Environmental geochemistry study of arsenic in Western Hunan mining area,P.R. China

The geochemical characteristics of arsenic in the soil of the Western Hunan mining area of P.R. China were systematically studied. The results show that the strata of Western Hunan are rich in arsenic and that Western Hunan is a geochemically abnormal region for arsenic. The experimental study on speciation in the strata also indicates that the speciation of arsenic in the Neoproterozoic-Cambrian strata are mainly easily transferred speciation (exchangeable, carbonate-bound, sulfides-bound), which are approaching or exceed 60%. Arsenic content in the main soil of Western Hunan is in the range of 8.8–22.8 μg g⁻¹, the mean value is 16.1 μg g⁻¹, which is larger than the arsenic background value of Hunan soil. The distribution of rock with high arsenic content or high easily transferred arsenic speciation is consistent with the distribution of high arsenic content soil. In the mining region, part soils and river/brook waters were polluted by mine tailings and mining/smelting waste water. The arsenic content in polluted paddy soils and river/brook water is 46.26–496.19 μg g⁻¹, 0.3–16.5 mgL⁻¹, respectively. The positive abnormality and pollution of arsenic in the soil and water affects the arsenic content of the crop and the inhabitants’ health.     

土壤砷的环境基准研究

本文论述了砷在土壤中的分布和存在形态,探讨了土壤砷环境基准值的确定依据。考虑到土壤性质等的影响,应用国内的研究成果,确定了土壤砷的环境基准值。     

莲花山矿区土壤-农作物系统中重金属调控

以广东省莲花山钨矿区耕地为研究点,研究土壤金属含量分布、形态特征及其调控措施。分析耕地土壤中Zn、Cu、Mn、Ni、Pb、Cd、As含量特征,以碱石灰、MnO2、Fe2O3和钙镁磷肥作为改良剂,对矿区污染耕地土壤进行改良,并种植萝卜Raphanus sativus,分析各改良剂对土壤金属形态及其在土壤-农作物界面迁移的影响。研究表明,矿区耕地土壤酸化, Zn、Mn、Pb、Cd和As超过土壤背景值,其中Cd和As污染严重,分别超过背景值的10.2-16.7倍和1.1-1.3倍。碱石灰有效降低耕地土壤pH值,降低土壤Zn、Cu、Mn、Ni、Pb、Cd可溶态含量,减少其在萝卜中积累。萝卜对Pb、Zn、Cd、Cu、Ni累积量与其可溶态含量相关性显著,与总量相关性不显著。Fe2O3、MnO2、钙镁磷肥对耕地土壤Zn、Cu、Ni、Mn、Pb、Cd 生物有效性及其在农作物中累积量无显著影响。矿区耕地土壤分别添加碱石灰、Fe2O3、MnO2,土壤中砷松散结合态含量降低,农作物砷累积量减少。钙镁磷肥对土壤砷形态无显著影响,但能显著降低萝卜中砷的累积量。碱石灰分别与Fe2O3、MnO2、钙镁磷肥相结合改良耕地土壤,比单一改良剂更能有效降低萝卜中砷的累积量。萝卜中砷累积量与松散结合态存在显著正相关性,与Ca-As存在显著负相关性。碱石灰分别和Fe2O3、钙镁磷肥同时加入土壤,能同时地有效降低Zn、Cu、Mn、Ni、Pb、Cd、As的有效性,及其在农作物累积量,因此,这2种改良方式是莲花山矿区土壤金属固定的有效措施。     

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.     

广州市蔬菜地土壤重金属污染状况调查及评价

探讨了广州市蔬菜地土壤重金属污染状况,测定了95份土壤样品中铅、镉、铬、砷、汞的含量水平。土壤中铅、镉、铬、砷、汞的含量分别在6.44～153.10mg/kg、0-0.682mg/kg、5.82～101.60mg/kg、0.04～45.36mg/kg、0.01～O.32mg/kg之间。就污染的普遍性而言,铅污染最为普遍,其次是砷污染;就污染的程度而言,镉污染最严重.其次为砷、汞。对比今昔污染变化.广州市土壤污染治理已取得显著成效,但仍需努力。土壤中镉、砷、汞三种元素的变异系数,特别是镉的变异系数较大,这可能预示着点源性污染的存在。     

Stabilization of the As-contaminated soil from the metal mining areas in Korea

The stabilization efficiencies of arsenic (As) in contaminated soil were evaluated using various additives such as limestone, steel mill slag, granular ferric hydroxide (GFH), and mine sludge collected from an acid mine drainage treatment system. The soil samples were collected from the Chungyang area, where abandoned Au-Ag mines are located. Toxicity characteristic leaching procedure, synthetic precipitation leaching procedure, sequential extraction analysis, aqua regia digestion, cation exchange capacity, loss on ignition, and particle size distribution were conducted to assess the physical and chemical characteristics of highly arsenic-contaminated soils. The total concentrations of arsenic in the Chungyang area soil ranged up to 145 mg/kg. After the stabilization tests, the removal percentages of dissolved As(III) and As(V) were found to differ from the additives employed. Approximately 80 and 40% of the As(V) and As(III), respectively, were removed with the use of steel mill slag. The addition of limestone had a lesser effect on the removal of arsenic from solution. However, more than 99% of arsenic was removed from solution within 24 h when using GFH and mine sludge, with similar results observed when the contaminated soils were stabilized using GFH and mine sludge. These results suggested that GFH and mine sludge may play a significant role on the arsenic stabilization. Moreover, this result showed that mine sludge can be used as a suitable additive for the stabilization of arsenic.     

Stabilization of the As-contaminated soil from the metal mining areas in Korea

The stabilization efficiencies of arsenic (As) in contaminated soil were evaluated using various additives such as limestone, steel mill slag, granular ferric hydroxide (GFH), and mine sludge collected from an acid mine drainage treatment system. The soil samples were collected from the Chungyang area, where abandoned Au–Ag mines are located. Toxicity characteristic leaching procedure, synthetic precipitation leaching procedure, sequential extraction analysis, aqua regia digestion, cation exchange capacity, loss on ignition, and particle size distribution were conducted to assess the physical and chemical characteristics of highly arsenic-contaminated soils. The total concentrations of arsenic in the Chungyang area soil ranged up to 145 mg/kg. After the stabilization tests, the removal percentages of dissolved As(III) and As(V) were found to differ from the additives employed. Approximately 80 and 40% of the As(V) and As(III), respectively, were removed with the use of steel mill slag. The addition of limestone had a lesser effect on the removal of arsenic from solution. However, more than 99% of arsenic was removed from solution within 24 h when using GFH and mine sludge, with similar results observed when the contaminated soils were stabilized using GFH and mine sludge. These results suggested that GFH and mine sludge may play a significant role on the arsenic stabilization. Moreover, this result showed that mine sludge can be used as a suitable additive for the stabilization of arsenic.     

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.     

链霉菌的抗砷特性及其对蜈蚣草富集砷的作用

本文研究了链霉菌Streptomyces sp.的耐砷特性及其对蜈蚣草富集砷的影响。结果表明,Streptomyces sp.可在100mmo·lL-1的砷酸盐溶液中生长,具有较强的抗砷毒害能力,且在48h内对As(Ⅴ)的还原率达96.5%。施用Streptomyces sp.能促进植物对砷的吸收,蜈蚣草地上部砷浓度为930mg·kg-1,地上部砷累积量达到对照组的2.09倍。加入Streptomyces sp.后,能促进根际土壤中As(Ⅴ)还原成As(Ⅲ),大幅度降低根际土壤残渣态砷含量,从48.15mg·kg-1下降至28.75mg·kg-1。Streptomyces sp.通过影响蜈蚣草根际环境,提高根际土壤pH,增加DOC含量,促使砷形态变化,从而增加砷生物可利用性。该菌可作为强化蜈蚣草修复砷污染土壤的材料。     

Synergistic degradation of pyrene and volatilization of arsenic by cocultures of bacteria and a fungus

The combination of two bacteria (Bacillus sp. PY1 and Sphingomonas sp. PY2) and a fungus (Fusarium sp. PY3), isolated from contaminated soils near a coking plant, were investigated with respect to their capability to degrade pyrene and volatilize arsenic. The results showed that all strains could use pyrene and arsenic as carbon and energy sources in a basal salts medium (BSM), with the combined potential to degrade pyrene and volatilize arsenic. Bacillus sp. PY1, Sphingomonas sp. PY2 and Fusarium sp. PY3 were isolated from the consortium and were shown to degrade pyrene and volatilize arsenic independently and in combination. Fungal-bacterial coculture has shown that the most effective removal of pyrene was 96.0% and volatilized arsenic was 84.1% after incubation in liquid medium after 9 days culture, while bioremediation ability was 87.2% in contaminated soil with 100 mg·kg^-1 pyrene. The highest level of arsenic volatilization amounted to 13.9% of the initial As concentration in contaminated soil after 63 days. Therefore, a synergistic degradation system is the most effective approach to degrade pyrene and remove arsenic in contaminated soil. These findings highlight the role of these strains in the bioremediation of environments contaminated with pyrene and arsenic.     

Evaluation of Electrokinetic Remediation of Arsenic-contaminated Soils

The potential of electrokinetic (EK) remediation technology has been successfully demonstrated for the remediation of heavy metal-contaminated fine-grained soils through laboratory scale and field application studies. Arsenic contamination in soil is a serious problem affecting both site use and groundwater quality. The EK technology was evaluated for the removal of arsenic from two soil samples; a kaolinite soil artificially contaminated with arsenic and an arsenic-bearing tailing-soil taken from the Myungbong (MB) gold mine area. The effectiveness of enhancing agents was investigated using three different types of cathodic electrolytes; deionized water (DIW), potassium phosphate (KH₂PO₄) and sodium hydroxide (NaOH). The results of the experiments on the kaolinite show that the potassium phosphate was the most effective in extracting arsenic, probably due to anion exchange of arsenic species by phosphate. On the other hand, the sodium hydroxide seemed to be the most efficient in removing arsenic from the tailing-soil. This result may be explained by the fact that the sodium hydroxide increased the soil pH and accelerated ionic migration of arsenic species through the desorption of arsenic species as well as the dissolution of arsenic-bearing minerals.     

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.     

Status and fuzzy comprehensive assessment of metals and arsenic contamination in farmland soils along the Yanghe River,China

Concentrations of metals and arsenic in farmland soils along the Yanghe River, upstream of Guanting Reservoir, were evaluated using fuzzy comprehensive assessment (FCA). FCA is an emerging methodology for assessing environmental status based on fuzzy logic which can model linguistic data and represent chaotic conditions. The ratio of concentrations of metals and arsenic (As) in surface soils of farmland along the Yanghe River to the corresponding reference values decreased in the order Cd>Zn>Cr>Ni>Pb>Cu>As. Based on the FCA, 86% of surface soils along the Yanghe River were classified as grade C, which is suitable for forestry with a greater absorption capacity, suggesting that most farmland along the Yanghe River has to be abandoned as farmland. In order to improve the quality of soil along the Yanghe River and avoid degeneration of water quality in the river and the Guanting Reservoir, remediation of farmland soils along the river is suggested.     

Application of geostatistical methods to arsenic data from soil samples of the Cova dos Mouros mine (Vila Verde-Portugal)

A total of 286 soil samples were collected in the Cova dos Mouros area. All samples were dry sieved into the <200 mesh size fraction and analysed for Fe, Cu, Zn, Pb, Co, Ni, Bi and Mn by atomic absorption spectrometry (AAS) and for As, Se, Sb and Te by atomic absorption spectrometry-hydrid generation (AAS-HG). Only the results of arsenic are discussed in this paper although the survey was extended to all analysed chemical elements. The purpose of this study was to make a risk probability mapping for arsenic that would allow better knowledge about the vulnerability of the soil to arsenic contamination. To achieve this purpose, the initial variable was transformed into an indicator variable using as thresholds the risk-based standards (intervention values) for soils, as proposed by [Swartjes 1999. Risk based assessment of soil and groundwater quality in the Netherlands: Standards and remediation. J. Geochem. Explor.73 1–10]. To account for spatial structure, sample variograms were computed for the main directions of the sampling grid and a spherical model was fitted to each sample variogram (arsenic variable and indicator variables). The parameters of the spherical model fitted to the arsenic variable were used to predict arsenic concentrations at unsampled locations. A risk probability mapping was also done to assess the vulnerability of the soil towards the mining works. The parameters of the spherical model fitted to each indicator variable were used to estimate probabilities of exceeding the corresponding threshold. The use of indicator kriging as an alternative to ordinary kriging for the soil data of Cova dos Mouros produced unbiased probability maps that allowed assessment of the quality of the soil.     

矿区砷污染对土壤线虫群落结构特征的影响

对湖南省石门县雄黄矿区不同As污染程度土壤线虫群落结构特征进行了研究.共获得线虫27属,食真菌线虫滑刃属(Aphelenchoides)在3种土壤中均为优势属.食细菌和食真菌线虫分别为低As和中As土壤的优势营养类群,而植物寄生线虫为高As土壤的优势营养类群.低As和中As土壤的自由生活线虫成熟度指数(IM)和瓦斯乐斯卡指数(IW)显著高于高As土壤,但植物寄生线虫成熟度指数(IPP)和IPP/IM比值则表现出相反的趋势.可见,高As土壤的食物网受到As污染的干扰较大,群落环境质量较差.因此,土壤线虫群落结构对土壤质量或生态系统的变化具有很好的生物指示作用.     

Ecological risk assessment from the perspective of soil heavy metal accumulations in Xiamen city,China

Contamination of soils by heavy metals is of rising concern in many cities in China undergoing rapid urbanization. Here, we evaluate the severity of soil contamination by four heavy metals (arsenic, chromium, copper, and lead) at 146 urban and suburban sites within the city of Xiamen, Fujian, China. A multivariate regression model was proposed and developed to simulate heavy metals accumulation in urban and suburban soils, to identify the concentration and spatial distribution of heavy metals in soils, and to assess ecological risks by 2020. Results showed that, overall, Xiamen soils should be subject to low ecological risks due to heavy metals contamination by 2020, the ecological risks for urban soils were greater than suburban soils, nearly half of Xiamen soils are at moderate ecological risks, and many suburban soils experience low ecological risks. The methods demonstrate the potential to predict future ecological risks from heavy metals contamination which could inform pollution prevention and control measures.     

Arsenic toxicity in crop plants: physiological effects and tolerance mechanisms

Heavy metals are toxic substances released into the environment, contributing to a variety of toxic effects on living organisms in food chain by accumulation and biomagnifications. Certain pollutants such as arsenic (As) remain in the environment for an extensive period. They eventually accumulate to levels that could harm physiochemical properties of soils and lead to loss of soil fertility and crop yield. Arsenic, when not detoxified, may trigger a sequence of reactions leading to growth inhibition, disruption of photosynthetic and respiratory systems, and stimulation of secondary metabolism. Plants respond to As toxicity by a variety of mechanisms including hyperaccumulation, antioxidant defense system, and phytochelation. Arbuscular mycorrhizae symbiosis occurs in almost all habitats and climates, including disturbed soils. There is growing evidence that arbuscular mycorrhizae fungi may alleviate metal/metalloid toxicity to host plant. Here, we review (1) arsenic speciation in the environment and how As is taken up by the roots and metabolised within plants, and (2) the role of arbuscular mycorrhizae in alleviating arsenic toxicity in crop plants.     

叶面喷施硒硅复合溶胶抑制水稻砷积累效应研究

砷是一种毒性较强的类金属元素,稻米砷污染是近年来环境科学关注的难点和热点问题。为了控制稻米对砷的吸收积累,利用水热合成法制备了一系列浓度硒掺杂硅复合溶胶。采用盆栽和大田试验结合的方法,研究了硒掺杂纳米硅溶胶对水稻（Oryza sativa L.）砷吸收积累的影响。结果显示,叶面喷施硒掺杂纳米硅溶胶可以有效缓解水稻砷毒害,增加稻米硒含量,抑制稻米砷积累。盆栽试验结果表明：叶面喷施质量分数1%的硒掺杂纳米硅溶胶（1%Se-Si处理）后,水稻籽粒干质量比对照增加了43.8%,砷含量下降了46%,硒含量由对照的0.050 mg·kg-1增加到0.272 mg·kg-1。且与喷施亚硒酸钠相比（1%Se处理）,喷施硒掺杂纳米硅溶胶更有利于水稻生长,抑制稻米砷积累。与喷施硒质量分数1%的亚硒酸钠（1%Se处理）相比,喷施质量分数1%的硒掺杂纳米硅溶胶（1%Se-Si处理）后,水稻籽粒干质量增加了65.4%,砷含量下降了33.1%。大田试验结果也表明：叶面喷施硒硅复合溶胶可以显著抑制稻米砷积累,且随着硒掺杂量的增加,稻米砷含量显著降低、硒含量显著增加;硒的最佳掺杂量质量分数为0.5%,叶面喷施这种硒掺杂硅溶胶,稻米总砷质量分数由对照的0.25 mg·kg-1下降到0.14 mg·kg-1,稻米中硒的质量分数为0.26 mg·kg-1,符合富硒大米标准。砷污染稻田上,叶面喷施硒硅复合溶胶不仅使稻米砷含量达标,而且可以生产出富硒大米。因此,叶面喷施硒硅复合溶胶可能是治理稻米砷污染的新途径。     

沙颍河沈丘段底泥、土壤中砷及重金属污染与潜在生态风险评价

为查明沙颍河沈丘段底泥、土壤中砷(As)和重金属污染状况及其潜在生态风险,对底泥和土壤样品中的砷(As)、铬(Cr)、汞(Hg)、镉(Cd)和铅(Pb)的含量水平进行测定,并进行潜在生态风险指数计算。结果表明,沙颍河沈丘段底泥中As含量为9.206～11.641mg·kg-1,距河5km的白果村农田土壤中As含量为8.52～80.31mg·kg-1,超标率达到57.8%,Cr、Hg、Cd和Pb的超标率分别达到32.8%、59.4%、67.2%和39.1%。沙颍河沈丘段底泥和附近村庄农田土壤中As和4种重金属的总潜在生态风险为中等生态风险,主要来源于Hg和As。     

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。