污染土壤中铅、砷的生物可给性研究进展

土壤铅、砷污染已成为重要的环境问题,并可对人体健康造成严重危害。对食物链途径的有效控制使得从口部无意摄入的土壤铅、砷对人体,特别是对儿童铅、砷摄入总量的贡献率越来越大,甚至成为主要来源。土壤中铅、砷直接进入人体的消化系统并可被人体胃肠道溶解出的部分称为其生物可给性。有效、准确地判定土壤中铅、砷的生物可给性已经成为解决儿童铅、砷中毒的关键科学问题。因此,有关土壤中铅、砷的生物可给性及其在人体健康风险评价中的应用受到了越来越多的关注。文章综述了污染土壤中铅、砷生物可给性的研究方法及各方法的优缺点,并从土壤性质、模拟胃肠条件等方面分析了影响土壤中铅、砷生物可给性的主要因素和存在的问题,还进一步论述了土壤中铅、砷生物可给性在人体健康风险评价中的应用。最后,提出了今后该领域应重点加强土壤铅、砷生物可给性的标准参考物、模拟胃肠条件的优化以及土壤铅、砷生物可给性在人体健康风险评价中的应用等方面的研究。以期充分发挥铅、砷等环境污染物的生物可给性研究方法的潜力,更好地为控制土壤污染、保护人类健康服务。     

茶叶中砷含量特征及不同摄入方式对茶叶中砷生物可给性的影响

本研究选取不同产地不同品种的茶叶作为研究对象,分析其砷含量特征,并采用人工胃肠模拟系统,研究茶叶以不同摄入方式(茶水、原茶、粉末)进入人体对砷生物可给性的影响.结果显示,17个不同产地不同种类茶叶样品中砷含量为ND—1.16±0.03 mg·kg-1,23.5%的样品未检测出砷浓度,11.8%的样品砷含量超过绿色食品-代用茶《中华人民共和国农业行业标准》(0.5 mg·kg-1),这是因为在加工过程中硫磺熏制干燥会造成茶叶砷污染;选择含砷量较高的茶叶样品研究不同摄入方式对砷生物有效性的影响,结果表明在胃肠阶段茶水中砷生物可给性显著大于原茶和粉末的摄入方式,其中在胃阶段粉末样品砷生物可给性显著大于原茶样品砷生物可给性,而在肠阶段原茶和粉末样品砷生物可给性差异不大.茶以3种不同摄入方式进入人体,在胃肠液中溶出浓度为0.02—2.80μg·L-1,小于WHO和我国《生活饮用水卫生标准》(GB5749—2006)中砷的限量标准10μg·L-1,不会对人体造成健康风险.     

含雄黄的中成药中砷的生物可给性及其初步风险评价

为研究含雄黄中成药中砷的含量状况,探明其中砷对人体的健康风险,选取含雄黄的中成药为研究对象,分析其中砷含量;通过人工胃肠体外模拟系统研究中成药中砷的生物可给性,并在此基础上进行初步的人体健康风险评价。结果显示,含雄黄中成药样品中砷全量为9.9×102～8.8×104mg·kg-1。中成药砷的生物可给性在胃阶段为0.20%～2.17%,小肠阶段为0.26%～2.43%。以WHO每日允许摄入量(ADI)为标准的健康风险评价结果表明,若以砷全量衡量,所有含雄黄中成药均对人体健康具有巨大风险;若以小肠阶段可给砷含量评价,砷日摄入量与ADI比值范围为1.48%～879.68%,约70%含雄黄的中成药的可给砷含量仍足以威胁人体健康。     

砷在海洋食物链中的生物放大潜力及发生机制探讨

砷是世界范围内危害最大的环境污染物之一,也是近海区域一种常见污染物。本文综述了近年来砷在海洋生态系统中累积、转化及传递的最新研究进展。海洋生物普遍具有较高含量的砷,这些砷主要为低毒性的有机砷形态。砷在许多海洋食物链/网中被生物放大,造成高营养级生物中的砷富集,可对生物与人类健康产生潜在危害;这与砷在淡水食物链/网中普遍被生物减小的现象形成鲜明对比。海洋鱼类和贝类等生物可将吸收的无机砷通过生物转化合成砷甜菜碱等有机砷形态,而有机砷比无机砷具有更高的食物链传递能力,可导致海洋鱼类富集更高浓度的砷。因此,砷在海洋生物中的有机形态可能有助于砷沿着海洋食物链/网富集,在某些情况下被生物放大。今后应该加强对不同砷形态在海洋食物链/网中传递及相应影响因素的研究,并通过室内模拟实验与野外调查相结合进行验证,从而加深对砷的生态毒理和生物地球化学作用的科学认识,对准确评估预测砷的生态风险和保障海洋生态安全有重要意义。     

污染场地土壤多环芳烃(PAHs)生物可利用浓度的健康风险评价方法

随土壤不慎经口摄入是PAHs对人体健康造成危害的重要途径之一,目前该暴露途径下PAHs的健康风险计算主要基于土壤中总PAHs浓度进行计算。但是,这种计算方法并未考虑PAHs在土壤中的赋存状态及经口摄入后在人体不同器官中的毒理动力学过程,导致计算结果过于保守,修复目标过于严格,修复成本过高。针对这一问题国外相关研究人员已开展基于土壤中PAHs生物可利用性的健康风险评价研究并取得较大进展,但在国内就如何在风险评价过程中引入PAHs生物可利用性及其面临的障碍缺乏系统性报道。在对土壤中PAHs赋存形态及其随土壤经口腔摄入后在人体消化及循环系统中的动态分配最新研究成果进行综述的基础上,通过对该暴露途径下现有风险计算模型存在问题及原因进行分析,提出基于土壤中PAHs可利用浓度进行风险计算,并对相应计算模型进行推导以及模型参数的获取方法进行了简要概括,以解决目前模型计算结果过于保守的问题。同时,对于在现有分层次进行场地健康风险评价思路中如何科学地纳入基于土壤中PAHs可利用浓度进行风险计算的思路以及在实际风险评价中应用该思路还需进行的研究工作进行了简要讨论。     

污染场地土壤多环芳烃（PAHs）生物可利用浓度的健康风险评价方法

随土壤不慎经口摄入是PAHs对人体健康造成危害的重要途径之一,目前该暴露途径下PAHs的健康风险计算主要基于土壤中总PAHs浓度进行计算。但是,这种计算方法并未考虑PAHs在土壤中的赋存状态及经口摄入后在人体不同器官中的毒理动力学过程,导致计算结果过于保守,修复目标过于严格,修复成本过高。针对这一问题国外相关研究人员已开展基于土壤中PAHs生物可利用性的健康风险评价研究并取得较大进展,但在国内就如何在风险评价过程中引入PAHs生物可利用性及其面临的障碍缺乏系统性报道。在对土壤中PAHs赋存形态及其随土壤经口腔摄入后在人体消化及循环系统中的动态分配最新研究成果进行综述的基础上,通过对该暴露途径下现有风险计算模型存在问题及原因进行分析,提出基于土壤中PAHs可利用浓度进行风险计算,并对相应计算模型进行推导以及模型参数的获取方法进行了简要概括,以解决目前模型计算结果过于保守的问题。同时,对于在现有分层次进行场地健康风险评价思路中如何科学地纳入基于土壤中PAHs可利用浓度进行风险计算的思路以及在实际风险评价中应用该思路还需进行的研究工作进行了简要讨论。     

不同含磷化合物修复铅污染土壤后的人体健康风险评价

磷酸盐钝化铅是铅污染土壤的重要修复技术之一.但磷酸盐修复土壤铅污染后,土壤铅对人体的健康风险仍缺乏系统研究.本研究通过向铅污染土壤添加五种不同的含磷化合物(KH_2PO_4、NH_4H_2PO_4、CaHPO_4,植酸和卵磷脂),分析了其对铅污染土壤的钝化效果,运用in vitro和SHIME模型评估修复后土壤铅对人体的健康风险.结果表明,添加含磷化合物30 d后,五种处理均有效降低了铅的DTPA和CaCl_2可提取态,分别降低了62.5%—66.5%和27.8%—49.5%,其中植酸和CaHPO_4处理效果较好,卵磷脂处理效果较差.5种处理中,铅的生物可给性在胃、小肠和结肠阶段有显著差异,分别为8.67%—9.31%、0.88%—1.55%、2.06%—2.76%,由于受pH的影响,铅在胃阶段生物可给性最高且各处理之间差异不明显,在小肠阶段KH_2PO_4处理土壤铅的生物可给性最低,卵磷脂处理铅的生物可给性最高,结肠阶段NH_4H_2PO_4处理土壤铅的生物可给性最低,卵磷脂处理铅的生物可给性最高.结肠阶段铅的生物可给性均高于小肠阶段的,可见肠道微生物促进了土壤中Pb的溶出,提高了铅的生物可给性,增加了人体的健康风险.在添加同等含量的含磷化合物修复铅污染土壤后,KH_2PO_4处理对人体健康风险最小,卵磷脂最大.     

小白菜的干鲜状态对其铅的生物可给性的影响(Effects of Dry and Fresh States of Brassica chinensis on the Oral Bioaccessibility of Lead)

为了研究小白菜的干鲜状态对其铅的生物可给性的影响,设置了对照(不添加铅,本底值为32.37mg·kg-1)、300mg·kg-1和500mg·kg-13种土壤铅浓度处理的盆栽实验,并将收获的小白菜分别以干样和鲜样进行基于生理学的invitro人工胃肠模拟实验,测定其中铅的生物可给性.结果表明:栽种2个月后,小白菜铅含量分别达到0.38mg·kg-1、4.55mg·kg-1和12.50mg·kg-1(干重),对铅的富集系数分别为0.012、0.015和0.025,可能存在较高的健康风险.invitro实验表明:样品干鲜状态、铅浓度处理以及二者的交互效应是影响铅的生物可给性的重要因素.无论干样还是鲜样,铅在胃阶段和小肠阶段的溶解态量均随样品铅含量的增加而线性增加;对于同一铅浓度处理,鲜样中铅的生物可给性无论在胃阶段还是小肠阶段均显著高于干样(p<0.01).使用干样进行健康风险评价可能会低估小白菜中的铅对人体的健康风险.     

中国关于砷的研究进展

综述了近年来有关中国的砷污染状况、相关的分析监测技术及砷化合物毒性的研究进展.在中国部分地区,长期砷暴露导致了严重的区域性的砷中毒,主要的暴露途径是饮用水、食物和煤炭的燃烧.样品前处理、砷的富集和形态分析技术的丰富和发展,为环境科学、毒理学和流行病学的研究提供了可靠的技术支持.生物检测是一种直接有效的污染物健康风险评估...     

砷化合物的摄入调控机制

流行病学结果显示慢性砷暴露可导致人群罹患皮肤癌、膀胱癌、肺癌等恶性疾病,但其致毒/癌机制尚不明确.目前关于砷暴露致毒/癌机理的讨论主要集中在砷的胞内作用途径,而较少关注砷摄入调控过程对其暴露致毒/癌的贡献.在生理条件下,部分砷化合物由于结构与磷酸根、葡萄糖、甘油等天然底物相近,可借由相应的载体被细胞摄入,摄入途径和效率存在显著的砷形态依赖性.此外,砷化合物的生物毒性效应与其赋存形态直接相关.可见,砷的摄入调控对于砷的暴露致毒/癌具有重要作用.本文主要综述了在哺乳动物体系中不同砷形态的摄入载体、载体调控及对应的砷摄入分布、效率和暴露毒性,在此基础上,强调了以往在砷致毒/癌机制研究中被忽视的砷摄入调控途径.然而,砷摄入调控过程中的诸多重要环节如砷胁迫下的摄入启动和调控机制等都是空白,需进一步系统深入地研究,为深入理解砷的致毒机制提供了新的视角和研究思路.     

Effect of biogeochemical interactions on bioaccessibility of arsenic in soils of a former smelter site in Republic of Korea

The total concentration-based regulations for soil remediation do not consider the possible changes in bioaccessibility of remaining arsenic (As) in soils due to biogeochemical interactions after remediation. This study used As-contaminated soil and pore water samples that were collected from the rice paddy and forest/farmland located in the vicinity of a former smelter site in Republic of Korea to elucidate the changes in As bioaccessibility due to biogeochemical interactions. Bioaccessibility and chemical forms of As in soils were determined by using an in vitro method and sequential extraction, respectively, and soil microbial community was evaluated. Bioaccessibility of As in the rice paddy soil samples was higher than that in the forest/farmland soil samples. This could be attributed to relatively higher dependence of bioaccessible As in the rice paddy soils on the soil concentration of iron (Fe), aluminum, or manganese, which could lead to greater changes in bioaccessible As via reductive dissolution. The strong linear relationship (R ² = 0.90, p value ≤0.001) between the pore water As and Fe concentrations, and the greater portion of bacterial species related to reductive dissolution of Fe oxides in the rice paddies can support the higher As bioaccessibility promoted by reductive dissolution. Therefore, it is necessary to consider the potential changes in the bioaccessible As due to biogeochemical interactions in remediation of As-contaminated soils, particularly when soils are likely to be reused under reductive dissolution-promoting conditions (e.g., flooded conditions).     

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.     

Influence of diet,vitamin, tea,trace elements and exogenous antioxidants on arsenic metabolism and toxicity

Health risk of arsenic (As) has received increasing attention. Acute and chronic exposure to As could cause several detrimental effects on human health. As toxicity is closely related to its bioaccessibility and metabolism. In real environment, many factors, such as diet and nutrition, can influence As bioaccessibility, metabolism and toxicity. This paper mainly reviews the influences of diets and elements on As bioaccessibility, metabolism and toxicity and their underlying mechanisms to provide suggestions for future investigations. Vitamins, jaggery, fruit, tea, glutathione, N-acetylcysteine and zinc could reduce the As-induced toxicity by increasing antioxidative enzymes to antagonize oxidative stress caused by As and/or increasing As methylation. However, bean and betel nut could increase risk of skin lesions caused by As. Interestingly, high-fat diet, selenium and iron have incompatible effects on As bioaccessibility, metabolism and toxicity in different experimental conditions. Based on current literatures, the As methylation and As-induced oxidative damage might be two main ways that the diets and elements influence As toxicity. Combined application of in vitro human cell lines and gastrointestinal models might be useful tools to simultaneously characterize the changes in As bioaccessibility and toxicity in the future research.     

Elemental concentrations and in vitro bioaccessibility in Canadian background soils

Elemental concentrations and bioaccessibility were determined in background soils collected in Canada as part of the North American Geochemical Landscapes Project. The concentrations of As, Cr, Cu, Co, Ni and Zn were higher in the C-horizon (parent material) compared to 0–5 cm (surface soil), and this observation along with the regional distribution suggested that most of the variability in concentrations of these elements were governed by the bedrock characteristics. Unlike the above-stated elements, Pb and Cd concentrations were higher in the surface layer reflecting the potential effects of anthropogenic deposition. Elemental bioaccessibility was variable decreasing in the order Cd > Pb > Cu > Zn > Ni > Co > As > Cr for the surface soils. With the exception of As, bioaccessibility was generally higher in the C-horizon soils compared to the 0–5 cm soils. The differences in metal bioaccessibility between the 0–5 cm and the C-horizon and among the provinces may reflect geological processes and speciation. The mean, median or 95th percentile bioaccessibility for As, Cr, Cu, Co, Ni and Pb were all below 100 %, suggesting that the use of site-specific bioaccessibility results for these elements will yield more accurate estimation of the risk associated with oral bioavailability for sites where soil ingestion is the major contributor of human health risk.     

Anomalous arsenic concentrations in groundwaters of an island community, Bowen Island, British Columbia

Recently, occurrences of elevated arsenic concentrations in bedrock groundwaters used for individual and municipal water supplies have been recognised along the mainland coast of southern British Columbia, Canada. An area on Bowen Island (Queen Charlotte Heights community) was chosen to investigate the source(s) of arsenic, geochemical processes controlling its aqueous uptake, the role of geology and structure in the formation of these waters, and the use of hydrogeochemical survey methods for detecting arsenious groundwater regions. Pyrite- arsenopyrite-Cu mineralisation in the Queen Charlotte Heights area is present as veins associated with NE-trending fault zones and as disseminations in marginal breccia and stockwork zones of a ryhodacite porphyry stock. Near surface mineralisation was later altered by supergene events to form minor pyrite- arsenopyrite in a matrix of limonite and clay. Geochemical factors that control the concentration and mobility of arsenic in these groundwaters include: (a) anion exchange of arsenic from clay minerals during cation divalent/univalent exchange processes (water softening) which leads to waters of high pH and high anion exchange capacities; (b) desorption of arsenic from Fe and Al oxyhydroxide minerals during pronounced shifts in pH from acid to alkaline conditions brought on by the water softening process; and (c) stepwise oxidation of arsenopyrite mineralisation to form arsenious sulphate-bearing groundwaters. The inconsistent behaviour of the As3+ and As5+ ions during the complex waterrock interaction processes described above, precludes the use of detailed chemical analyses to predict relative abundances of the more toxic As3+ species. For a full appreciation of the toxic impact of groundwaters containing total arsenic concentrations that are above regulatory guidelines an arsenic speciation analysis is required.     

Fractionation and speciation of arsenic in fresh and combusted coal wastes from Yangquan, northern China

In this study, the content and speciation of arsenic in coal waste and gas condensates from coal waste fires were investigated, respectively, using the digestion and sequential extraction methods. The fresh and fired-coal waste samples were collected from Yangquan, which is one of the major coal production regions in northern China. High-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) was used to determine the concentrations of four major arsenic species [As(III), As(V), monomethylarsonic acid (MMA) and dimethylarsenic acid (DMA)] in the extracts, while ICP-MS was used to measure total As content. Arsenic content in the investigated coal wastes and the condensate ranges between 23.3 and 69.3 mg/kg, which are higher than its reported average content in soils. Arsenic in coal waste exists primarily in the residual fraction; this is followed in decreasing order by the organic matter-bound, Fe–Mn oxides-bound, exchangeable, carbonates-bound, and water-soluble fractions. The high content of arsenic in the condensates indicates that combustion or spontaneous combustion is one of the major ways for arsenic release into the environment from coal waste. About 15% of the arsenic in the condensate sample is labile and can release into the environment under leaching processes. The water extractable arsenic (WEA) in the fresh coal waste, fired coal wastes, and the condensate varied between 14.6 and 341 μg/kg, with As(V) as the major species. Furthermore, both MMA and DMA were found in fresh coal wastes, fired coal wastes, and the condensate.     

土著细菌对江汉平原浅层含水层沉积物中砷迁移的影响

对江汉平原水文地质调查发现,该地区地下水砷含量已远超国家饮用水标准。以沉积物培养的土著细菌混合液为生物材料,以江汉平原高砷含水层沉积物为研究对象,在实验室内模拟地下水系统,研究厌氧环境条件下,不同生物量土著细菌和pH值对沉积物中砷迁移转化的影响,以及土著细菌活动下砷在不同沉积物中的迁移转化。结果表明,不同生物量菌悬液都能促进沉积物中As的释放,增加总As和As(III)的浓度,但150mL处理组,在研究后期,总As和As(III)的浓度呈现减缓趋势;在初始生物量一定的条件下,沉积物中As含量越高,细菌活动下总As相对释出量就越低,而且As(III)占所释出总As的比值就越高,但两个高砷含量沉积物组的差异较小;在初始pH值为5、7和9的培养条件下,细菌都能加速砷的迁移,但pH值为5的处理组(简称pH5处理组)最弱,在前8天,pH9处理组较pH7处理组的低,随后超过pH7处理组。研究表明,土著细菌悬液能加速As从沉积物中释出,并且释出的As以As(III)为主;在耐受的弱碱性环境条件下,细菌对砷的迁移和转化随环境的pH值增加而增强。     

An assessment of sampling,preservation, and analytical procedures for arsenic speciation in potentially contaminated waters

This study was undertaken to ascertain optimal methods of sampling, preserving, separating, and analyzing arsenic species in potentially contaminated waters. Arsenic species are readily transformed in nature by slight changes in conditions. Each species has a different toxicity and mobility. The conventional field sampling method using filters of 0.45 μm in size could overestimate the dissolved arsenic concentrations, as passing suspended particles that can act as a sink or source of arsenic depending on the site condition. For arsenic species in neutral pH and iron-poor waters, the precipitation can be stable for up to 3 days without any treatment, but for longer periods, a preservative, such as phosphoric acid, is required. Also, the analytical procedure must be selected carefully because the levels and hydride generation efficiencies of arsenic in different species can vary, even for the same amount of arsenic. For arsenic speciation in samples that also include organic species, a hybrid high-performance liquid chromatography (HPLC) column and inductively coupled plasma mass spectrometry (ICP-MS) gave the best resolution and lowest detection limits. However, the procedure using a solid phase extraction (SPE) cartridge can be used economically and conveniently for analyzing samples containing only inorganic arsenic species, such as groundwater, especially that related to mine activity.     

Arsenic trophodynamics along the food chains/webs of different ecosystems: a review

In drinking water, arsenic (As) food chain accumulation may pose a risk to human health. An attempt was made to synthesise the published information concerning As trophic transfer along the food chain/web of various marine, freshwater, and terrestrial ecosystems. Some investigations included As speciation. Further objectives were to outline the factors potentially influencing As trophodynamics and to understand the consequence of As trophic transfer in the environment.