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.     

土壤中铜的生物可给性及其对人体的健康风险评价

为了研究土壤中铜的生物可给性与土壤理化性质之间的相互关系以及人体无意摄入土壤铜的风险,采集我国一些地区的15个土壤样品,利用in vitro方法研究了这些土壤中铜的生物可给性及其对人体的健康风险。结果表明,有2个土壤样品中铜的含量高过我国土壤环境质量标准的三级标准,有8个土壤样品中铜的含量高过二级标准;土壤中铜的溶解态浓度及其生物可给性变化很大,胃肠阶段铜的溶解态含量分别为5.2~308.8 mg·kg~(-1)和5.9~348.5 mg·kg~(-1),平均值分别为74.8 mg·kg~(-1)和82.0 mg·kg~(-1);而铜的生物可给性分别为183%~66.6%和213%~77.4%,平均值分别为442%和51.1%。胃阶段铜的生物可给性与土壤有机质和pH呈显著正相关,而与粘粒呈显著负相关,与铁铝氧化物有显著相关性;小肠阶段铜的生物可给性与土壤有机质和pH呈显著正相关,与土壤中总铜和锰氧化物含量呈显著负相关。如以胃阶段为判断,无意摄人土壤中铜对儿童的TDI(tolerable daily intake)贡献率除浙江富阳为2.51%外,有12个土壤样品低于1.00%,最低为0.11%。如以小肠阶段为判断,无意摄入土壤中铜对儿童的TDI贡献率除浙江富阳和浙江台州的土壤分别为2.83%和2.01%,另有12个土壤样品低于1.00%。可见,对于本研究中大多数土壤,通过口部无意摄入土壤中铜的对人体并没有很高的风险。     

肠道微生物对土壤中铜、锌、锰生物可给性的影响

为了更全面、准确地评价土壤中金属元素对人体的健康风险,研究土壤中金属元素在结肠阶段的生物可给性具有重要意义。通过采集我国一些地区的6种土壤,利用in vitro方法(PBET和SHIME联用)研究土壤中Cu、Zn、Mn在胃、小肠、结肠阶段的生物可给性。研究显示,土壤中Cu、Zn、Mn在胃阶段的生物可给性分别为23.8%~63.0%、21.2%~64.4%、11.7%~35.6%;从胃阶段到小肠阶段,土壤中Cu的生物可给性提高了0.4%~14.4%,而土壤中Zn在小肠阶段的生物可给性降低了6.7%~38.7%。结肠阶段,土壤中Cu、Zn、Mn的生物可给性分别为2.4%~12.9%、5.7%~18.7%、6.2%~18.9%,与小肠阶段相比,分别降低了21.7%~56.9%、0.4%~36.8%、4.5%~19.1%。结果表明,在肠道微生物存在的情况下,土壤中Cu、Zn、Mn在结肠阶段有较低的人体健康风险。     

淮北煤矿周边土壤重金属生物可给性及人体健康风险

为了探究煤矿周边农田土壤重金属污染状况以及评估可能对人体带来的健康危害,本研究以安徽省淮北地区3座主要煤矿为研究区,对土壤重金属含量进行分析,并采用体外胃肠模拟方法(PBET),计算土壤中重金属的生物可给性,并以此修正健康风险评价计算方法.结果表明,土壤中重金属含量平均值(mg·kg~(-1))分别为Cd (0.16)、Cr (11.82)、Cu (12.03)、Ni (21.86)、Pb (55.09)、Zn (41.46),与国内不同类型矿区相比,淮北煤矿区周边土壤重金属含量较低;重金属的生物可给性平均值大小顺序是:胃阶段:Pb (61.69%)Cu (51.88%)Cd (43.88%)Cr (26.48%)Zn (17.45%)Ni (14.57%),小肠阶段为:Cr (58.80%)Cu (55.71%)Zn (51.40%)Ni (39.44%)Pb (7.59%)Cd (7.32%);由生物可给性校正后,成人和儿童不同重金属非致癌风险暴露量均小于1,说明成人和儿童均不存在非致癌风险,不同种类重金属的致癌风险为:CrCdNi,其中,Cr的致癌风险介于10~(-6)—10~(-4)之间,表明Cr对人群有一定的致癌风险,但在可接受的范围内,且儿童的致癌风险高于成人,经手-口无意摄入是土壤重金属最主要的暴露途径.     

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。     

应用四种体外消化方法比较研究场地土壤中重金属的生物可给性及其人体健康风险

本研究采用PBET(physiologically based extraction test)、DIN(Deutsches Institut für Normung)、IVG(Invitro Gastrointestinal)和UBM(Unified BARGE Method)等4种体外消化方法,比较8个工矿废弃场地土壤中6种典型重金属的生物可给性并进行健康风险评估分析.结果显示,在4种方法的胃阶段,土壤Co、Ni、Cu、Zn、As和Cd的生物可给性范围分别为1.57%—88.07%、6.69%—129.78%、8.68%—122.62%、18.55%—128.75%、4.17%—61. 14%和32. 22%—118. 44%;小肠阶段分别为0—43. 49%、3. 12%—61. 94%、4. 75%—123. 91%、1.48%—99.02%、5.93%—39.70%和8.48%—67.83%.总体而言,采集的场地土壤中多数重金属生物可给性在各方法的胃阶段均显著高于小肠阶段.土壤重金属在胃阶段的生物可给性分析显示,Co、Ni、Cu和As在UBM和IVG方法中较高,Zn在DIN方法中最高,Cd在UBM和DIN方法中高于其他方法.土壤重金属在小肠阶段的生物可给性分析显示,Co和Ni在UBM方法中最高,Cu在DIN和UBM方法中高于PBET和IVG方法; Zn生物可给性的顺序为DINPBETIVGUBM; As和Cd在IVG方法中均较高.与基于总量的重金属健康风险评估相比,采用生物可给性为评估参数,对8个场地土壤进行的评估分析显示风险水平显著降低,本研究中的场地土壤若采用基于总量的评估方法可能会高估重金属污染的风险.     

土壤中金属的生物可给性及其动态变化的研究

土壤中金属的生物可给性常应用于人体健康风险评价,如能准确地判定土壤中金属在胃肠阶段不同时间的溶出动态,研究者就可以更好地分析其对人体的健康风险。本文采集5种不同地区的重金属污染的土壤,利用改进的PBET方法,分别在胃阶段的20、40、60、80 min以及小肠阶段的1、2、3、4、5 h时取样并分析,探究土壤中8种金属元素（As、Al、Cd、Cr、Fe、Mn、Ni、Pb）的生物可给性和溶出动态,探讨造成金属溶出动态变化的影响因素,对其溶出机理进行初步探究。研究结果表明,Fe、Al的生物可给性较低,并且在胃肠阶段差异较小。与胃阶段相比,土壤中Pb、Cd的生物可给性在小肠阶段明显降低,而As、Mn、Cr、Ni的生物可给性在小肠阶段均升高。升幅最大的两个元素是Ni、Cr,其小肠阶段的平均生物可给性分别升高61.4%、29.9%。在溶出量随时间变化方面,在胃阶段,假定1 h时溶出率为100%。20 min时,土壤中Fe、Ni的平均溶出率较低,分别为59.3%、56.8%,其他6种金属元素的平均溶出率在71.2%~79.5%。As、Cd、Pb的溶出速率是先快后慢,Cr和Ni的溶出速率是先慢后快,而Fe、Mn、Al的溶出速率基本保持不变。在小肠阶段,假定4 h时溶出率为100%。Al、As、Cd、Mn的溶出率基本不变。1 h时,土壤中Cr（土壤A除外）、Ni的平均溶出率最低,分别为31.5%、32.7%,而5 h时,Fe、Cr、Ni的溶出率还在升高。由此可见,土壤中不同金属元素的生物可给性以及溶出动态是有明显差异的。     

贵阳建筑灰尘重金属的生物可给性及其对人体的健康风险评估

为了研究城市建筑灰尘重金属的生物可给性及其影响因素,评估人体无意摄入建筑灰尘重金属的健康风险,以贵阳市4个建筑工地的楼内、楼梯、建筑区门口、办公区、休息区、建筑区内道路、建筑区外道路、木材堆放区和金属堆放区为研究区,采用in vitro方法研究了这些区域灰尘在胃和肠阶段Cu、Pb、Zn的溶解态量和生物可给性,并以此为基础进行健康风险评估。结果表明,建筑灰尘中Cu、Pb、Zn的溶解态量和生物可给性在各区域差异很大,3种重金属的生物溶解态量与重金属总量呈显著相关(P0.05),而生物可给性与灰尘p H和有机质无显著相关关系,其大小与重金属总量的高低也无直接关系。各区域建筑灰尘Cu、Zn对人体健康风险较低,但Pb对儿童存在较高的健康风险。其中,在胃阶段,办公区和建筑区内道路对儿童健康风险的贡献率超过30%;在肠阶段,建筑区内道路、办公区、建筑区外道路对儿童健康风险的贡献率超过3%。只有当3种重金属总量很高且生物可给性也较高时,才会对人体产生较高风险。     

铅暴露对人体健康风险评价的模型综述

铅是一种在暴露环境下,可以通过手口途径或者皮肤接触而进入人体,从而对人体许多组织器官都产生毒性作用的重金属,其对儿童的危害尤为突出.我国对暴露在铅环境下人体健康的风险评价研究起步较晚,基于血铅指标的铅污染土壤风险评估方法导则仍在探讨建立中.而国外已经存在一些较为成熟的用于成人及儿童的铅暴露吸收和生物动力学模型,其中被广泛接受和使用的是成人血铅模型(ALM)以及儿童在铅中的综合暴露吸收生物动力学模型(IEUBK).前者描述了关于非居住区土壤中铅暴露物对成人风险的评估,且重点针对污染土壤的铅暴露物所导致的孕妇体内胎儿的血铅浓度进行评估;后者则重点预测6—84个月的儿童在铅的综合暴露下的健康风险.本文旨在通过对这些模型进行对比总结,从而提出可用于我国铅污染风险评估的理论依据及指导方法.     

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.     

Assessment of bioaccessibility and exposure risk of arsenic and lead in urban soils of Guangzhou City,China

Soil ingestion is an important human exposure pathway of heavy metals in urban environments with heavy metal contaminated soils. This study aims to assess potential health risks of heavy metals in soils sampled from an urban environment where high frequency of human exposure may be present. A bioaccessibility test is used, which is an in vitro gastrointestinal (IVG) test of soluble metals under simulated physiological conditions of the human digestion system. Soil samples for assessing the oral bioaccessibility of arsenic (As) and lead (Pb) were collected from a diverse range of different land uses, including urban parks, roadsides, industrial sites and residential areas in Guangzhou City, China. The soil samples contained a wide range of total As (10.2 to 61.0 mg kg⁻¹) and Pb (38.4 to 348 mg kg⁻¹) concentrations. The bioaccessibility of As and Pb in the soil samples were 11.3 and 39.1% in the stomach phase, and 1.9 and 6.9% in the intestinal phase, respectively. The As and Pb bioaccessibility in the small intestinal phase was significantly lower than those in the gastric phase. Arsenic bioaccessibility was closely influenced by soil pH and organic matter content (r ² = 0.451, p < 0.01) in the stomach phase, and by organic matter, silt and total As contents (r ² = 0.604, p < 0.001) in the intestinal phase. The general risk of As and Pb intake for children from incidental ingestion of soils is low, compared to their maximum doses, without causing negative human health effects. The exposure risk of Pb in the soils ranked in the order of: industrial area/urban parks > residential area/road side. Although the risk of heavy metal exposure from direct ingestion of urban soils is relatively low, the risk of inhalation of fine soil particulates in the air remains to be evaluated.     

Lead availability in soils from Portugal’s Centre Region with special reference to bioaccessibility

Previous environmental biomonitoring studies indicated higher environmental lead (Pb) pollution levels at the districts of Aveiro and Leiria (Portugal). In evaluating the risk for human health, which is associated with contaminated soils after oral uptake, total soil concentrations have generally been held against criteria established from toxicological studies based upon the assumption that the uptake of the contaminant is similar in the toxicological studies and from the soils assessed. This assumption is not always valid, as most toxicological studies are carried out with soluble forms of the contaminants, whereas many soil contaminants are or become embedded in the soil matrix and thus exhibit limited availability. This study intends to estimate the soluble fraction of Pb in the soils from central Portugal, and to assess the bioaccessibility of Pb and, hence, infer exposure and risk for human health. Yet, as the physical–chemical properties of the soil exert some control over the solubility of Pb in the surface environment, the relation between such soil properties and the estimated soluble and/or bioaccessible fractions of Pb is also investigated. Other objective, with a more practical nature, was to give some contribution to find a suitable in vitro mimetic of the gastrointestinal tract environment. The results indicate relatively low total metal concentrations in the soils, even if differences between regions were observed. The Aveiro district has the higher total Pb concentration and the metal is in more soluble forms, that is, geoavailable. Soils with higher concentrations of soluble Pb show higher estimates of bioaccessible Pb. Soil pH seems to influence human bioaccessibility of Pb.     

Enrichment and solubility of trace metals associated with magnetic extracts in industrially derived contaminated soils

Magnetic fractions (MFs) in industrially derived contaminated soils were extracted with a magnetic separation procedure. Total, soluble, and bioaccessible Cr, Cu, Pb and Zn in the MFs and non-magnetic fractions (NMFs) were analyzed using aqua regia and extraction tests, such as deionized water, toxicity characteristic leaching procedure (TCLP), and gastric juice simulation (GJST) test. Compared with the non-magnetic fractions, soil MFs were enriched with Fe, Mn, Pb, Cd, Cr, Cu, and Ni. Extraction tests indicated that soil MFs contained higher water, TCLP, and GJST-extractable Cr, Cu, Pb, and Zn concentrations than the soil NMFs. The TCLP-extractable Pb concentration in the MFs exceeded the USEPA hazardous waste criteria, suggesting that soil MFs have a potentially environmental pollution risk. Solubility of trace metals was variable in the different extraction tests, which has the order of GJST?>?TCLP?>?water. TCLP test showed Cu and Zn were more mobile than Cr and Pb while bioaccessibility of trace metal defined by GJST test showed the order of Cu?≈?Cr?≈?Zn?>?Pb. These findings suggested that the MFs in the industrially derived contaminated soils had higher possibility of polluting water bodies, and careful environmental impact assessment was necessary.     

The relationship between soil geochemistry and the bioaccessibility of trace elements in playground soil

A total of 32 samples of surficial soil were collected from 16 playground areas in Madrid (Spain), in order to investigate the importance of the geochemistry of the soil on subsequent bioaccessibility of trace elements. The in vitro bioaccessibility of As, Co, Cr, Cu, Ni, Pb and Zn was evaluated by means of two extraction processes that simulate the gastric environment and one that reproduces a gastric?+?intestinal digestion sequence. The results of the in vitro bioaccessibility were compared against aqua regia extractions (“total” concentration), and it was found that total concentrations of As, Cu, Pb and Zn were double those of bioaccessible values, whilst that of Cr was ten times higher. Whereas the results of the gastric?+?intestinal extraction were affected by a high uncertainty, both gastric methods offered very similar and consistent results, with bioaccessibilities following the order: As?=?Cu?=?Pb?=?Zn?>?Co?>?Ni?>?Cr, and ranging from 63 to 7?%. Selected soil properties including pH, organic matter, Fe and CaCO₃ content were determined to assess their influence on trace element bioaccessibility, and it was found that Cu, Pb and Zn were predominantly bound to organic matter and, to a lesser extent, Fe oxides. The former fraction was readily accessible in the gastric solution, whereas Fe oxides seemed to recapture negatively charged chloride complexes of these elements in the gastric solution, lowering their bioaccessibility. The homogeneous pH of the playground soils included in the study does not influence trace element bioaccessibility to any significant extent except for Cr, where the very low gastric accessibility seems to be related to the strongly pH-dependent formation of complexes with organic matter. The results for As, which have been previously described and discussed in detail in Mingot et al. (Chemosphere 84: 1386–1391, 2011), indicate a high gastric bioaccessibility for this element as a consequence of its strong association with calcium carbonate and the ease with which these bonds are broken in the gastric solution. The calculation of risk assessments are therefore dependant on the methodology used and the specific environment they address. This has impacts on management strategies formulated to ensure that the most vulnerable of society, children, can live and play without adverse consequences to their health.     

典型农耕区黑土和沼泽土团聚体颗粒中重金属的分布特征解析

了解重金属在土壤中的富集特征是其风险评价和土壤修复的基础。分别以黑龙江省典型的农耕黑土和沼泽土为研究对象,采用干筛法获得〉4000、4000～2000、2000～1000、1000～250、250～53和〈53衄16个粒级的土壤团聚体颗粒组。利用等离子质谱（ICP-MS）测定了本土和各级团聚体颗粒中Cr、Cd、As和Pb的含量,并对其颗粒组分布特征及对有机碳的响应进行了解析。研究表明,2种土壤中的重金属Cr、Cd和Pb的富集因子均大于1,而As则存在明显的流失。除了黑土中的As和Pb外,其他重金属随着团聚体粒径的增加而呈现富集减弱的趋势。其中,cr和cd主要趋向分布在粉．黏团聚体（〈53wn）颗粒中;Pb在黑土中易赋存于1000～2000μm大团聚体中,在沼泽土中则富集于53～250μm的微团聚体中;As不但趋向被吸附在53～250μm的微团聚体中,而且在黑土中也容易被吸附在〉l000μm的大团聚体中。金属质量负载计算表明,大粒径颗粒组对土壤中重金属含量的总体贡献较大。土壤中有机碳含量均随着团聚体粒径减小而升高,cr和Cd分布与颗粒有机碳含量正相关,黑土中As的分布与颗粒中有机碳含量负相关而在沼泽土中呈弱正相关,Pb的分布则与有机碳含量均无明显的相关性。     

Effect of red mud addition on the fractionation and bio-accessibility of Pb,Zn and As in combined contaminated soil

Using soil incubation experiments, the effect of red mud addition on the fractionation and bioaccessibility of Pb, Zn and As in combined contaminated soil was studied. The results showed that red mud addition could significantly decrease the concentration of HOAc-extractable Pb and Zn in soil. Compared with the control, 5% red mud addition could significantly reduce the concentrations of HOAc-extractable Pb and Zn in soil after 1, 2 and 3 months of incubation [62.5, 65.3 and 73.5% decrease (Pb), 56.7, 65.8 and 67.4% decrease (Zn)]. Whereas adding red mud could remarkably increase the concentrations of specific absorbed As and residual As in soil. The result of a simple bioavailability extraction test (SBET) indicated that all treatments with red mud addition markedly reduced the concentration of bioaccessible Zn but increased the concentration of bioaccessible As in soil, while having little effect on the concentration of bioaccessible Pb in soil. After 3 months incubation, all treatments including 1, 2 and 5% red mud addition reduced the concentration of bioaccessible Zn by 53.1–56.7% compared with the control, but increased the concentration of bioaccessible As by 1.81–6.25 times. The results suggested that red mud is an additive with potential for the remediation soil contaminated soil by combinations of heavy metals, although it should be added based on the different heavy metals in the soil. Combined use of red mud and hyperaccumulators to remediate heavy metal contaminated soil needs further study.     

Assessing Cd,Pb, Zn human bioaccessibility in smelter-contaminated agricultural topsoils (northern France)

The extractability of Cd, Pb, and Zn was investigated in contaminated agricultural topsoils located in an area highly affected by the past atmospheric emissions of two smelters in northern France in order to assess their mobility and human bioaccessibility. The determination of Cd, Pb, and Zn bioaccessibility (Unified Barge Method, in vitro test) was made to evaluate the absolute trace element (TE) bioavailability. The results highlighted differences in bioaccessibility between Cd, Pb, and Zn (Cd > Pb > Zn). The mean values of the bioaccessible fractions of Cd, Pb, and Zn during the gastric phase were 82, 55, and 33%, respectively, of the pseudototal concentrations, whereas during the gastrointestinal phase, the bioaccessible fractions of metals decreased to 45, 20, and 10%, respectively. Stepwise multiple regression analysis showed that human bioaccessibility was affected by various physicochemical parameters (i.e., sand, carbonates, organic matter, assimilated P, free Al oxides, and pseudototal Fe contents). Sequential extractions were performed as an indication of the TE availability in these soils. Cadmium occurred in the more available fractions, Pb was mostly present as bound by oxides, and a significant contribution to the pseudototal Zn concentration was defined as the unavailable residual form related to the crystalline structures of minerals. The concepts of bioavailability and bioaccessibility are important for quantifying the risks associated with exposure to environmental pollutants and providing more realistic information for human health.