峰和吴淞口处分别为8.78μg/L和10.54μg/L;PO43-和HCO3-对A(sV)的释放影响明显,A(sV)释放量随溶液中PO43-和HCO3-浓度的增大而增大。     

Novel Fe/glass composite adsorbent for As(V) removal

An effective adsorbent for arsenic removal was synthesized by hydrothermal treatment of waste glass powder (GP), followed by loading Fe(Ⅲ) oxyhydroxide onto the surface of waste glass powder. The ≡Si-O-H group was formed on the surface of GP and the specific surface area of GP powder was slightly increased after hydrothermal treatment. FeOOH was loaded onto the surface of hydrothermally treated waste glass powder (HGP) by the hydrolysis of FeCl3. The formation conditions of FeOOH were also investigated. The...     

Stability of Fe–As composites formed with As(V) and aged ferrihydrite

During the aging process, ferrihydrite was transformed into mineral mixtures composed of different proportions of ferrihydrite, goethite, lepidocrocite and hematite. Such a transformation may affect the fixed ability of arsenic. In this study, the stability of Fe-As composites formed with As(V) and the minerals aged for 0, 1, 4, 10 and 30 days of ferrihydrite were systematically examined, and the effects of molar of ratios Fe/As were also clarified using kinetic methods combined with multiple spectroscopic techniques. The results indicated that As(V) was rapidly adsorbed on minerals during the initial polymerization process, which delayed both the ferrihydrite conversion and the hematite formation. When the Fe/As molar ratio was 1.875 and 5.66, the As(V) adsorbed by ferrihydrite began to release after 6 hr and 12 hr, respectively. The corresponding release amounts of As(V) were 0.55 g/L and 0.07 g/L, and the adsorption rates were 92.43% and 97.50% at 60 days, respectively. However, the As(V) adsorbed by the transformation products aged for 30 days of ferrihydrite began to release after adsorbed 30 days. The corresponding release amounts of As(V) were 0.25 g/L and 0.03 g/L, and the adsorption rates were 84.23% and 92.18% after adsorbed 60 days, for the Fe/As=1.875 and 5.66, respectively. Overall, the combination of As(V) with ferrihydrite and aged products transformed from a thermodynamically metastable phase to a dynamically stable state within a certain duration. Moreover, the aging process of ferrihydrite reduced the sorption ability of arsenate by iron (hydr)oxide but enhanced the stability of the Fe-As composites.     

腐植酸中不同分子量组分与As(Ⅲ)的络合性能

采用超滤方法将腐植酸（HA）分成5个不同分子量组分,利用平衡透析法研究HA中不同分子量组分与As（III）的络合特征和作用机理,计算络合过程的条件分配系数、表观稳定常数.结果表明,腐植酸组分的分子量对HA与As（III）的络合过程有显著的影响,当分子量小于10kDa时,HA与As（III）络合能力明显强于其他条件.其中羧基和酚羟基在HA与砷络合中起重要作用,为主要络合位点.采用Scatchard分析和双位点配体模型对络合结果进行拟合,发现HA中不同分子量组分和As（III）的络合过程中均存在强和弱2种络合位点.     

腐植酸中不同分子量组分与As(Ⅲ)的络合性能

采用超滤方法将腐植酸（HA）分成5个不同分子量组分,利用平衡透析法研究HA中不同分子量组分与As（III）的络合特征和作用机理,计算络合过程的条件分配系数、表观稳定常数.结果表明,腐植酸组分的分子量对HA与As（III）的络合过程有显著的影响,当分子量小于10kDa时,HA与As（III）络合能力明显强于其他条件.其中羧基和酚羟基在HA与砷络合中起重要作用,为主要络合位点.采用Scatchard分析和双位点配体模型对络合结果进行拟合,发现HA中不同分子量组分和As（III）的络合过程中均存在强和弱2种络合位点.     

Effects of arbuscular mycorrhizal (AM) fungi inoculation on arsenic (As) accumulation by tobacco (Nicotiana tabacum L.)

under As stress, proper mechanisms are employed by AM fungi to protect tobacco against As uptake. Results confirm that AM fungi can play an important role in food quality and safety.     

羟基铁柱撑蒙脱石同时吸附水溶液中Cd(Ⅱ)和As(Ⅴ)的研究

为同时去除水溶液中的Cd（Ⅱ）和As（Ⅴ），采用羟基铁柱撑改性获得改性蒙脱石，并深入研究了其吸附性能和吸附机理.同时，采用BET比表面积、SEM、XRD和XPS等手段分析了改性前后蒙脱石的结构特征；采用批实验分别研究了改性蒙脱石对水体中Cd（Ⅱ）和As（Ⅴ）的吸附动力学和热力学特征，并探讨了Cd（Ⅱ）-As（Ⅴ）复合体系中镉、砷相互作用对改性蒙脱石等温吸附镉、砷的影响.结果表明，改性蒙脱石的比表面积较改性前增加了28.2%，XPS测试结果表明改性蒙脱石成功引入羟基铁.改性蒙脱石单一吸附Cd（Ⅱ）和As（Ⅴ）的最优初始pH分别为6.5和5.5，且25℃时分别在10 h和5 h内达到吸附平衡，吸附过程均符合准二级动力学方程；Langmuir等温吸附模型能更好地描述改性蒙脱石对Cd（Ⅱ）的吸附，最大吸附量为21.36 mg·g^-1，该吸附过程是离子交换和化学络合共同作用的结果；Freundlich等温吸附模型能更好地解释改性蒙脱石对As（Ⅴ）的吸附，最大吸附量为11.45 mg·g^-1，该吸附过程是化学络合作用的结果（改性剂投加量均为2 g·L^-1）.在Cd（Ⅱ）-As（Ⅴ）复合体系中，镉、砷之间存在相互作用，pH为5.5时，吸附量高于改性蒙脱石对单一Cd（Ⅱ）和As（Ⅴ）的吸附量，分别增加了14.4%和23.7%，表明合成的羟基铁柱撑蒙脱石对镉、砷复合污染农田具有同时去除Cd（Ⅱ）和As（Ⅴ）的修复潜力.     

Simultaneous adsorption of As(Ⅲ) and Pb(Ⅱ) by the iron-sulfur codoped biochar composite:Competitive and synergistic effects

Simultaneous elimination of As(Ⅲ) and Pb(Ⅱ) from wastewater is still a great challenge.In this work,an iron-sulfur codoped biochar (Fe/S-BC) was successfully fabricated in a simplified way and was applied to the remediate the co-pollution of As(Ⅲ) and Pb(Ⅱ).The positive enthalpy indicated that the adsorption in As-Pb co-pollution was an endothermic reaction.The mechanism of As(Ⅲ) removal could be illustrated by surface complexation,oxidation and precipitation.In addition to precipitation and com...     

壳聚糖海藻酸钠铁锰泥吸附剂制备与除As(V)研究

将生物除铁除锰水厂反冲洗铁锰泥包埋在壳聚糖海藻酸钠水凝胶中,成功制备了一种具有高机械强度和稳定性的复合除砷吸附剂（CAFB）.表征结果显示,其表面粗糙,铁锰元素含量为69.31%,比表面积达117.20m²/g,且具有介孔结构.吸附动力学数据更符合准二级动力学模型（R²=0.963）.Langmuir等温吸附模型能更好地描述As （V）吸附过程（R²=0.969）,25℃时最大吸附容量为15.80mg/g.酸性条件有利于As （V）的吸附,在pH=3~7范围内As （V）去除率能达到80%以上.H²PO₄^-,SiO₃^2-离子对吸附过程抑制作用明显.用0.1mol/L的NaOH溶液再生4次后吸附量能达到初始值的70.68%,具有在工程上运用的前景.