Arsenic bioaccessibility in a gold mining area: a health risk assessment for children

High concentrations of total arsenic (As) have been measured in soils of gold mining areas of Brazil. However, bioaccessibility tests have not yet been conducted on those materials, which is essential for better health risk estimates. This study aimed at?evaluating As bioaccessibility in samples from a gold mining area located in Brazil and assessing children's exposure to As-contaminated materials. Samples were collected from different materials (a control and four As-contaminated soils/sediments) found in a gold mine area located in Paracatu (MG), Brazil. Total and bioaccessible As concentrations were determined for all samples. The control soil presented the lowest As concentrations, while all other materials contained high total As concentrations (up to 2,666?mg?kg(-1)) and low bioaccessible As percentage (<4.2%), indicating a low risk from exposure of resident children next to this area. The calculated dose of exposure indicated that, except for the pond tailings, in all other areas, the exposure route considering soil ingestion contributed at most to 9.7% of the maximum As allowed ingestion per day (0.3?μg?kg(-1) BW day(-1)).     

福建省稻米中的砷水平及其健康风险研究

为更好了解区域水平上水稻(OryzasativaL.)砷所引起的健康风险,在福建省9个地区采集了206份水稻样品并对其总砷和无机砷含量进行了分析,然后在此基础上建立风险评价模型并对其健康风险进行了评价。结果表明,福建省水稻精米中总砷平均含量为(0.105±0.091)mg·kg-1,无机砷平均含量为(0.045±0.019)mg·kg-1。全省所有样品中无机砷含量符合中国国家标准规定的限量标准(MCL)0.15mg·kg-1。通过膳食调查的数据和水稻无机砷含量对每天通过稻米消费无机砷摄入量进行了计算,全省平均每天无机砷摄入量为13.50μg,并且9个地区每天无机砷摄入量均超过了美国国家研究委员会所规定的最大限量标准10μg·d-1。根据无机砷摄入量和癌症斜率因子所构建的癌症风险模型结果表明,福建省稻米无机砷所引起的癌症风险为每100000有37.5人,虽然低于中国的平均水平(每100000有61人),但是超过了美国国家环境保护局所规定的可以接受的癌症风险的上限(每100000人有10人)。因此,需要进一步通过流行病学方面的调查来确定福建省稻米无机砷摄入和健康风险之间的关系。     

珠江三角洲稻田土壤砷及其向水稻籽粒迁移特征

采集珠江三角洲区域水稻(Oryze sativa L.)植株的根系、秸秆、稻谷和对应的耕层土壤(0～15锄)样品,分析土壤和水稻植株中砷含量,初步研究土壤砷与土壤基本理化性质的关系及砷在土壤-水稻系统中的迁移规律.结果表明,土壤砷含量在1.83～18.14 mg·kg~(-1)之间,土壤砷与土壤有机质、砂粒含量呈显著负相关,与土壤粉粒含量呈显著正相关.糙米中的砷含量在0.21～0.43mg·kg~(-1)之间,均未超过国家食品卫生标准(0.7mg·kg~(-1)),砷在水稻植株中的分布规律为根>秸秆>颖壳>糙米.糙米砷含量与秸秆砷含量呈极显著正相关,与秸秆中P/As、Si/As摩尔比呈极显著负相关,因此,降低秸秆中As的积累、增加秸秆中P、Si的积累可降低水稻籽粒中的砷含量.     

广东省土壤砷元素空间变异与环境意义

利用广东省260个土壤剖面数据,开展区域尺度下的土壤砷（As）元素质量分数的空间分布和垂直变异研究。结果显示,研究区土壤砷的几何平均质量分数为10.4 mg.kg-1,高于全国的平均水平9.6 mg.kg-1。表层土壤As的上基线质量分数为23.4 mg.kg-1。土壤As的空间分布特征主要决定其成土母岩的类型,主要表现为A、B、C 3层土壤As的空间展布形式相似,高As背景质量分数主要分布于石灰岩和砂页岩地区。此外,由A层至C层,As质量分数呈逐渐增加的趋势（由低到高依次为10.4 mg.kg-1,10.7 mg.kg-1,11.3 mg.kg-1）,但无底层富集特征,这种垂直变异特征与低有机质含量和强烈的土壤侵蚀作用有关。计算得出,研究区由土壤侵蚀引发的流入周边水体的土壤As每年可高达1 040 t。     

崇明东滩湿地沉积物砷的形态特征

于2008年4月在崇明东滩湿地开展野外调查,采集表层沉积物样品,参考Walter W W等提出的砷5步提取法进行总砷、砷的形态分析。结果表明:东滩湿地沉积物总砷含量5.33~19.74 mg/kg,各形态砷所占比例:弱交换态0.6%(0.5%~0.7%);强交换态5%(3%~7%);非晶形铁铝锰氧化物结合态28%(26%~29%);晶形铁铝锰氧化物结合态21%(19%~24%);残渣态46%(42%~51%)。     

Land use change and nitrogen enrichment of a Rocky Mountain watershed.

Headwater ecosystems may have a limited threshold for retaining and removing nutrients delivered by certain types of land use. Nitrogen enrichment was studied in a Rocky Mountain watershed undergoing rapid expansion of population and residential development. Study sites were located along a 30-km transect from the headwaters of the Blue River to Lake Dillon, a major source of drinking water for Denver, Colorado. Ground water in residential areas with septic systems showed high concentrations of nitrate-N (4.96 +/- 1.22 mg/L, mean +/- SE), and approximately 40% of wells contained nitrate with delta15N values in the range of wastewater. Concentrations of dissolved inorganic nitrogen (DIN) in tributaries with residential development peaked during spring snowmelt as concentrations of DIN declined to below detection limits in undeveloped tributaries. Annual export of dissolved organic nitrogen (DON) was considerably lower in residential streams, suggesting a change in forms of N with development. The seasonal delta15N of algae in residential streams was intermediate between baseline values from undeveloped streams and stream algae grown on wastewater. Between 19% and 23% of the annual N export from developed tributaries was derived from septic systems, as estimated from the delta15N of algae. This range was similar to the amount of N export above background determined independently from mass-balance estimates. From a watershed perspective, total loading of N to the Blue River catchment from septic and municipal wastewater (2 kg x ha(-1) x yr(-1)) is currently less than the amount from background atmospheric sources (3 kg x ha(-1) x yr(-1)). Nonetheless, nitrate-N concentrations exceeded limits for safe drinking water in some groundwater wells (10 mg/L), residential streams showed elevated seasonal patterns of nitrate-N concentration and ratios of DIN to total dissolved phosphorus, and seasonal minimum concentrations of nitrate-N in Lake Dillon have increased exponentially to 80 microg/L over the last decade from an initial value near zero. Results suggest that isotopic ratios in autotrophs can be used to detect and quantify increases in N enrichment associated with land use change. The biotic capacity of headwater ecosystems to assimilate increases in inorganic N from residential development may be insufficient to prevent nitrogen enrichment over considerable distances and multiple aquatic ecosystems downstream.     

湘南4个矿区稻田As污染状况的初步调查

通过实地调查以及土壤和水稻样品分析,研究了湘南郴州柿竹园铅锌矿、郴州界牌岭锡多金属矿、衡阳水口山有色金属矿、衡阳龙王山金矿4个矿区稻田的As污染状况.结果表明:4个矿区的稻田土壤和水稻植株均已受到严重的As污染.矿区稻田土壤As含量范围为30.0～225.7mg·kg-1,超过国家土壤环境质量3级标准;水稻根系、秸秆、谷壳、糙米As含量范围分别为115.6～588.2、4.19～20.88、1.388～5.374、0.214～0.892mg·kg-1,除部分糙米样品外,均超过我国食品中As限量卫生标准.矿区稻田土壤同时受到As和重金属的复合污染,综合污染指数(P)范围为0.76～13.12.矿区稻田的As污染主要由矿产的开采和冶炼造成,其中,水口山有色金属矿区和龙王山金矿区As污染以及As和重金属复合污染最为严重,柿竹园铅锌矿区污染面积较大,界牌岭锡多金属矿区由于发生过地质灾害改变了地表面貌,污染情况更为复杂.     

Bioaccessibility of arsenic in soils developed over Jurassic ironstones in eastern England

Jurassic ironstones outcropping over parts of eastern England give rise to soils with arsenic concentrations in excess of the UK soil guideline value of 20 mg kg⁻¹ for residential areas. Total arsenic concentrations were determined for 73 ironstone derived soils and bioaccessible arsenic determined using an in vitro physiologically based extraction test. The bioaccessible arsenic concentration for these soils was found to be well below the soil guideline value with a mean concentration of 4 mg kg⁻¹ and a range of 2–17 mg kg⁻¹. The bioaccessible fraction ranges from 1.2 to 33%. Data from a sequential extraction test based on the use of aqua regia as the main extractant is presented for a subset of 20 of the soils. Chemometric data reduction is used to demonstrate that the bioaccessible arsenic is mainly contained within calcium iron carbonate (sideritic) assemblages and only partially iron aluminosilicates, probably berthierine, and iron oxyhydroxide phases, probably goethite. It is suggested that the bulk of the non-bioaccessible arsenic is bound up with less reactive iron oxide phases.     

Arsenic in garden soils and vegetable crops in Cornwall,England: Implications for human health

Total concentrations of arsenic in surface (0–15cm) garden soils in the historical mining area of Hayle-Camborne-Godolphin, Cornwall, England are large and range widely (144–892 g/g). Amounts of water soluble and acid-fluoride extractable soil arsenic are significantly correlated with total content.Examination of 6 salad and vegetable crops grown in 32 gardens has shown arsenic concentrations in the edible tissues to be only slightly elevated. There were strong correlations between arsenic in beetroot, lettuce, onion and peas and soil arsenic (total, water soluble and acid extractable). Regression equations have been calculated. Ridge regression analysis applied to test the importance of other soil variables has shown both iron and phosphorus to influence the uptake of arsenic.Arsenic in all the vegetables sampled was below the statutory limit in the U.K. of 1 mg/kg fresh weight. Implications for health should be assessed in relation to other exposure routesvia water, air and directly ingested dust and soil.     

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     

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。     

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。     

Arsenic contamination in water,soil, sediment and rice of central India

Arsenic contamination in the environment (i.e. surface, well and tube-well water, soil, sediment and rice samples) of central India (i.e. Ambagarh Chauki, Chhattisgarh) is reported. The concentration of the total arsenic in the samples i.e. water (n=64), soil (n=30), sediment (n=27) and rice grain (n=10) were ranged from 15 to 825 μg L⁻¹, 9 to 390 mg kg⁻¹, 19 to 489 mg kg⁻¹ and 0.018 to 0.446 mg kg⁻¹, respectively. In all type of waters, the arsenic levels exceeded the permissible limit, 10 μg L⁻¹. The most toxic and mobile inorganic species i.e. As(III) and As(V) are predominantly present in water of this region. The soils have relatively higher contents of arsenic and other elements i.e. Mg, Al, Si, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Ga, Zr, Sn, Sb, Pb and U. The mean arsenic contents in soil of this region are much higher than in arsenic soil of West Bengal and Bangladesh. The lowest level of arsenic in the soil of this region is 3.7 mg kg⁻¹ with median value of 9.5 mg kg⁻¹. The arsenic contents in the sediments are at least 2-folds higher than in the soil. The sources of arsenic contamination in the soil of this region are expected from the rock weathering as well as the atmospheric deposition. The environmental samples i.e. water, soil dust, food, etc. are expected the major exposure for the arsenic contamination. The most of people living in this region are suffering with arsenic borne diseases (i.e. melanosis, keratosis, skin cancer, etc.).     

不同磷浓度下水稻短根突变体与野生型对五价砷吸收和转运的差异

为研究水稻根形态及磷营养状况对水稻吸收和转运五价砷的调控作用,采用水培的方法,研究了在不同外部磷浓度(0、10、50、150、300μM KH2PO4)下水稻(Oryza sativa L.)短根突变体与野生型短期内对五价砷(10μM Na3AsO4)吸收和转运的差异.结果表明,水稻根形态(短根突变体与野生型)和磷营养状况均能对水稻吸收和转运五价砷产生显著影响:1)磷能竞争性抑制水稻对五价砷的吸收,随营养液中磷浓度的增加,水稻地上部和地下部五价砷含量、单位根干重砷吸收量(根系砷吸收能力)均显著降低;2)水稻短根突变体对五价砷的吸收能力低于野生型,但转运能力高于野生型.     

两种通气组织不同的水稻品种根表铁膜的形成及砷吸收积累的差异（Differences of Iron Plaque Formation and As Accumulation between Two Rice Cultivars with Different Aerenchyma Tissue）

采用土壤盆栽试验方法,比较了两种通气组织结构不同的水稻品种(扬稻6号和农垦57)根表铁膜的形成及其吸收积累As的差异.结果表明,通气组织结构不同对水稻根表铁膜的形成及其对As的吸收积累有显著影响.通气组织结构发达的扬稻6号根表铁膜数量和铁膜中As含量均显著高于农垦57,扬稻6号根表铁膜量为431.53g·kg-1,铁膜中As含量达到220.2mg·kg-1,分别是农垦57的1.3和1.7倍.发达的通气组织结构显著抑制了As由水稻地下部到地上部的转运以及地上部对As的吸收:扬稻6号地上部As含量为10.77mg·kg-1,显著低于农垦57(12.85mg·kg-1);扬稻6号对As的转移系数(TF)为0.067,仅为农垦57的73.6%.     

硅促进水稻种子萌发及缓解幼苗砷毒性的效应研究

通过As~(Ⅲ)胁迫下水稻种子的发芽试验和幼苗毒性试验,研究了外源硅对水稻种子发芽率、幼苗生长的影响及其缓解幼苗砷毒性的效应。外源硅的2种处理方式为种子萌发时添加外源硅(Si1)和采用硅处理液浸种(Si2)。结果表明,发芽时介质中As浓度达到10 mg·L~(-1)时显著抑制水稻种子萌发(P0.05),发芽率仅为80%,但是Si1和Si2处理下发芽率则提高到97%和100%,这说明外源硅可促进砷胁迫下水稻种子萌发;砷浓度≥5 mg·L~(-1)时,Si1和Si2处理均可提高水稻的相对幼苗高度和根耐性指数,提高幅度分别为6.00%~16.8%和57.9%~77.0%、7.10%~23.5%和54.2%~61.2%,并且降低了水稻幼苗砷含量,降低幅度分别为17.8%~21.4%和31.0%~49.1%。这说明外源硅处理可促进砷胁迫下水稻幼苗的生长;不同砷浓度处理与水稻芽长、根长及幼苗干重之间存在"S"型的剂量-效应关系,且外源硅显著提高了相应的EC50,缓解了砷对水稻幼苗生长的毒性。综上所述,砷胁迫下水稻种子萌发时添加外源硅或采用硅处理液浸种均可促进水稻种子萌发和幼苗生长,并降低了幼苗砷累积和缓解砷对水稻幼苗的毒性。     

锑和砷对固氮菌的毒性效应及其机制研究

锑作为一种具有毒性和致癌性的类金属,其不合理的开发造成了严重的生态环境污染,尤其是土壤中高浓度锑和砷污染导致了环境中多种营养元素的缺乏。其中,氮素的缺乏严重阻碍了环境的恢复。然而,固氮微生物不仅能为氮素匮乏环境提供稳定的氮素来源,而且其固氮潜能可以作为监测土壤金属污染的敏感指标。为此,该文通过乙炔还原法(ARA)微宇宙培养试验手段,研究了不同价态锑和砷(三价及五价)在不同质量浓度(100、200、500、1 000、2 500、5 000 mg·L^-1)水平下对棕色固氮菌固氮潜能的影响,同时进一步探究了土壤固氮菌群落固氮潜能对土壤中主要锑和砷价态[Sb(Ⅴ)和As(Ⅴ)]的响应机制。结果表明,锑和砷浓度与棕色固氮菌和土壤固氮微生物的固氮潜能均呈显著负相关,验证了以固氮微生物固氮潜能作为生物指示物的可行性。此外,Sb(Ⅴ)对土壤固氮微生物的毒性显著小于As(Ⅴ)。三价锑和砷污染对固氮菌固氮潜能的毒性高于五价[As(Ⅲ)>Sb(Ⅲ)>As(Ⅴ)>Sb(Ⅴ)],这可能是由于Sb(Ⅲ)和As(Ⅲ)对细胞的致裂性强于Sb(Ⅴ)和As(Ⅴ)。相较于Sb(Ⅴ)和As(Ⅴ)对于棕色固氮菌固氮潜能的抑制作用,其对土壤固氮菌群落的固氮潜能的影响相对较弱。这一差异可能是由于土壤复杂的理化性质以及微生物群落和功能多样性而导致的。     

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。     

Arsenic in groundwater in six districts of West Bengal,India

Arsenic in groundwater above the WHO maximum permissible limit of 0.05 mg l^–1 has been found in six districts of West Bengal covering an area of 34 000 km² with a population of 30 million. At present, 37 administrative blocks by the side of the River Ganga and adjoining areas are affected. Areas affected by arsenic contamination in groundwater are all located in the upper delta plain, and are mostly in the abandoned meander belt. More than 800 000 people from 312 villages/wards are drinking arsenic contaminated water and amongst them at least 175 000 people show arsenical skin lesions. Thousands of tube-well water in these six districts have been analysed for arsenic species. Hair, nails, scales, urine, liver tissue analyses show elevated concentrations of arsenic in people drinking arsenic-contaminated water for a longer period. The source of the arsenic is geological. Bore-hole sediment analyses show high arsenic concentrations in only few soil layers which is found to be associated with iron-pyrites. Various social problems arise due to arsenical skin lesions in these districts. Malnutrition, poor socio-economic conditions, illiteracy, food habits and intake of arsenic-contaminated water for many years have aggravated the arsenic toxicity. In all these districts, major water demands are met from groundwater and the geochemical reaction, caused by high withdrawal of water may be the cause of arsenic leaching from the source. If alternative water resources are not utilised, a good percentage of the 30 million people of these six districts may suffer from arsenic toxicity in the near future.     

砷胁迫对不同烟草品种光合色素和叶绿素荧光特性的影响

为了研究不同浓度砷(As)对烟草光合色素和叶绿素荧光特性的影响,首先将3个烟草品种翠碧1号、K326和云烟-87幼苗种植在从0到100 mg·kg-1亚砷酸钠(Na As O2)的6个浓度组中进行盆栽试验,并定期进行烟草受害症状的观测,测定叶片的光合色素含量、叶绿素荧光参数。结果表明:烟草在As胁迫下的反应因As胁迫浓度、胁迫时间和烟草品种而异。烟草光合色素含量、叶绿素荧光参数均表现为低浓度下有促进效应和高浓度下有抑制效应,同时3种烟草在40 mg·kg-1As浓度处理下出现生长受阻,且浓度越高胁迫症状越明显。K326和云烟-87表观症状较明显,对As毒害的敏感性高于翠碧1号。随着As胁迫时间的延长,烟草的耐性增强,对As胁迫的敏感性减弱。