砷浓度、形态及碳酸氢盐对蜈蚣草吸收砷的影响

为了探讨超富集植物蜈蚣草在处理高砷地下水方面的可行性,研究了水培条件下砷的浓度、形态和碳酸氢盐(HCO-3)对超富集植物蜈蚣草吸收砷的影响。实验中使用了浓度为0.1～100mg·L-1的As(III)和As(V)溶液。HCO-3处理中,HCO-3浓度范围为0.5～20mmol·L-1,As(III)或As(V)的浓度为5mg·L-1。结果表明,在水培条件下,蜈蚣草具有明显的耐高砷特征。当介质砷含量高达100mg·L-1时,砷的去除率可达到80%,且对As(III)的吸收效率高于As(V)。植物体内砷形态研究表明,蜈蚣草体内2种形态砷的含量与外源砷形态有一定的关系,As(V)处理条件下,植物体中的As(V)比例较As(III)处理高。高浓度的HCO-3(20mmol·L-1)处理对蜈蚣草地上部分生物量没有明显影响,但是抑制了地下部分的生长,并且对砷的吸收表现出明显的抑制作用。     

16S rDNA克隆文库解析江汉平原高砷地下水系统中的细菌多样性

为研究江汉平原高砷地下水系统中细菌多样性和种群结构,以2011年11月采自江汉平原仙桃市沙湖镇高砷含水层沉积物为研究对象,沉积物采自同一50m钻井,分别选取埋深9.9～10.1m和15.7～16.0m样品。提取沉积物中总DNA,采用16SrDNA克隆文库方法,分析高砷含水层沉积物中土壤细菌的多样性。结果发现,伯克氏菌目(Burkholderiales)、假单胞杆菌目(Pseudomonadales)和肠杆菌目(Enterobacteriales)构成了高砷系统中抗砷的优势菌群。结果表明,高砷含水层中生活有大量微生物,这些微生物在砷的地球化学循环中扮演着重要角色。     

AM真菌对烟草砷吸收及根际pH的影响

采用矿区3种砷(As)含量土壤水提液的琼脂培养基变色试验,研究接种土著(Glomus spp.,Acaulospora spp.)与外源(Glomus caledonium)AM真菌对煳草(Nicotiana tabacum L.)As吸收以及根际pH的影响.结果表明,除无As水平下的烟草对照苗根际pH持续升高外,其它处理的烟草化苗根际pH都有先升高后降低的规律,而且菌根化苗根际pH的降低速度快于对照苗.烟草地上部分As含量在所有处理中没有表现出显著的差异.在无As水平下,烟草地下部分As含量依次为外源菌根化苗>土著菌根化苗>对照苗.在低As、中As、高As水平下,土著菌根化苗的地下部分As含量显著高于外源菌根化苗以及对照苗.可见,接种AM真菌可以降低烟草根际pH,从而影响烟草的As吸收,这也显示了AM真菌应用于烟草安全的可能性.此外,本研究表明土著AM真菌与外源AM真菌对培养基质中的同一As水平有着不同的响应.     

不同价态无机砷对罗非鱼肝脏砷积累及GSH/GST解毒代谢的影响

低剂量中长期暴露下的氧化胁迫是砷对水生生物致毒的重要机制之一。本文通过对罗非鱼进行32 d的食物相砷暴露,测定不同时间点罗非鱼肝脏中谷胱甘肽(glutathione,GSH)含量和谷胱甘肽巯基转移酶(glutathione S-transferase,GST)活性,揭示不同价态无机砷对罗非鱼肝脏中GSH/GST的影响机制。经三价砷(As(III))暴露后,砷含量在2 d内显著增加而在随后的30 d内无显著性差异; 0～2 d内GSH含量显著增加,后降低,13 d后GSH含量均低于空白组; 0～6 d GST活性均大于空白组,6～8 d GST活性降低,8 d后活性高于空白组,且32 d达到最大值。经五价砷(As(V))暴露后,罗非鱼肝脏中砷含量逐渐增加,在20 d时达到最大值而后无显著性差异; 0～2 d时GSH含量降低,随后逐渐增加,在16 d达到最大值,16 d后GSH含量均低于空白组; 0～8 d时GST被大量诱导合成,8～20 d时GST合成被抑制,20 d后活性增加,在32 d达到最大值。As(III)和As(V)对罗非鱼GSH/GST的不同影响与其在罗非鱼体内的积累量有关。As(III)暴露后各时间点罗非鱼肝脏中的砷含量与GSH含量呈统计学正相关,而As(V)暴露无明显相关性。这是因为As(V)进入罗非鱼肝脏后会还原为As(III),进而GSH作为可提供巯基的还原剂而被大量消耗。另外,As(III)暴露后各时间点罗非鱼肝脏中的砷含量与GST活性呈显著负相关,而As(V)暴露却呈现出很强的滞后性,这是由于进入生物体内的As(V)需转化为As(III)后,才可直接作用于酶系统。可见,不同形态砷对水生生物的致毒机制需进一步深入研究。     

抗氧化系统在蜈蚣草细胞砷解毒机制中的作用

砷超富集植物——蜈蚣草体内可以富集高浓度的砷且不表现出受害症状,暗示蜈蚣草细胞具有较强的砷解毒机制.为探讨抗氧化系统在蜈蚣草砷解毒机制中的作用,测定了0、0.5、1和2mmol/L的砷酸盐[As(Ⅴ)]、亚砷酸盐[As(Ⅲ)]和二甲基胂酸盐(DMA)处理下蜈蚣草愈伤组织的丙二醛(Malonyldiadehyde,MDA)含量、非酶类抗氧化物质含量和酶类抗氧化物质的活性.结果表明,0.5mmol/L As(Ⅴ)和DMA就可以诱导氧化胁迫的产生,浓度越高胁迫程度也越严重.而1mmol/L的As(III)仍未使蜈蚣草愈伤组织产生氧化胁迫.在As(Ⅲ)处理下,酸溶性巯基含量增加,叶绿素和类胡萝卜素含量不变,过氧化氢酶(Catalase,CAT)和过氧化物酶(Peroxidase,POD)活性增加.在As(Ⅴ)处理下,酸溶性巯基含量减少,叶绿素和类胡萝卜素含量略有上升;CAT和POD活性先增加后减少.在DMA处理下,酸溶性巯基含量减少,叶绿素含量降低而类胡萝卜素含量增加,CAT和POD活性先增加后减少.与As(Ⅴ)和DMA相比,As(Ⅲ)处理下高酸溶性巯基含量、高氧化酶活性和低MDA含量暗示As(Ⅲ)对蜈蚣草的毒性可能比As(Ⅴ)和DMA要小.这些结果表明,酸溶性巯基和酶类抗氧化物质(CAT和POD)在蜈蚣草细胞砷解毒机制中发挥着重要作用.图4参22     

山阴地区高砷饮用水处理技术

通过对山西省山阴县高砷地下水分布和污染程度的实地调查,对高砷水环境中砷的形态及富集转化规律进行了研究,并在此基础上形成一套以曝气氧化和加药(加入FeCl2和FeCl3的混合物作为混凝剂)过滤工艺为基础的联合水处理方法.结果表明,在山阴县砷污染严重的地段,地下水的氧化还原电位Eh为-50～142 mV,pH值为8.28～8.73,这种Eh下降、pH升高的地下环境给高砷地下水的形成创造了条件.当地下水中ρ(硫化氢)<140μg·L-1时,用功率为5 W的松宝SB-648双头氧气泵连续曝气1.5 h即可达到基本去除的效果.以25 m深处地下水为例,其ρ(As)为275 μg·L-1,待硫化氢去除后在水中加入摩尔比n(FeCl2):n(FeCl3)=1:1的混合物,连续曝气5 h,水体中60%以上的As(Ⅲ)可转变为As(V).经投加药品和曝气氧化处理后的地下水若能及时通过简易过滤装置,过滤后的水体中ρ(As)仅为5～8 μg·L-1,达到GB 5749-2006<活饮用水卫生标准>,且过滤后的水体中ρ(Fe)为0.03 mg·L-1,远小于GB/T 14848-93<地下水水质标准>规定的Ⅰ类标准.该水处理方法可快速有效地将As(Ⅲ)转化为As(V),并使As(V)与混凝剂发生吸附共沉淀反应,从而达到高效除砷的效果.过滤过程则可以防止氢氧化物胶体与砷酸盐形成的絮体二次进入环境,同时进一步降低水体中铁离子含量.该方法适用于我国广大高砷水地区家庭分散式供水的处理.     

大同盆地富砷地下水的水化学与地球化学研究

为弄清大同盆地地下水中影响砷的迁移、富集的主要地球化学与生物地球化学过程,为区域供水安全提供指导作用,针对高砷地下水系统开展了水文地球化学与含水层沉积物全岩地球化学研究;并在此基础上探讨了研究区高砷地下水成因。结果表明,研究区高砷地下水为偏碱性、强还原环境,砷含量为0.31～452μg·L-1,主要以砷酸盐形式存在,地下水中砷与三价铁的浓度有显著的相关性。高砷含水层沉积物中有机质、铁与砷含量表现出显著相关性。以上结果说明,碱性还原环境有利于地下水中砷的富集;微生物参与下,沉积物相有机质的氧化和Fe氧化物/氢氧化物的还原过程是本区高砷地下水形成的主控因素。     

厌氧微生物作用下土壤中砷的形态转化及其分配

厌氧微生物作用下土壤中砷的形态转化及分配比例对砷的环境行为与归趋具有重要影响。实验利用张士污灌区土壤负载低浓度砷,研究了厌氧微生物作用下砷的形态转化过程,并通过磷酸盐及盐酸提取土壤中的砷、铁和硫,探讨了砷在土壤中结合形态的变化及土壤矿物结构转化与砷环境行为的关联。实验结果表明,微生物作用下土壤负载的砷被迅速还原为As(III)并释放进入液相,培养24h后液相累积的As(T)量达到16.9μmol·L-1,其中As(III)占液相总砷含量的91%以上;48h后释放的砷被再次固持,液相残留的As(III)浓度仅为1.5μmol·L-1。尽管微生物还原作用造成土壤中铁氧化物的活化,但固相中磷酸盐提取态与盐酸提取态砷所占的比例分别从载砷量的45.3%和49.8%降低到22.0%与0.22%,而体系中硫酸盐还原产生的硫离子的量与砷的释放量保持负相关。可见微生物还原作用下砷发生了活化,释放和再固定的过程,土壤负载的砷从溶解态、吸附态及铁氧化物结合态逐渐被转化为更稳定的硫化物结合态。此研究对于预测土壤中砷的行为与归趋及污染土壤修复具有一定意义。     

中国饮水型砷中毒区的水化学环境与砷中毒关系

中国各饮水型砷中毒区的水化学特点受沉积环境和气候因素所控制,砷中毒的流行和发病程度与其地下水的水化学环境、水中砷的形态和价态有密切联系。在实地考察监测和对台湾、新疆、内蒙古、山西、吉林饮水型砷中毒病区环境和地下水水化学特征总结的基础上,系统分析了饮水水源中总As、As(III)、甲基胂、腐植酸与砷中毒的关系,揭示了不同病区病情差异的原因。研究表明,除台湾外,各砷中毒区均分布在干旱半干旱区;各病区多分布在沉积盆地中心或平原内相对低洼的地带,饮用的地下水均取自中新生代地层;砷中毒病情不仅与总砷含量有明显的剂量-效应关系,还与As(III)和甲基胂的浓度直接相关。台湾、内蒙古和山西病区地下水为富含有机质的复杂还原环境,水中不仅As(III)含量高,且检出有机物、腐植酸和甲基胂,新疆和吉林病区地下水为以无机砷中As(V)为主的氧化环境,吉林病区未检测出甲基胂,这是新疆与吉林病区患病率较低的主要原因。研究成果可为区域防病改水、砷中毒的预报提供重要技术支撑。     

上海市河网水体中As的分布特征及其生态风险评价

2012年4月,在上海市河网采集表层水和沉积物样品各53个,测定其As含量,并采用潜在生态风险指数法对沉积物As的污染状况进行了评价。研究结果表明,上海市河网表层水和沉积物中As的含量分别为0.47～8.84μg·L-1和3.72～12.65μg·g-1,其中表层水中As的浓度处于中国地表水环境质量标准Ⅰ类水平,沉积物中As的浓度有15个样点超过了上海市土壤背景值,但均低于欧盟标准推荐值;表层水中As的浓度与pH呈显著正相关,说明pH值影响河水中As的迁移和转化;沉积物中As的浓度与总有机碳含量呈显著性正相关,说明沉积物中的As主要与总有机碳结合在一起;潜在生态风险评价结果显示,上海市河网沉积物中的As属于低生态风险。     

Species distribution of arsenic in sediments after an unexpected emergent discharge of high-arsenic wastewater into a river

The unexpected emergent discharge of high-arsenic wastewater into water environments results in significantly increased levels of arsenic in water; however, the species distribution of arsenic in sediments has never been reported before for such cases. This study focuses on an As pollution accident in the Dasha River, and uses sequential extraction procedures with deionized water, 1?mol·L^-1 MgCl₂ at pH= 8, 1?mol·L^-1 NaH₂PO₄ at pH= 5, and 1?mol·L^-1 HCl to investigate four binding phases of arsenic (i.e., water soluble, ion-exchangeable, strongly-bound, and precipitates) in sediments at different layers in different cross-sections along the river. The average ratio of arsenite (As(III)) to arsenate (As(V)) was found to decrease from 0.74:1 in river water to 0.48:1 in sediment, owing to its higher affinity toward As(V) than As(III). The content of arsenic in the sediments was relatively low and the maximum content was observed to be 36.3?mg·kg^-1 for As(III) and 97.5?mg·kg^-1 for As(V). As(III) and As(V) showed different binding phases in sediments, and the average fractions of these four species were determined to be 0.09, 0.11, 0.17, and 0.63 for As(III) and 0.03, 0.14, 0.63, and 0.20 for As(V), respectively. For all the sediment samples, the content of arsenic showed no relationship with the characteristics of the sediments such as the particle diameter, the content of organic carbon, Fe, and Mn, although a negative correlation with particle diameter was observed for the sediments in the uppermost 2-cm layer. The unexpected emergent As incident results in the high content of total arsenic in the surface sediment, which may be potential secondary source to the elevated As levels in surface water.     

Mobilization of arsenic in groundwater of Bangladesh: evidence from an incubation study

The extensive extraction of arsenic (As)-contaminated groundwaters for drinking, household and agricultural purposes represents a serious health concern in many districts of Bangladesh. This laboratory-based incubation study investigated the sources and mechanisms of As mobilization in these groundwaters. Several incubation studies were carried out using sediments collected from the Bangladesh aquifer that were supplemented, or not, with different nutrients, followed by an analysis of the sediment suspensions for pH, ORP (oxidation-reduction potential), EC (electrical conductivity) and As and Fe(ΙΙ) concentrations. In the substrate-amended sediment suspensions incubated under anaerobic environment, there was a mobilization of As (maximum: 50–67 μg/l) and Fe(ΙΙ) (maximum: 182 μg/l), while the ORP value decreased immediately and drastically (as much as −468 mV to −560 mV) within 5–6 days. In the sediment suspensions incubated under control and aerobic conditions, no significant As mobilization occurred. The simultaneous mobilization of As and Fe(ΙΙ) from sediments is a strong indication that their mobilization resulted from the reduction of Fe oxyhydroxide by the enhanced activity of indigenous bacteria present in the sediments; this phenomenon also provides insights on the mobilization mechanism of As in groundwater. The concentrations of As in the sediments used in the incubation studies were strongly linked to the gradients of redox potential development that was stimulated by the quantity of organic nutrient (glucose) used. The penetration of surface-derived organic matter into the shallow aquifer may stimulate the activity of microbial communities, thereby leading to a reduction of iron oxyhydroxide and As release.     

内蒙古自治区河套平原砷中毒高发区作物中砷的检测及健康风险评价

为了研究地方性砷中毒高发区作物中砷含量及其对人体健康的威胁,在内蒙古自治区河套平原4个自然村采集了72个谷物蔬菜水果、81份人体尿样和8个自来水样品。用高效液相色谱-电感耦合等离子体质谱(HPLC-ICP-MS)分析测定采集的样品中各形态砷及其含量;用ICP-MS分析测定消解后的作物样品中砷总量。结果表明,自来水中总砷含量均小于1.0μg·L-1。尿液样品中总砷含量为4.50～319μg·L-1(平均值为56.9μg·L-1),二甲基砷(DMA)是尿砷的主要形态(>70%)。作物中砷的主要形态有无机三价砷As(III)、无机五价砷As(V)和DMA。谷物和蔬菜水果中总砷含量的最大值分别为102和335μg·kg-1。成人和儿童最大日摄入砷量分别为232和205μg。通过分析采样地人体尿砷、作物砷和地方性砷中毒发病率的相关性得出,作物中砷的含量虽未明显超过国家标准,但对人体健康有明显的潜在威胁。政府改水后(饮用水由井水变为达标的自来水),人体的健康风险主要来自作物中的砷,而不是饮用水中的砷。     

Sediment geochemistry and arsenic mobilization in shallow aquifers of the Datong basin,northern China

Understanding the mechanism of arsenic (As) mobilization from sediments to groundwater is important for water quality management in areas of endemic arsenic poisoning, such as the Datong basin in northern China. The bulk geochemistry analysis of sediment samples from three 50-m boreholes drilled specifically for this study at As-contaminated aquifers, the groundwaters of which have an As concentration up to 1060 μg/l, revealed that the average bulk concentrations of major and trace elements of the samples are similar to those of the average upper continental crust. The average As content of the sediment samples (18.7 mg/kg) is higher than that of modern unconsolidated sediments (5–10 mg/kg). Moreover, the abundance of elements varied with grain size, with higher concentrations in finer fractions of the sediments, such as silt and clay. The concentration of NH₂OH–HCl-extracted iron (Fe) strongly correlated with that of extracted As, suggesting that Fe oxyhydroxides may be the major sink of As in the aquifer. The results of microcosm experiments showed that As mobilization from sediments to groundwater is probably mainly related to changes in the redox conditions, with moderately reducing conditions being favorable for As release from sediments into groundwater.     

微生物砷还原机制的研究进展

砷是一种剧毒物质,环境中的砷对人体健康存在潜在威胁,因此长期以来备受关注.微生物的各种代谢过程对砷在环境中的归趋起着重要作用,其中砷还原微生物能将吸附于固体矿物中的As(Ⅴ)还原为可溶性强的As(Ⅲ),使砷进入液相,从而加剧了地下水等饮用水源的砷污染.论文主要介绍了两种微生物砷还原机制(异化砷还原和细胞质砷还原)在作用...     

Effect of natural organic matter on arsenic release from soils and sediments into groundwater

Arsenic (As) contamination in groundwater has received significant attention recently. Natural and anthropogenic sources contribute to the worldwide occurrence of As contamination. As speciation is an important factor related to its toxic and mobile behavior. The release of As from soils and sediments into groundwater is governed by several geophysicochemical processes, of which, As sorption behavior is of principle significance. This review paper summarizes existing information regarding the effects of natural organic matter (NOM) on the fate and mobility of As species in the environment. NOM may enhance the release of As from soils and sediments into the soil solution, thereby facilitating As leaching into the groundwater. The main influencing mechanisms include competition for available adsorption sites, formation of aqueous complexes, and/or changes in the redox potential of site surfaces and As redox speciation. NOM may also serve as binding agents, thereby reducing As mobility. However, comparably little research has been performed on this aspect. Since most investigations have been done on purified minerals under laboratory conditions, further research involving various geological materials under natural environmental conditions is required. Development of proper geochemical conceptual models may provide means of predicting the role of NOM in arsenic leaching and/or immobilization.     

砷浓度、形态及碳酸氢盐对蜈蚣草吸收砷的影响

大同盆地是典型的高砷地下水分布区。利用从地方性砷中毒严重病区山阴县采集的高砷地下水样品,用稀释培养法实验研究了外加砷源对地下水中微生物数量的影响;同时基于生物学可培养法和16S rDNA序列比对法,选取代表性高砷水样,研究了耐砷菌的种群特征。结果表明,外加砷源对地下水中微生物数量影响显著,高浓度砷会抑制大部分微生物生长,使微生物数量减少;低浓度砷对微生物生长具有一定促进作用。通过多次分离、纯化从3个不同砷含量地下水样中分离到多株砷抗性菌,经鉴定属于主要为Bacillus、Pseudomonas、Paenibacillus、Aeromonas、Enterobacter5个属。从RDP(Ribosomal Database Project)分析显示3个水样可培养微生物组成不同,都有生存能力强能够耐低浓度NaAsO₂的Bacillales,优势耐砷菌是γ-proteobacteria,其中Enterbacter具有耐高浓度NaAsO₂的能力。