Groundwater arsenic removal by coagulation using ferric(III) sulfate and polyferric sulfate: A comparative and mechanistic study

Elevated arsenic (As) in groundwater poses a great threat to human health. Coagulation using mono-and poly-Fe salts is becoming one of the most cost-effective processes for groundwater As removal. However, a limitation comes from insufficient understanding of the As removal mechanism from groundwater matrices in the coagulation process, which is critical for groundwater treatment and residual solid disposal. Here, we overcame this hurdle by utilizing microscopic techniques to explore molecular As surface complexes on the freshly formed Fe flocs and compared ferric(III) sulfate (FS) and polyferric sulfate (PFS) performance, and finally provided a practical solution in As-geogenic areas. FS and PFS exhibited a similar As removal efficiency in coagulation and coagulation/filtration in a two-bucket system using 5 mg/L Ca(ClO)₂. By using the two-bucket system combining coagulation and sand filtration, 500 L of As-safe water (<10 μg/L) was achieved during five treatment cycles by washing the sand layer after each cycle. Fe k-edge X-ray absorption near-edge structure (XANES) and As k-edge extended X-ray absorption fine structure (EXAFS) analysis of the solid residue indicated that As formed a bidentate binuclear complex on ferrihydrite, with no observation of scorodite or poorly-crystalline ferric arsenate. Such a stable surface complex is beneficial for As immobilization in the solid residue, as confirmed by the achievement of much lower leachate As (0.9 μg/L-0.487 mg/L) than the US EPA regulatory limit (5 mg/L). Finally, PFS is superior to FS because of its lower dose, much lower solid residue, and lower cost for As-safe drinking water.     

Groundwater arsenic removal by coagulation using ferric(Ⅲ)sulfate and polyferric sulfate: A comparative and mechanistic study

Elevated arsenic(As) in groundwater poses a great threat to human health. Coagulation using mono- and poly-Fe salts is becoming one of the most cost-effective processes for groundwater As removal. However, a limitation comes from insufficient understanding of the As removal mechanism from groundwater matrices in the coagulation process, which is critical for groundwater treatment and residual solid disposal. Here, we overcame this hurdle by utilizing microscopic techniques to explore molecular As surface complexes on the freshly formed Fe flocs and compared ferric(III) sulfate(FS) and polyferric sulfate(PFS)performance, and finally provided a practical solution in As-geogenic areas. FS and PFS exhibited a similar As removal efficiency in coagulation and coagulation/filtration in a two-bucket system using 5 mg/L Ca(ClO)_2. By using the two-bucket system combining coagulation and sand filtration, 500 L of As-safe water( 10 μg/L) was achieved during five treatment cycles by washing the sand layer after each cycle. Fe k-edge X-ray absorption near-edge structure(XANES) and As k-edge extended X-ray absorption fine structure(EXAFS) analysis of the solid residue indicated that As formed a bidentate binuclear complex on ferrihydrite, with no observation of scorodite or poorly-crystalline ferric arsenate. Such a stable surface complex is beneficial for As immobilization in the solid residue, as confirmed by the achievement of much lower leachate As(0.9 μg/L–0.487 mg/L)than the US EPA regulatory limit(5 mg/L). Finally, PFS is superior to FS because of its lower dose, much lower solid residue, and lower cost for As-safe drinking water.     

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.     

Arsenic uptake and transport of Pteris vittata L. as influenced by phosphate and inorganic arsenic species under sand cu｜ture

In order to understand the similarity or difference of inorganic As species uptake and transport related to phosphorus in As-hyperaccumulator, uptake and transport of arsenate (As(Ⅴ)) and arsenite (As(Ⅲ)) were studied using Pteris vittata L. under sand culture. Higher concentrations of phosphate were found to inhibit accumulation of arsenate and arsenite in the fronds of P. vittata. The reduction in As accumulation was greater in old fronds than in young fronds, and relatively weak in root and rhizome. Moderate increases, from 0.05 to 0.3 mmol/L, in phosphate reduced uptake of As(Ⅲ) more than As(Ⅴ), while the reverse was observed at high concentrations of phosphate (≥ 1.0 mmol/L). Phosphate apparently reduced As transport and the proportion of As accumulated in fronds of P. vittata when As was supplied as As(Ⅴ). It may in part be due to competition between phosphorus and As(Ⅴ) during transport. In contrast, phosphate had a much smaller effect on As transport when the As was supplied as As(Ⅲ). Therefore, the results from present experiments indicates that a higher concentration of phosphate suppressed As accumulation and transport in P. vittata, especially in the fronds, when exposure to As(Ⅴ); but the suppression of phosphate to As transport in the root or rhizome may be insignificant when P. vittata when exposure to As(Ⅲ) under sand culture conditions. The finding will help to understand the interaction of P and As during their uptake process in P. vittata.     

植物砷吸收与代谢的研究进展

砷(As)作为一种植物非必需的类金属元素广泛存在于自然界中,砷过量摄人不仅会对植物生长产生毒害作用,而且在植物的可食部位累积并通过食物链对人体健康构成威胁.生长介质中的砷酸盐(五价砷)一般是通过磷酸盐转运蛋白被植物吸收的,而亚砷酸(三价砷)和没有解离的甲基化砷则主要是通过质膜上的水通道蛋白被植物吸收的.在植物体内五价砷...     

广州及周边地区森林土壤As、Se、Hg质量分数特征及污染评价

研究了广州及周边地区5处代表性森林土壤（鼎湖山、西樵山、华南植物园、黄埔和南昆山）As、Se、Hg质量分数特征及污染状况。结果表明,上述5地森林表层土壤As质量分数平均值分别为18.6、18.0、12.2、11.4、26.1 mg.kg-1,Se质量分数平均值分别为0.360、0.729、0.286、0.421、0.434 mg.kg-1,Hg质量分数平均值分别为0.201、0.270、0.139、0.224、0.087 mg.kg-1。除植物园土壤Se质量分数、南昆山土壤Hg质量分数较接近背景值外,5林地As、Se、Hg质量分数均超过背景值,可能存在外源As、Se、Hg输入。其中,南昆山As输入,西樵山Se、Hg输入,黄埔、鼎湖山Hg输入较明显。单因子污染指数分析结果表明在南昆山As为最严重的污染物,而在鼎湖山、植物园、西樵山和黄埔Hg为最严重的污染物。综合污染指数分析结果表明5林地土壤均受到不同程度的污染,其中西樵山土壤属重度污染,南昆山、黄埔、鼎湖山属中度污染,植物园污染较轻,属轻度污染。     

含铁材料对污染水稻土中砷的稳定化效果

通过化学实验方法,向砷污染水稻土中添加4种含铁材料(FeCl3、FeCl2、Fe0和Fe2O3),分析稳定后土壤中pH、砷形态及砷毒性浸出量的变化,研究4种含铁材料对污染水稻土中砷的稳定化效果。结果表明,FeCl3和FeCl2处理降低了土壤pH,Fe0和Fe2O3处理对土壤pH影响不大。4种含铁材料均明显降低了土壤中易溶态砷(WE-As)和毒性浸出砷含量。在最大添加量为8.00 g/kg时,FeCl3、FeCl2、Fe0和Fe2O3分别使易溶态砷比对照降低了86.4%、63.6%、77.3%和36.4%,使毒性浸出砷比对照降低了96.3%、88.9%、70.4%和30.4%。4种含铁材料均对水稻土壤中砷具有较好的稳定化效果,且能力大小依次为:FeCl3FeCl2、Fe0Fe2O3。Fe0和Fe2O3处理使WE-As、铝型砷(Al-As)、铁型砷(Fe-As)向钙型砷(Ca-As)和残渣态砷(RS-As)转化;FeCl3处理使土壤WE-As、Al-As向Fe-As、Ca-As和RS-As转化;FeCl2处理使土壤WE-As、Ca-As向Al-As、Fe-As转化,对RS-As影响不明显。说明Fe0固砷的机理与Fe2O3相似,与FeCl3有一定差异,与FeCl2的差异可能更大。     

A(sⅢ)和A(sⅤ)对小球藻(Chlorella sp).的生长影响研究

砷是广泛存在于自然界中最常见的毒性污染物,包括土壤,沉积物,水体,大气层,甚至生物体,毒性极强。环境中砷的污染严重威胁人类的健康,已被视为一个全球性的公共卫生问题。为了研究砷对小球藻的生长影响,文章通过实验室培养方式,选取了6个不同浓度的As(Ⅲ()0.5、1.0、2.0、5.0、10.0、20.0 mg/L)和As(Ⅴ()1.0、5.0、10.0、20.0、50.0、100.0 mg/L)的培养处理,以在680 nm下小球藻的吸光度(OD680)作为衡量因子,对小球藻Chlorella sp(.100 ai)在不同浓度砷离子的培养液中的细胞密度进行了试验,整个实验共进行了7 d。结果表明,As(Ⅲ)和As(Ⅴ)浓度分别在10.0 mg/L和20.0 mg/L以上时抑制100 ai细胞生长,导致其密度下降。用概率统计方法计算得到A(sⅢ)对100 ai的96 h半数有效抑制浓度EC50值为25.79 mg/L。参照藻类生长抑制评价标准,A(sⅢ)对100 ai的毒性比A(sⅤ)大。     

长期施肥对旱地红壤及作物中砷累积的影响

以湖南祁阳农田生态系统国家野外试验站的土壤为研究对象,分析了长期施肥措施对砷在土壤及作物籽粒和秸秆中累积的影响.供试土壤选择了4个不同施肥处理：不施肥（CK）、单施化肥（NPK）、单施有机肥（M）和化肥有机肥配施（NPKM）.结果表明,与不施肥相比,长期（26 a）施肥措施（NPK、M和NPKM）均显著增加了红壤中总砷（As）和有效态砷含量,其中,NPK处理的红壤中砷含量超过国家标准值（40 mg·kg^-1）.长期施肥处理对非专性吸附态As影响最大,其次为残渣态As,晶型氧化物结合态As,但对专性吸附态As和无定型铁铝氧化物结合态As的影响较小.与CK、NPK、M处理相比,NPKM处理能显著降低土壤中As（Ⅲ）和As（Ⅴ）含量.此外,施用有机肥（猪粪）会导致玉米籽粒和秸秆中As的累积,而不会导致小麦籽粒和秸秆中的As累积.同步辐射红外显微成像和微束X射线荧光谱图显示了红壤样品中As、黏土矿物和有机官能团在微空间尺度上的高度异质性特征,表明As的有效性主要受铁氧化物和羟基碳的影响.     

天然浮石去除水中As(Ⅴ)的试验研究

通过静态吸附试验,研究了天然浮石对高砷地下水中As(Ⅴ)的吸附去除效果及影响因素.结果表明,增加浮石投加量,As(Ⅴ)的去除率随之逐渐升高,但当浮石投加量超过10 g/L时,继续增加浮石投加量,As(Ⅴ)的去除率趋于平稳.随吸附时间延长,As(Ⅴ)的去除率逐渐升高,9h后吸附达到平衡.浮石对As(Ⅴ)的吸附量随As(Ⅴ)初始质量浓度增大而升高,而As(Ⅴ)的去除率则随之降低.酸性条件下(pH=2～6),浮石对As(Ⅴ)的去除效果较好,当pH=4时,浮石对As(Ⅴ)的去除率最高;在碱性条件下(pH＞7),浮石去除As(Ⅴ)的效果较差,并且,随pH值增大,As(Ⅴ)的去除率降低.采用Langmuir和Freundlich等温吸附模型分别对吸附数据进行拟合,浮石对As(Ⅴ)的吸附符合Langmuir等温吸附规律,其饱和吸附量为2.53 mg/g.采用准一级和准二级动力学模型对吸附平衡前的数据进行拟合,准二级动力学模型更符合浮石吸附As(Ⅴ)的动力学过程.研究表明,天然浮石是一种能够有效吸附高砷地下水中As(Ⅴ)的吸附剂.