Mobilization of natural arsenic in groundwater: targeting low arsenic aquifers in high arsenic occurrence areas

研究表明饮用水中微小数量的砷会对人类健康产生不利影响.世界上居住在贫穷地区的人数超过了100万,目前他们正直接饮用来自含水层中砷离子含量(>10μg/L)非安全标准的地下水.砷有时称为毒中之王,在水环境中常常以五价氧化物形式出现.自2000年以来,许多国家开始执行更为严格的10μg/L(WHO认可的居民安全饮水标准)饮用水标准,可以确定地说,在世界范围内的饮用水中检测到砷的情况越来越多.亚洲地区砷中毒的人数比世界其他地区总和还多.最受影响的地区位于南亚和东南亚富砷带,环绕恒河一雅鲁藏布江-梅克纳河三角洲及恒河平原上游的冲洪积扇含水层、红河三角洲、湄公河和伊洛瓦底江;在中国境内包括内蒙黄河冲积盆地,山西大同盆地、新疆准噶尔盆地,其中的地下水富含砷和氟化物而引发砷中毒和氟中毒.尽管还未完全掌握其中的水文地质及生物地球化学作用的详细过程,但对大多数沉积介质含水层,在还原条件下砷离子容易从沉积介质转移到地下水中.孟加拉研究实例表明地质时期尺度的冲刷降低了沉积介质中的As和有机物含量从而形成低砷地下水.这一认识为孟加拉国的降砷策略提供了科学指导,是未来水文学,矿物学,地质学和生物地球化学方面很有意义的研究方向,并有利于地砷病区低砷地下水的可持续利用.     

山西临汾-运城盆地土壤中As含量的变化规律

通过对临汾-运城盆地表层和深层土壤中As含量变化规律的研究,发现表层土壤的As含量稍高于全国土壤的背景值,不同相态的含量差异较大。土壤pH、磁化率、有机质、粘粒含量等理化性质对不同形态的As有着不同程度的影响：研究区水溶态的As受土壤pH值的控制,腐殖质结合态的As与有机质呈明显的正相关关系,磁化率、粘粒含量与土壤As的含量都有明显的正相关关系。研究结果表明,As与Fe、Mn、Cu、Zn、Mg、K、F等元素的相关性非常显著,说明研究区表层土壤中的As主要是自然成因的。进一步的回归分析表明,土壤的As含量随着铁氧化物、氢氧化物和硫化物含量的增加而增加。研究区土壤As的纵向分布特点是中层多、上下层少,这可能与研究区As的污染状况、土壤的碱性环境、植物的吸收作用、磷肥的施用等因素有关。     

土壤中不同形态砷的分析方法

选取磷酸作为提取剂,比较了超声和水浴两种方法辅助提取土壤中不同形态的砷,离子色谱一氢化物发生原子荧光光谱联用法(IC-HGAFS)测定砷的4种形态,即As(Ⅲ)、As(Ⅴ)、MMA (甲基胂酸)和DMA(二甲基胂酸)。从测定结果可以看出,水浴的提取效果明显高于超声的提取效果。土壤中砷以无机态为主,而无机态砷又以As(Ⅴ)为主,没有检测到有机砷。测定土壤中各种形态砷的加标回收率为72.0%～105.4%,相对标准偏差(RSD,n=5)为2.61%～8.19%。     

Arsenic in geothermal sources at the north-central Andean region of Ecuador: concentrations and mechanisms of mobility

The arsenic content of geothermal hot springs and their sediments in the north-central Andean region of Ecuador has been investigated. The area of study is located between parallels 1°11′N and 1°30′S and includes five provinces. The area is rich in geothermal surface manifestations that are mainly used for medicinal baths in recreational complexes. Unfortunately, water residuals without treatment are released from the recreational facilities to surrounding water bodies. The results indicate that total arsenic in geothermal waters in this region has a range of 2–969 μg As/L, and sediments contain arsenic ranging from 1.6 to 717.6 mg/kg. Chemical analyses of sediment samples show the presence of sulfur, iron, aluminum and calcium. A high concentration of natural organic matter was also found in some samples (20–29.5%); thus sorption and coprecipitation can be the main mechanisms of As immobilization on mineral phases and natural organic matter.     

山西山阴、应县一带砷中毒区砷的环境地球化学研究

通过对山西省大同盆地砷中毒区的环境地球化学调查,对病区环境中砷的来源、价态及砷的迁移、富集、转化规律进行了研究。结果表明,盆地周边岩石、煤系地层为富砷岩系,构成砷的原生物源。自然和人为作用将环境中的砷释放出来,在第四系含水层湖冲积物中富集成次生富砷储集层,为水砷的直接来源。由于含砷水在黄水河构造凹地的深层滞留,加之干旱蒸发使水中砷进一步浓集成高砷水,富炭质含水层的还原环境促使Ａｓ５＋向Ａｓ３＋转化,提高了水的毒性,加剧了砷中毒的发生。     

Arsenic Speciation in a Contaminated Gold Processing Tailings Dam

Gold recovery in ores containing arsenopyrite releases significant amounts of arsenic into the environment due to mineral processing and oxidation during storage. The extent of arsenic weathering in a tailings dam has been investigated. Speciation of As in surface and pore waters and pond sediments showed that for gold tailings in the dam, As enrichment took place in the pore water relative to the surface water. In pond sediments As was predominantly present as residual arsenopyrite and partly as a substance co-precipitated with iron hydroxide. The arsenic release from the sediment results from a reductive dissolution of the arsenopyrite and Fe oxides. In the surface water, arsenate and arsenite are the main arsenic species (arsenate is dominant), but in the pore waters methylation processes play a significant role. Arsenic transport is accompanied by the transformation of As into the less toxic compounds (methylated species) co-existing with the most toxic species (arsenite).     

地下水中砷形态标准物质研制

砷元素的不同形态对人体有不同的毒性,无机砷的毒性最大,有机砷毒性较小,准确测定水体中尤其是地下水中砷形态的含量对于人体健康和环境保护有重要意义。但目前国内外尚缺乏地下水中砷形态的标准物质。文章研制了5个地下水砷形态标准物质,候选物样品采自山西和内蒙古高砷地区,在样品的采集和制备过程中使用冷冻干燥法和加保护剂两种方法保证砷形态稳定,定值参数为砷全量、As(Ⅲ)、As(Ⅴ),定值方法采用氢化物发生-原子荧光光谱法、电感耦合等离子体光谱法、电感耦合等离子体质谱法、高效液相色谱-电感耦合等离子体质谱法。经检验,制备的砷形态标准物质具有良好的均匀性和稳定性。该系列标准物质研制中首次应用冷冻干燥技术,样品保存问题得到了很好的解决,采用多家实验室协作定值,测试方法准确、可靠,标准值和不确定度合理,填补了国内外砷形态标准物质研制的空白。     

河水入渗过程中近岸带地下水中砷的形成与影响因素研究

沈阳黄家水源地是我国北方地区典型的傍河地下水水源地,近岸带地下水中铁(Fe)、锰(Mn)、砷(As)含量严重超标。为查明地下水中As的来源与影响因素,对研究区河水、地下水以及土壤样品进行采集与测试,分析了水样常规指标与碳硫稳定同位素、土样中典型矿物、砷的含量及赋存形态。结果表明,研究区河水中As含量很低,而地下水中As含量普遍超标。河水入渗初期,氧化性河水使部分含As矿物发生氧化而释放As;随着河水入渗,地下水向还原环境转变,含As的Fe/Mn矿物发生还原性溶解,地下水中As含量逐渐升高。研究区典型矿物有黄铁矿、菱铁矿、软锰矿、赤铁矿、针铁矿、菱锰矿等,通过可交换态砷解吸、有机质结合态砷氧化、铁锰氧化物结合态砷还原性溶解等,介质中的As释放至地下水中。地下水中As含量与酸碱度(pH)、氧化还原电位(Eh)呈一定负相关,与溶解有机碳(DOC)、 {\mathrm{HCO}}_3^{-}、Fe、Mn含量呈正相关。     

铁盐絮凝法对阳宗海湖泊水体的除砷效果及底泥的稳定性考察

2008年,昆明阳宗海受到严重砷污染,砷浓度高达0.134 mg/L。项目组充分考虑其受污染水体容量大、砷浓度低的实际情况,提出了安全、廉价、高效的FeCl3絮凝法治理方案。实验室小试结果表明,提出的FeCl₃絮凝法对As(Ⅲ)及As(V)均有理想的去除效果,并且湖水中大量存在的阴离子HCO^-₃可使治理过程中水体pH值基本保持不变。因此该方案摒弃了文献普遍报道所需要的预氧化及调节pH值的工艺步骤,将固体FeCl₃·6H₂O溶解、用湖水稀释后通过喷洒船将最终浓度为1%左右的FeCl₃水溶液喷洒到湖面上,使湖水中的AsO^3-₄及AsO^-₂与FeCl₃水解过程产生的Fe(OH)3胶体絮凝形成稳定的沉淀物被固定于底泥中。在对阳宗海进行降砷工程化治理期间,2009年11月-2010年9月砷浓度从0.117 mg/L快速下降到0.021 mg/L并可持续达到Ⅱ-Ⅲ类水标准(<0.05 mg/L),总除砷率高达 82.05%。沉积物中的As绝大部分以残渣态的形式被固定在沉积物中,生态风险很低。     

Arsenic exposure through groundwater in the middle Ganga plain in the Varanasi environs,India: A future threat

The study area covers an about 100 km² of the middle Ganga plain in Uttar Pradesh, experiencing intensive groundwater extraction. In order to recognize the arsenic contamination zones of the Varanasi environs, sixty eight groundwater samples have been collected and analyzed for major ions, iron and arsenic. Twenty one sediment samples in the four boreholes were also collected to deduce the source of arsenic in the groundwater. The preliminary survey reports for the first time indicates that part of rural and urban population of Varanasi environs are drinking and using for irrigation arsenic contaminated water mostly from hand tube wells (<70 m). The study area is a part of middle Ganga plain which comprises of Quaternary alluvium consists of an alternating succession of clay, clayey silt and sand deposits. The high arsenic content in groundwater samples of the study area indicates that 14% of the samples are exceeding the 10 μg/l and 5% of the samples are exceeding 50 μg/l. The high arsenic concentration is found in the villages such as Bahadurpur, Madhiya, Bhojpur, Ratanpur, Semra, Jalilpur, Kateswar, Bhakhara and Kodupur (eastern side of Ganga River in Varanasi), situated within the newer alluvium deposited during middle Holocene to Recent. The older alluvial aquifers situated in the western side of the Ganga River are arsenic safe (maximum As concentration of 9 μg/l) though the borehole sediments shows high arsenic (mean 5.2 mg/kg) and iron content (529 mg/kg) in shallow and medium depths. This may be due to lack of reducing conditions (i.e organic content) for releasing arsenic into the groundwater. Rainfall infiltration, organic matter from recently accumulated biomass from flood prone belt in the newer alluvium plays a critical role in releasing arsenic and iron present in sediments. The main mechanism for the release of As into groundwater in the Holocene sandy aquifer sediments of Varanasi environs may be due to the reductive dissolution of Fe oxyhydroxide present as coatings on sand grains as well as altered mica content. The high societal problems of this study will help to mitigate the severity of arsenic contamination by providing alternate drinking water resources to the people in middle Ganga plain and to arrange permanent arsenic safe drinking water source by the authorities.     

砷的水地球化学及其环境效应

砷在水环境中的迁移和富集可以产生严重的砷污染，砷在自然水系中主要以无机砷酸盐（AsO4^3-）和亚砷酸盐（AsO3^3-）两种形式存在，而砷的有机化合物的含量一般都很低，砷酸盐在富氧化性的水体中占优势，而亚砷酸盐则富集于还原性水体中，水体中As3 和As5 的相对含量主要受氧化还原条件和一些吸附一解吸平衡过程控制，As3 类比As5 类的毒性强得多，而无机砷化合物比有机砷化合物的毒性大，在pH值为5－6时，As^5 不易被还原成气态AsH3，而s^3 却能定量地被还原出来，根据这一性质，可完成水体中As3 和As5 的测定，砷在饮用水中的安全阀值仅为10ug/L，水体中高砷的危害可以通过水质净化予在消除或降低，铁的化学沉淀和吸附法，石灰软化法，活性氧化铝净化法和逆流渗透法等都可以有效地去除或降低饮用水中砷的含量。     

Arsenic distribution and hydrochemical factors in urban groundwater,Foshan City,South China

The distribution of arsenic （As） in shallow groundwater of eastern Chancheng District in Foshan City as a function of season and water table was investigated, and the influence of hydrochemical factors on the As distribution was discussed. The groundwater samples were collected from 20 sites in dry season and 9 sites in wet season. As concentrations in 20% groundwater samples exceeded value of the WHO guideline （10 μg/L）, and the highest As concentration of 23.5 μg/L occurred in dry season. It is observed that groundwater As concentration decreased with the increase of depth of water table in dry season, and were generally higher in wet season than that in dry season, indicating that ground surface As might be one of the main sources for shallow groundwater As in study area, especially in wet season. Groundwater As concentration in study area had significantly positive correlation with the concentration of Fe, Mn, NH4, F, and COD, and was positively correlated to pH, but negatively correlated to Eh and K, indicating that reductive dissolution of Fe and Mn （oxy）hydroxides might be one of the main control mechanisms for groundwater As mobilization, while pH and F also played an important role in controlling the groundwater As mobilization in study area.     

岩溶地下河中砷迁移过程及其影响因素分析——以广西南丹县里湖地下河为例

以广西南丹县里湖地下河作为研究区,对砷在地下河中的存在形态,迁移过程及其影响因素进行了分析。结果发现,里湖地下河中砷浓度较高且与人类活动密切相关;由于地下河中相对较低的氧化还原环境,使毒性更强的 As（Ⅲ）含量超过 As（V）,占总无机砷的53%,增加了该地区发生砷中毒的风险;总 As、As （III）和 As（V）在地下河中衰减了51%、36%、59%。相关性分析结果表明,沉积物中的 Fe、Ca、Mn、有机质及水体中的 Ca2＋与沉积物中的砷呈现显著正相关关系,有助于水体中砷的吸收;而水体中的 Cl-、SO 2-4、HCO -3与沉积物中的砷呈现负相关关系,不利于砷的吸附,其中 HCO -3的抑制作用最为明显。与非岩溶区水体相比,Ca 和 HCO -3成为影响砷迁移转化的主要因素,因此在岩溶地下河砷污染治理中应考虑岩溶区的水文地质特点,提高砷的污染治理效率。     

氢化物发生-原子荧光光谱法测定植物样品中汞硒砷

植物样品经硝酸-高氯酸一次湿法消解后,用氢化物发生-原子荧光光谱法同时测定汞、硒、砷。测定时加入消泡剂磷酸三丁酯,可有效消除泡沫,降低记忆效应,提高精密度。方法精密度(RSD,n=12)为汞2.96%,硒0.96%,砷2.49%。经加标回收试验和国家一级标准物质验证,测定结果与标准值吻合。     

吉林西部地区高砷地下水砷的阈值分析及风险评价

高砷地下水导致的砷中毒是吉林西部地区近年来新发现的地方病。为评价饮用水中砷对人体健康产生的潜在危害,在野外调查、采样分析的基础上,开展了水砷安全阈值分析 ,确定了砷的总质量浓度0.05 mg/L为研究区的水砷安全阈值,建立了地下水健康风险评价模型,进行了地下水砷健康风险评价。结果表明:研究区地下水砷引起的个人年均风险度最高达2.11×10^-3 a^-1,其中高砷的第四系承压水中97.06%的采样点水砷对人体的个人年均致癌风险度,大于国际辐射防护委员会(ICRP)推荐的最大可接受值5.0×10^-5 a^-1;作为备用水源的第三系大安组、泰康组承压水69.57%采样点砷的致癌风险度也超过最大可接受风险水平。通过对风险度评价结果与砷中毒病情等资料的对比分析,风险评价结果与砷中毒病情基本一致,验证了评价结果的合理性。     

Arsenic sequestration by sorption processes in high-iron sediments

High-iron sediments in North Haiwee Reservoir (Olancha, CA), resulting from water treatment for removal of elevated dissolved arsenic in the Los Angeles Aqueduct system, were studied to examine arsenic partitioning between solid phases and porewaters undergoing shallow burial. To reduce arsenic in drinking water supplies, ferric chloride and a cationic polymer coagulant are added to the aqueduct upstream of Haiwee Reservoir, forming an iron-rich floc that scavenges arsenic from the water. Analysis by synchrotron X-ray absorption spectroscopy (XAS) showed that the aqueduct precipitate is an amorphous hydrous ferric oxide (HFO) similar to ferrihydrite, and that arsenic is associated with the floc as adsorbed and/or coprecipitated As(V). Arsenic-rich floc and sediments are deposited along the inlet channel as aqueduct waters enter the reservoir. Sediment core samples were collected in two consecutive years from the edge of the reservoir along the inlet channel using 30- or 90-cm push cores. Cores were analyzed for total and extractable arsenic and iron concentrations. Arsenic and iron speciation and mineralogy in sediments were examined at selected depths by synchrotron XAS and X-ray diffraction (XRD). Sediment-porewater measurements were made adjacent to the core sample sites using polyacrylamide gel probe samplers. Results showed that sediment As(V) is reduced to As(III) in all cores at or near the sediment-water interface (0-4 cm), and only As(III) was observed in deeper sediments. Analyses of EXAFS spectra indicated that arsenic is present in the sediments mostly as a bidentate-binuclear, inner-sphere sorption complex with local atomic geometries similar to those found in laboratory studies. Below about 10 cm depth, XAS indicated that the HFO floc had been reduced to a mixed Fe(II, III) solid with a local structure similar to that of synthetic green rust (GR) but with a slightly contracted average interatomic Fe-Fe distance in the hydroxide layer. There was no evidence from XRD for the formation of a crystalline GR phase. The release of dissolved iron (presumably Fe²⁺) and arsenic to solution, as monitored by in situ gel probes, was variable but, in general, occurred at greater depths than arsenic reduction in the sediments by spectroscopic observations and appears to be near or below the depth at which sediment GR was identified. These data point to reductive dissolution of the sorbent iron phase as the primary mechanism of release of sorbed arsenic to solution.     

氧化还原生物对石门雄黄矿区尾矿砷释放行为研究

对石门4处典型不同种类的含砷尾矿进行样品采集,并采用1种氧化菌(氧化亚铁硫杆菌,Thiobacillus ferrooxidans,简称T.f)和2种还原菌(硫酸盐还原菌,sulfate reducing bacteria,简称SR;嗜酸铁还原菌,Acidiphilium cryptum JF-5,简称JF-5)分别对其进行作用,据此研究生物还原和氧化条件下原生和次生含砷矿物的释砷情况,进而确定潜在的释砷风险。ICP-OES定量分析显示,3种细菌作用后,雄黄矿和雌黄矿的砷释出浓度都不断升高。168 h氧化菌T.f作用后的砷释出顺序为雌黄矿>淋滤液次生含砷矿物>雄黄矿>含砷夹矸尾矿。LC-AFS原子荧光分析释出液砷形态结果表明:①T.f作用后,雄黄矿和雌黄矿表现出非常明显的差异;1.5 h作用后4种含砷矿物释放As(Ⅴ)的顺序为含砷夹矸尾矿>雄黄矿>淋滤液次生含砷矿物>雌黄矿;②2种还原菌作用后,SR更能促进雌黄矿释放的As(Ⅲ),其释放量是JF-5的2倍;雌黄矿释出As(Ⅲ)在168 h达到20.64 mg/L(SR)和9.54 mg/L(JF-5)。96 h SR作用后4种含砷矿物释放As(Ⅲ)的顺序为雌黄矿>淋滤液次生含砷矿物>含砷夹矸尾矿>雄黄矿。96 h JF-5作用后4种含砷矿物释放As(Ⅲ)的顺序为雄黄矿>雌黄矿>含砷夹矸尾矿>淋滤液次生含砷矿物。     

Stabilization of Fe/Cu nanoparticles by starch and efficiency of arsenic adsorption from aqueous solutions

Due to the severity of arsenic contamination of soil and water resources around the world, finding new adsorbents for arsenic removal from the water is of high importance. The present study investigates the possible use and effectiveness of starch-stabilized Fe/Cu nanoparticles for adsorption of arsenic from aqueous solutions. First, Fe/Cu nanoparticles at various starch concentrations of 0, 0.02, 0.04 and 0.06 wt% were synthesized and characterized by X-ray diffraction, transmission electron microscopy and zeta potential/particle size analyzer. Then 0.04 wt% stabilized Fe/Cu nanoparticles were tested for the sorption of As(III) and As(V) from synthetic arsenic-contaminated water. To have an understanding about the arsenic adsorption mechanism of nanoparticles, X-ray photoelectron spectroscopy (XPS) was performed before and after adsorption. The results showed that starch provides nanoparticles with a neutral surface and stabilization of nanoparticles is possible with 0.04 wt% or higher concentrations of starch. For 0.04 wt% starch-stabilized Fe/Cu nanoparticles, the adsorption isotherms fit well within the Langmuir equation, with maximum sorption capacities of 90.1 mg/g for As(III) and 126.58 mg/g for As(V) at a pH of 7.0 from the aqueous arsenic solutions. Examining the XPS spectra of nanoparticles before and after adsorption showed that arsenic adsorption by this nanoparticle can be due to the formation of inner-sphere arsenic complexes on the particle surface, and the surface oxygen-containing functional groups involved in adsorption. The high sorption capacity suggests the potential for applying starch-stabilized Fe/Cu nanoparticles to the contaminated waters for removal of arsenic.     

Natural attenuation of geothermal arsenic from Yangbajain power plant discharge in the Zangbo River,Tibet, China

The Yangbajain geothermal field located in central Tibet is characterized by the highest measured reservoir temperature among all hydrothermal systems in China. The high-temperature geothermal fluid extracted from Yangbajain has been used for electricity generation for over 30 years. The geothermal wastewater generated by the Yangbajain power plants, with arsenic (As) concentrations up to 3.18 mg/L, drains directly into the Zangbo River, the major surface water at Yangbajain, which has elevated arsenic concentrations in the segments downstream of wastewater discharges. However, along the flow direction of the river, the arsenic concentration decreases sharply. Further inspection reveals that the concentrations of weakly bound arsenic, strongly adsorbed arsenic and total arsenic in riverbed sediment were affected by the drainage of geothermal wastewater, indicating that the sediment serves as a sink for geothermal arsenic. A logarithmic relationship between the integrated attenuation coefficients (IAC) for three river segments and the corresponding adsorption distribution coefficients of riverbed sediment samples also suggests that besides the dilution of geothermal arsenic in the Zangbo River, natural attenuation of arsenic may be caused by sorption to riverbed sediment, thereby reducing its health threat to local residents using the Zangbo River as a drinking water source.     

Saraca indica leaf powder for decontamination of Pb: removal, recovery, adsorbent characterization and equilibrium modeling

The present study explores the effectiveness of Saraca indica leaf powder, a surplus low value agricultural waste, in removing Pb ions from aqueous solution. The influence of pH, biomass dosage, contact time, particle size and metal concentration on the removal process were investigated. Batch studies indicated that maximum biosorption capacity for Pb was 95.37% at the pH 6.5. The sorption process followed the first order rate kinetics. The adsorption equilibrium data fitted best to both Langmuir and Freundlich isotherms. Morphological changes observed in scanning electron micrographs of untreated and metal treated biomass confirmed the phenomenon of biosorption. Fourier transform infrared spectroscopy of native and exhausted leaf powder confirmed lead biomass interactions responsible for sorption. Acid regeneration was tried for several cycles with a view to recover the sorbed metal ion and also to restore the sorbent to its original state. The findings showed that Saraca indica leaf powder can easily be envisaged as a new, vibrant, low cost biosorbent for metal clean up operations.