Competitive and cooperative adsorption of arsenate and citrate on goethite

The fate of arsenic in natural environments is influenced by adsorption onto metal (hydr)oxides. The extent of arsenic adsorption is strongly a ected by coexisting dissolved natural organic acids. Recently, some studies reported that there existed competitive adsorption between arsenate and citrate on goethite. Humic acid is known to interact strongly with arsenate by forming complexes in aqueous solution, hence it is necessary to undertake a comprehensive study of the adsorption of arsenate/citrate onto goethite in the presence of one another. The results showed that at the arsenate concentrations used in this study (0.006–0.27 mmol/L), citrate decreased arsenate adsorption at acidic pH but no e ect was observed at alkaline pH. In comparison, citrate adsorption was inhibited at acidic pH, but enhanced at alkaline pH by arsenate. This was probably due to the formation of complex between arsenate and citrate like the case of arsenate with humic acid. These results implied that the mechanism of the adsorption of arsenate and citrate onto goethite in the presence of one another involved not only competition for binding sites, but the cooperation between the two species at the watergoethite interface as well.     

Effect of external and internal phosphate status on arsenic toxicity and accumulation in rice seedlings

Phosphorus (P) deficiency is thought to exacerbate the arsenic (As) phytotoxicity in paddy rice. The experiments were conducted to investigate the e ects of external phosphate supply on As accumulation in rice and its toxicity under phosphate deficiency conditions. Rice seedlings pretreated with a phosphorus deficient nutrient solution (–P) for 14 d accumulated more As than those pretreated with a normal phosphorus supply nutrient solution (+P). Rice protreated with –P showed As toxicity symptoms after being exposed to 50 mol/L arsenate for 4 h, while +P rice did not show any toxicity symptoms. Arsenic toxicity symptoms can be alleviated by increasing external P concentrations. The arsenate uptake rate and accumulation corresponded with the As toxicity in rice plants. Arsenic concentrations in rice roots decreased with increasing external phosphate concentrations. The lowest As accumulation and the highest P accumulation were found when the external P concentration reached 100 mol/L. In short, P deficiency increased the sensitivity of rice to arsenate and increasing of external phosphate supply could alleviate As toxicity.     

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

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 sandculture.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.Moderateincreases,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 highconcentrations of phosphate(1.0 mmol/L).Phosphate apparently reduced As transport and the proportion of As accumulated in frondsof P.vittata when As was supplied as As(V).It may in part be due to competition between phosphorus and As(V)during transport.Incontrast,phosphate had a much smaller effect on As transport when the As was supplied as As(III).Therefore,the results from presentexperiments indicates that a higher concentration of phosphate suppressed As accumulation and transport in P.vittata,especially inthe fronds,when exposed to As(V);but the suppression of phosphate to As transport may be insignificant when P.vittata exposed toAs(III)under sand culture conditions.The finding will help to understand the interaction of P and As during their uptake process in P.vittata.     

阳离子表面活性剂改性的活性炭吸附砷(V)和砷(Ⅲ)

选用阳离子表面活性剂十六烷基三甲基氯化铵（CTAC）、癸基三甲基溴化铵（MTAB） 以及三甲基正十四烷溴化铵（DTAB） 改性活性炭. 结果发现,表面活性剂加载使得活性炭的比表面积、孔径体积和表面Zeta电位发生改变. 改性后的活性炭用来吸附水中的砷酸盐和亚砷酸盐. 吸附等温实验结果显示,改性后活性炭对砷酸盐的吸附能力有显著提高,但对亚砷酸盐则只有在pH>10才有明显吸附.无论对砷酸盐还是亚砷酸盐,CTAC改性效果均要好于MTAB和DTAB. 改性后活性炭对砷酸盐的吸附主要通过离子交换,但离子交换并不是唯一的吸附机理. 砷酸盐的吸附受到溶液pH值和水中其他阴离子的竞争吸附的影响.中性pH范围内吸附最佳,而阴离子对砷酸盐的竞争则是PO₄^3- >SO₄^2- > NO₃^-.     

人工合成铁、铝矿对As(V)吸附的研究

采用批实验方法研究了人工合成铁、铝矿物对As(V)的吸附,考察吸附时间及溶液pH值对As(V)吸附的影响.结果表明,不同类型铁、铝矿对As(V)的吸附量均表现出随初始As(V)浓度(0.1~100mg/L)的增加而增加的趋势,其中水铁矿的吸附量在整个浓度范围内始终呈上升趋势,初始浓度为100mg/L As(V)时的吸附量为22.56mg/g,而针铁矿、水铝矿和赤铁矿的吸附量在低初始浓度时上升较快,随浓度升高上升幅度减缓直至平衡,其中赤铁矿的吸附量最小,100mg/L As(V)时的吸附量为4.75mg/g.Freundlich方程对吸附数据的拟合效果优于Langmuir方程,吸附能力表现为水铁矿最高,水铝矿和针铁矿相近,赤铁矿较低.随着吸附时间的增加,4种铁、铝矿物对As(V)的吸附量都逐渐增加,尤其是水铁矿,10min内即达到平衡吸附量的96.3%;水铝矿和针铁矿在48h时吸附量分别为平衡吸附量的97.2%和97.4%;赤铁矿则需96h才基本达到平衡.除水铁矿外,4种动力学方程对其他矿物动力学曲线的拟合均较好,尤其是双常数方程.pH值对矿物吸附As(V)的影响受As(V)初始浓度的影响,初始浓度较低时,铁、铝矿的吸附量仅在极碱条件下(pH>10)降低,而初始浓度较高时则表现为随pH值升高直线下降的趋势.     

Biogeochemical reductive release of soil embedded arsenate around a crater area (Guandu) in northern Taiwan using X-ray absorption near-edge spectroscopy

This study investigates biogeochemical reductive release of arsenate from beudantite into solution in a crater area in northern Taiwan,using a combination of X-ray absorption near-edge structure (XANES) and atomic absorption spectrometry.Total arsenic (As) concentrations in the soil were more than 200 mg/kg.Over four months of laboratory experiments,less than 0.8% As was released into solution after reduction experiments.The 71% to 83% As was chemically reduced into arsenite (As(III)) and partially weathering into the soluble phase.The kinetic dissolution and re-precipitation of As,Fe,Pb and sulfate in this area of paddy soils merits further study.     

新型离子交换纤维去除水中砷酸根离子的研究

制备了一种新型离子交换纤维。研究表明,该离子交换纤维对砷酸根离子具有较高的吸附容量和较快的吸附速度,吸附动力学数据完全符合Lagergren二级速度方程,在所研究的砷浓度范围内,Freundlich型吸附等温式能很好地描述吸附平衡数据,去除砷酸根离子的最佳pH值范围是3．5－7．0。离子交换纤维柱吸附实验表明了较好的动态附特性,稀NaOH溶液是砷酸根离子的有效洗脱剂,30mL 0.5mol/L NaOH溶液可定量将96．0mg/g吸附量的砷从纤维柱上洗脱。     

Mg/Al双金属氧化物对As(V)吸附性能的研究

研究了以镁铝水滑石为原料制备的Mg/Al双金属氧化物对溶液中As(V)的吸附作用及其影响因素.结果表明：Mg/Al双金属氧化物对As(V)具有较强的吸附能力,吸附规律符合Langmuir等温吸附方程,根据计算所得的理论最大吸附量为51.02 mg·g-1,与实验得出的最大吸附量50.53 mg·g-1基本一致;运用3种...     

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.     

运用涂铁砂粒进行分散式饮水除砷的效果

采用铁盐处理普通河砂研制成涂铁砂粒(IOCS),通过静态和动态吸附试验观察其分散式饮水除砷效果,并选取地砷病现场进行了验证.结果表明,IOCS性质较为稳定,扫描电镜下可见铁氧化物呈片状分散的覆盖在砂粒表层;IOCS无需活化处理,其对砷的最大吸附发生在30min～60min;pH5～9时,五价砷的去除率随着pH值的升高而下降,三价砷的去除率变化不明显.IOCS对砷的吸附符合朗格缪尔(Langmuir)吸附方程;5次滤柱循环中,75g(50ml)的IOCS分别处理含砷1.0mg·L^-1的水样408～426床(三价砷),390～412床(五价砷),用0.2 mol·L^-1NaOH进行再生处理,砷回收率均在94%以上.充填IOCS 3.0kg的家庭用模拟装置处理含1.0mg·L^-1的五价砷209L和198L,三价砷196L和185L,并在现场实验期间,连续处理含砷0.202～1.733mg·L^-1的水样200L,对水质亦无不良影响.无论是经济上还是技术上,IOCS均是适合于分散式饮水除砷的一种新型除砷剂.     

不同磷水平下铜绿微囊藻对砷酸盐的吸收和净化

通过室内培养实验,研究了富磷(+P)和缺磷(–P)环境下,铜绿微囊藻对砷酸盐(As(Ⅴ))的累积和净化动力学特征,探讨了净化过程中培养介质砷形态的变化.结果表明:缺磷环境下虽然可显著提升铜绿微囊藻对砷酸盐的吸收,但该环境下的高砷藻体又具较高的砷释放风险.+P和–P环境下,藻体中分别有41.5%和46.3%的胞内砷可在快速清除阶段(2h)被迅速排出.+P环境下经10μmol/L As(Ⅴ)暴露后的含砷藻体,经13d净化培养后,+P培养介质中藻体以砷酸盐释放为主,-P培养介质中则存在砷的还原和甲基化现象,这表明不同磷水平下藻体对砷的净化机理可能存在明显差异.     

Synthesis of mesoporous Cu/Mg/Fe layered double hydroxide and its adsorption performance for arsenate in aqueous solutions

The mesoporous Cu/Mg/Fe layered double hydroxide(Cu/Mg/Fe-LDH) with carbonate intercalation was synthesized and used for the removal of arsenate from aqueous solutions.The Cu/Mg/Fe-LDH was characterized by Fourier transform infrared spectrometry,X-ray diffraction crystallography,scanning electron microscopy,X-ray photoelectron spectroscopy and Brunauer-Emmett-Teller.Effects of various physico-chemical parameters such as pH,adsorbent dosage,contact time and initial arsenate concentration on the adsorption of arsenate onto Cu/Mg/Fe-LDH were investigated.Results showed that it was efficient for the removal of arsenate,and the removal efficiency of arsenate increased with the increment of the adsorbent dosage,while the arsenate adsorption capacity decreased with increase of initial pH from 3 to 11.The adsorption isotherms can be well described by the Langmuir model with R 2 > 0.99.Its adsorption kinetics followed the pseudo second-order kinetic model.Coexisting ions such as HPO42-,CO32-,SO42and NO3could compete with arsenate for adsorption sites on the Cu/Mg/Fe-LDH.The adsorption of arsenate on the adsorbent can be mainly attributed to the ion exchange process.It was found that the synthesized Cu/Mg/Fe-LDH can reduce the arsenate concentration down to a final level of < 10 μg/L under the experimental conditions,and makes it a potential material for the decontamination of arsenate polluted water.     

Simultaneous removal of chromium and arsenate from contaminated groundwater by ferrous sulfate: Batch uptake behavior

Chromium and/or arsenate removal by Fe(II) as a function of pH, Fe(II) dosage and initial Cr(VI)/As(V) ratio were examined in batch tests. The presence of arsenate reduced the removal e ciency of chromium by Fe(II), while the presence of chromate significantly increased the removal e ciency of arsenate by Fe(II) at pH 6–8. In the absence of arsenate, chromium removal by Fe(II) increased to a maximum with increasing pH from 4 to 7 and then decreased with a further increase in pH. The increment in Fe(II) dosage resulted in an improvement in chromium removal and the improvement was more remarkable under alkaline conditions than that under acidic conditions. Chromium removal by Fe(II) was reduced to a larger extent under neutral and alkaline conditions than that under acidic conditions due to the presence of 10 mol/L arsenate. The presence of 20 mol/L arsenate slightly improved chromium removal by Fe(II) at pH 3.9–5.8, but had detrimental e ects at pH 6.7–9.8. Arsenate removal was improved significantly at pH 4–9 due to the presence of 10 mol/L chromate at Fe(II) dosages of 20–60 mol/L. Elevating the chromate concentration from 10 to 20 mol/L resulted in a further improvement in arsenate removal at pH 4.0–4.6 when Fe(II) was dosed at 30–60 mol/L.     

2006年春季长江口砷形态分析及其生物有效性

于2006年春季在长江河口开展野外调查.采集水和表层沉积物样品,并进行总砷、砷形态分析和生物有效性评估.将过滤水样用于测定溶解态砷含量,而未过滤水样经酸消解后用于测定总砷含量,两者之差则为颗粒态砷含量.结果表明.长江口青草沙水源地各层水体中总砷含量为0.88-1.35ug·L-1(涨憩),2.37-3.35ug·L-1(落憩).溶解态和颗粒态砷含量均随潮汐变化明显,各形态砷含量在落憩时均高于涨憩时,颗粒态砷所占总砷的比例也是落憩时明显高于涨憩时.以0.3 mol·L-1磷酸溶液为萃取剂.在微波辅助下可以有效地将沉积物中砷酸盐[As(V)]、亚砷酸盐[As(Ⅲ)]、一甲基胂酸盐(MMA)和二甲基胂酸盐(DMA)提取出来,然后利用高效液相色谱一氢化物发生.原子吸收光谱(HPLC-HG-AAS)联用技术进行检测.结果表明,长江口表层沉积物中总砷含量为6.3-30.7 mg·kg-1,主要为无机砷形态,在江心沙洲及离岸沉积物中且以砷酸盐为主.而在近岸沉积物中以亚砷酸盐为主;利用醋酸纤维素/氧化铁复合膜方法(FeO/CAM)所得沉积物中有嫂砷含量占总砷含量0.6%-3.9%,平均约为2.1%.有效砷含量与总砷含量没有显著相关性,与亚砷酸盐含量呈显著正相关性,与砷酸盐含量呈显著负相关性.结果还表明,长江口南支沉积物中的砷形态分布特征及其生物有效性受城市支流输入和排污活动影响显著.     

砷酸根对砖红壤中铜吸附和解吸影响的初步研究

研究了加砷酸根对砖红壤吸附铜及随后吸附性铜的解吸的影响.结果表明,加砷后土壤对铜的吸附量和解吸量均增加.随砷加入量的增加,土壤对铜的吸附量和吸附性铜的解吸量均增加.在pH值为3 4至5 2范围内,砷对铜吸附的促进作用随pH值的增加而增加,约在pH值为4 5时达最大,然后逐渐减小.表面电荷的测定结果和铜的解吸实验结果均说明砷酸根主要通过自身的吸附来增加土壤的表面净负电荷,从而增加土壤对铜的吸附量.     

光助MIL-101(Fe)活化过氧化氢氧化洛克沙胂及同步吸附生成的砷酸根

采用铁基金属有机框架(MIL-101(Fe))在模拟太阳光下活化过氧化氢氧化降解ROX—吸附去除生成的砷酸根.结果表明,光助MIL-101(Fe)(250mg/L)活化氧化剂H2O2(1.0mmol/L)体系可在120min内实现95.27％的ROX去除率,反应过程中形成的无机砷酸盐(As(Ⅴ))会吸附在MIL-101...     

两个品种水稻对砷的吸收富集与转化特征及其健康风险

以2个水稻品种威优402号和Ⅱ优416号为实验材料,采用温室栽培方法研究对比两个品种水稻在人工添加砷处理(0、10、20和40mg·kg-1)和模拟自然砷污染(贵州高砷土和北京褐土的混合土,质量比为1∶1)胁迫条件下的生长发育状况,分析砷在水稻不同部位的累积、形态转化及其健康风险.砷处理显著地抑制了两个品种水稻的生长,水稻地上与地下部生物量、株高和穗数随砷处理水平的提高均出现明显的下降,但Ⅱ优416号的下降幅度明显低于威优402号.两个品种水稻籽粒中砷含量随砷处理水平提高也显著升高,人工添加砷各处理条件下,两个品种水稻稻谷中砷含量没有显著性差异;而在模拟自然砷污染土中,Ⅱ优416号稻谷中砷含量平均值为0.062mg·kg-1,明显低于威优402号稻谷平均值的0.278mg·kg-1.两个品种水稻各部位砷的转运系数在低砷处理时(10mg·kg-1)出现显著的升高,而在其他处理条件下保持不变.无论何种水稻品种,水稻各部位砷形态的组成和比例无显著性差异,水稻根、茎、叶中主要为无机砷,稻谷中无机和有机砷各占60%和40%.依据WHO相关建议标准,种植水稻品种Ⅱ优416号的健康风险要明显低于种植威优402号.     

刁江底泥砷形态的化学分级法与XANES方法比较

采用XANES(X射线近边分析)方法和化学分级法,研究了刁江污染源区尾砂及刁江底泥的砷形态组成特征. XANES方法结果表明,尾砂中砷的形态主要以毒砂(FeAsS)存在,其相对百分含量为63%~99%;而刁江底泥中的砷形态主要是毒砂、砷酸盐和亚砷酸盐,其中毒砂的比例较高,表现出典型的尾砂污染特征. 化学分级法结果表明,尾砂中砷形态主要是残渣态砷(Res-As),而底泥中的砷主要以铁合态、钙合态及残渣态形式存在. 刁江底泥中毒砂相对百分含量和残渣态砷随着与污染源区距离的增大而减小,砷酸盐和亚砷酸盐则呈相反的趋势. 化学分级法和XANES方法所反映的刁江底泥和污染源的砷形态组成和变化趋势总体上较为一致,但这2种方法所获得的定量数据存在一定的差异.      

A comprehensive study of treatment of arsenic in water combining oxidation, coagulation, and filtration

Arsenic is one of the most common inorganic contaminants in groundwater worldwide, mainly due to the release of naturally occurring arsenic from aquifer sediments (Amini et al., 2008, Li and Cai, 2015 and Rahman et al., 2015). Naturally occurring arsenic exists predominantly in arsenate and arsenite species in groundwater.     

铁改性赤泥吸附剂的制备及其除砷性能研究

以氧化铝生产废渣--赤泥为原料,采用铁盐改性处理制备了新型羟基铁包覆型赤泥除砷吸附剂.研究考察了吸附剂吸附砷效能、投加量、吸附时间和pH值对吸附除砷效果的影响;采用扫描电镜(SEM)、红外光谱(IR)、比表面积(BET)等仪器对吸附剂进行了表征,并探讨了吸附机制.结果表明,铁盐改性赤泥吸附剂对As(V)具有显著吸附效能,在pH为7,初始砷浓度为1 mg·L-1,铁盐改性赤泥吸附剂饱和吸附容量为50.6mg·g-1时,除砷率高达99.9%,吸附后出水砷含量可达到0.01 mg·L-1以下,吸附规律符合Langmuir等温方程式;溶液pH值显著影响砷去除效果,吸附机制主要为羟基铁的表面吸附机制;吸附后的吸附剂可通过NaOH溶液再生,脱附率达到92.1%.