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。     

岩溶槽谷区土壤多环芳烃健康风险评价

以重庆老龙洞岩溶槽谷为例,利用BaP毒性当量浓度(BaP_(eq))和终生癌症风险增量模型对儿童和成人暴露于土壤PAHs的健康风险进行评价.研究结果表明,土壤中BaP_(eq)∑_(16)PAHs为87.5±156.6 ng·g~(-1),7种致癌性PAHs占了97.8%;BaP_(eq)∑_(10)PAHs平均值为32.9±37.4 ng·g~(-1),33.3%的采样点的BaP_(eq)超过了荷兰土壤环境质量标准目标参考值(33.0 ng·g~(-1)),表明土壤PAHs存在潜在风险;儿童和成人的终生癌症风险(ILCR)分别为1.17×10~(-7)—7.11×10~(-6),1.24×10~(-7)—7.52×10~(-6),平均值为8.8×10~(-7)和9.3×10~(-7),总体在可接受的风险范围内,但有部分存在潜在风险;DaA和BaP产生的致癌风险占到总风险的35.2%和30.4%,是最主要的贡献组成;不同暴露途径对人群的致癌风险水平为:皮肤接触经口摄入呼吸吸入.经口摄入和皮肤接触对总致癌风险的贡献几乎为100%,高出呼吸吸入10~2—10~6倍,是土壤PAHs致癌风险的主要暴露途径.     

典型城乡交错区土壤中多环芳烃污染及健康风险评价

以典型城镇化进程中武汉郊区-鄂州城市-鄂州郊区为研究对象,探讨城乡交错区多环芳烃(PAHs)污染水平和来源,并进行健康风险评价.研究区土壤中PAHs广泛存在,16种PAHs检出率达100%.土壤中∑16PAHs含量为16.60—1854.21 ng·g~(-1),均值为411.67 ng·g~(-1);7种致癌单体多环芳烃Σ7PAHs含量为4.17—1169.98 ng·g~(-1),均值为251.93 ng·g~(-1).不同点位PAHs污染水平差异较大,其中在居民密集区、城市建设及交通繁忙区域尤为显著,说明城乡交错区人为社会和经济活动在一定程度上对土壤中PAHs污染产生较大影响.采用组分特征比值和主成分分析污染来源,结果显示该地区土壤中PAHs主要源于煤燃烧和机动车尾气排放以及秸秆等生物质低温燃烧排放,同时存在石油源污染.在城市化建设发展中,城乡交错区工业、农业、交通及生活等各种区域相互交错重叠,人为活动异常活跃,产生大量PAHs输入源,逐渐成为影响生活和环境的重要影响因素之一.研究区对于成人和儿童通过呼吸暴露于土壤PAHs几乎不存在风险;而通过皮肤接触及经口摄入途径暴露于土壤PAHs存在一定潜在风险.此外,儿童通过3种途径暴露致癌风险低于成人;成人和儿童通过3种途径暴露的致癌风险大小顺序均为经口摄入皮肤接触呼吸.     

赣东北典型重(类)金属污染农田土壤人体健康风险评估

目前关于农田污染土壤直接接触人体的健康风险没有明确的评估规范,部分研究主要采用并不完全适用的建设用地相关参数对农田人群进行健康风险评估,更贴近农田暴露场景相关评估参数的选择仍需进一步探讨。本研究在江西省东北部采集了重(类)金属污染较重表层农田土壤样品,分析了土壤中6种重金属镉、砷、镍、锌、铊和铜的含量,利用我国生态环境部推荐的健康风险评价模型,以农民为暴露对象对该农田土壤进行人体健康风险评价,重点探讨了每日经口摄入土壤量(oral soil ingestion rate, OSIR)、空气中可吸入颗粒物浓度(air inhalable particulate matter concentration, PM₁₀)、每日呼吸空气量(daily air inhalation rate, DAIR)3个参数对评价结果的影响。对比建设用地风险评估推荐参数,更贴近农田暴露场景的上述3个评估参数主要通过增大经口暴露与经呼吸暴露途径的暴露量,显著提升风险水平,其中OSIR和PM₁₀的敏感性比例为100%。单因子砷、镍、镉致癌风险水平超过1.0×10     

RBCA、CLEA及CalTOX模型在苯并[a]芘污染场地健康风险评估中的应用比较

为探讨不同模型对污染场地健康风险评估结果的影响,以苯并[a]芘为例,采用RBCA、CLEA和CalTOX模型对某工业污染场地表层土壤进行健康风险评估,分析了评估结果的差异和原因,同时对模型的主要暴露参数进行了敏感性分析,并推导出基于风险概率分布的土壤修复限值。结果表明,RBCA、CLEA和CalTOX模型计算的苯并[a]芘致癌总风险分别为2.40×10-4、6.32×10-4和7.04×10-6,且经口摄入和皮肤接触2个途径对人体健康造成的危害最大。降解作用是影响CalTOX模型风险评估结果不同于RBCA和CLEA模型的重要因素,3个模型间参数取值及方法学的差异也会导致风险评估结果不同。各模型暴露参数的敏感性排序也有差异。采用基于风险概率分布的方法推导土壤修复限值,RBCA、CLEA和CalTOX模型所得结果分别为0.18、0.08、0.13(不考虑降解作用CalTOX模型)和10.74(考虑降解作用CalTOX模型)mg·kg-1,为各模型直接推导值的1.5～2.6倍。基于风险概率分布的方法可有效降低风险评估过程中参数不确定性的影响,为工业污染场地土壤修复值的制定提供参考。     

沈阳细河流域土壤和作物中汞的潜在生态危害及健康风险评价

为研究沈阳市细河流域土壤汞(Hg)的污染和健康风险状况,对该区土壤和农作物中Hg的含量和分布进行了调查和分析。采用Hakanson潜在生态风险危害指数法评价土壤Hg的污染状况,并利用健康风险评价模型对Hg通过不同暴露途径所引起的健康风险作出评价。研究结果表明,细河流域土壤Hg的潜在生态危害相对较大,其中43.21%样品处于中等危害程度,26.62%属于强及以上风险级别。健康风险评价模型计算表明,人体经食物摄取是土壤Hg暴露的主要途径,Hg日平均暴露剂量依次为食物摄取呼吸暴露皮肤暴露;成人和儿童的非致癌危害指数分别为0.315和0.713,均低于风险阈值1,表明Hg不会对人体造成健康危害。     

2种毒性评估方法对PAHs污染场地人体健康风险的比较研究

毒性评估是人体健康风险评价的重要部分,目前主要存在2种方法,一种基于PAHs相对于苯并[a]芘(BaP)的毒性当量因子,采用Ba P致癌斜率因子参数(方法 1),另一种直接采用各PAHs致癌斜率因子和非致癌参考剂量等参数(方法 2)。然而2种毒性评估方法得到的风险及修复量是否存在差异以及引起差异的原因等问题鲜有讨论。针对苏南某焦化厂PAHs污染土壤,采用分层土壤健康风险评价模型,对比了2种毒性评估方法确定的PAHs风险、修复目标污染物及土方量的差异,并对引起差异的关键因素进行探讨。结果表明:对于0.0~1.0 m表层土壤,方法 1和方法 2确定的致癌风险最大值分别1.48E-05和1.32E-05,均超过可接受致癌风险,修复土方量分别为27 846 m~3和28 667 m3,修复目标污染物均为Ba P和二苊烃(Acy)。对于1.0~3.0 m深层土壤,方法 1确定的致癌风险最大值为3.36E-08,低于可接受致癌风险,不需要修复;而方法 2确定的致癌风险最大值为3.73E-04,非致癌危害指数最大值为6.96E+01,分别超过可接受致癌风险和非致癌危害商,需要修复,修复目标污染物为萘(NaP),修复土方量为35 944 m~3。最终,方法 2确定的总修复土方量(64 611 m~3)为方法 1确定土方量(27 846 m~3)的2.45倍,而这种差异主要是由于方法 1低估了深层土壤中高挥发性PAH单体尤其是NaP的风险所致。因此,从保守角度建议采用方法 2进行PAHs风险评价。     

污染场地中挥发性有机物的扩散和人群暴露预测模型研究进展

污染场地中挥发性有机物(volatile organic compounds, VOCs)的精准风险评估是开展后续修复工作的重要依据。鉴于VOCs易挥发的特性,呼吸吸入气态污染物是可能对人体健康造成危害的最主要的暴露途径。目前常用基于实测土壤中VOCs浓度或基于实测土壤气中VOCs浓度的模型来计算呼吸吸入暴露途径下的健康风险。本文在分析污染场地土壤和土壤气2种不同介质中VOCs分布特点的基础上,总结了国内外常用的健康风险评估模型及应用情况,分析了可能对模型预测结果产生影响的因素,尤其是假设条件和模型输入参数。最后,本文建议加强土壤气中VOCs的调查与评估研究工作,同时加强实地调查、多渠道获取模型参数以建立本土化数据库并进行参数的精细化划分,以降低模型的不确定性。     

环境中有机磷农药污染状况、来源及风险评价

环境中农药的污染残留问题备受社会关注,尤其是食品安全这一方面.作为世界上有机磷农药(OPPs)生产和使用的大国,国内环境中OPPs的残留赋存问题尤其受到重视.残留在环境中水体、土壤、生物体的OPPs可能经口、皮肤接触、呼吸等暴露途径进入人体对人体健康造成风险.了解OPPs在国内主要江河湖泊、土壤、生物体中的残留赋存情况并进行风险评价至关重要.本文对比总结了中国环境中水体、土壤、生物体中主要OPPs的含量范围、检出率及其分布特征,并利用美国RBCA健康风险评价模型对其进行健康风险评价和RQ商值法进行水生生态风险评价.结果显示,中国地表水体含量最高的5种OPPs分别是敌敌畏、乐果、对硫磷、马拉硫磷、甲基对硫磷,浓度变化范围ND—30180 ng·L~(-1),北方水体的OPPs污染状况水平要高于南方水体.OPPs风险评价结果显示,地表水、土壤、蔬菜中OPPs的非致癌风险系数(HQ)分别为7.25×10~(-5)—6.93×10~(-1)、9.56×10~(-7)—5.30×10~(-2)、1.08×10~(-2)—7.01×10~(-1),都还未超过1的安全标准,对人体健康不会产生明显的不良影响.地表水中敌敌畏的致癌风险系数(R)范围为2.86×10~(-8)—6.25×10~(-6)在10~(-5)—10~(-6)安全范围内.对比地表水、土壤、蔬菜的HQ值,蔬菜中残留的单体OPPs对人体的健康风险大于地表水和土壤,水生生态风险评价结果中OPPs对糠虾和水蚤RQ值1,处于高风险.     

山西省典型燃煤污染区土壤中多环芳烃风险评价

在山西省临汾市南部燃煤污染代表性区域(1034 km~2)采集了128个表层土壤样品,采用气相色谱-质谱联用技术(GC-MS)分析了土壤中16种优控多环芳烃(PAHs)的含量,并对样品中PAHs的生态风险和人体健康风险进行了评价。结果显示,16种PAHs的质量分数为(723.2±1 230)μg·kg~(-1),组成成分以4~6环为主。根据Maliszewska-Kordybach分级评价标准,研究区域土壤中78.12%的样品受到PAHs不同程度的污染。基于内梅罗综合污染指数法评价结果,研究区域83.59%的样点存在PAHs污染,其中古城镇和新城镇60%以上的采样点达到了重度污染级别。基于毒性当量因子(Toxic Equivalency Factor,TEF)风险评价法的生态风险评价结果显示,荷兰土壤质量标准所涉及到的10种PAHs的苯并(a)芘(Bap)毒性当量浓度(Bap toxic equivalent quantity,TEQ_(Bap))为(67.50±137.7)μg·kg~(-1),其中42.19%的样点超过荷兰土壤TEQ_(Bap10)的标准限值,古城镇和新城镇土壤中PAHs平均超标3倍以上。对研究区域的暴露人群分别进行非致癌风险及致癌风险评价,结果显示研究区域土壤中的PAHs不会对成人和儿童产生明显的非致癌风险。而在古城镇、新城镇、陶寺乡、景毛乡和永固乡,土壤中PAHs引起的综合致癌风险已超过可接受致癌风险(10~(-6)),对人群健康构成了潜在威胁,需引起重视;其他研究区域的致癌风险仍在可接受范围(10~(-6))之内。     

Human bioaccessibility of Cr, Cu, Ni, Pb and Zn in urban soils from the city of Torino, Italy

Several physiologically based extraction procedures have been proposed to estimate the fraction of the potentially toxic element content that would be bioaccessible in the human gastro-intestinal tract following accidental ingestion of soil. Many of these procedures are complex, they have been applied to a very limited range of soils, and most work has focussed on arsenic and lead. In the present study, a simplified, two-stage extraction, simulating the human stomach and intestine, was developed and applied to urban soil samples from ten public-access areas in the City of Torino, Italy. The human oral bioaccessibility of chromium, copper, nickel, lead and zinc was estimated. Lead and zinc bioaccessibilities were found to be higher in the stomach, but chromium was more bioaccessible in the intestine. Analyte concentrations were higher in roadside soils than in soils from parks. A higher proportion of the soil metal content was found in bioaccessible forms at roadsides than in parks. Comparison of the current findings with results of earlier work involving sequential extraction of the same soils indicated that the sequential procedure gave a relative, but not an absolute, indication of bioaccessibility. Calculations based on the bioaccessible analyte concentrations suggest that ingestion of only 2–3 g of some of the roadside soil samples from Torino could deliver the tolerable daily oral intake of chromium, nickel and lead to a 20-kg child. The developed procedure is useful for preliminary screening of soils and prediction of whether their bioaccessible metal contents are likely to pose a risk to human health.     

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.     

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。     

Health risk assessment for arsenic contaminated soil

This paper describes risk assessment methods for two chronic exposure pathways involving arsenic contaminated soil, namely inhalation of fugitive dust emissions over a lifetime, and inadvertent soil/house dust ingestion. The endpoint in the first case is assumed to be lung cancer and in the second case skin cancer. In order to estimate exposures, inhalation rates and soil/dust ingestion rates are estimated for different age groups; indoor/outdoor time budgets for different age groups are developed; and indoor surface dust and air arsenic concentrations are estimated based on outdoor concentration measurements. Differences observed in indoor/outdoor ratios and arsenic containing dust particle size among different types of communities are noted, as well as possible relationship of particle size to bioavailability. Calculations of risk are presented using cancer potency factors developed by the U.S. Environmental Protection Agency, and uncertainties in these toxicity estimates are described based on: (1) evidence that arsenic may be neither a cancer initiator nor promotor, but may act instead as a late stage carcinogen and (2) evidence that the arsenic dose-response relationship for ingestion may be nonlinear at low doses due to increasing methylation of inorganic arsenic. The first of these considerations influences the relative importance ascribed to arsenic doses in different age groups. The latter consideration indicates that the risk estimates described here are probably very conservative.     

Potentially harmful elements in house dust from Estarreja,Portugal: characterization and genotoxicity of the bioaccessible fraction

Due to their behavioral characteristics, young children are vulnerable to the ingestion of indoor dust, often contaminated with chemicals that are potentially harmful. Exposure to potentially harmful elements (PHEs) is currently exacerbated by their widespread use in several industrial, agricultural, domestic and technological applications. PHEs cause adverse health effects on immune and nervous systems and can lead to cancer development via genotoxic mechanisms. The present study is an integrated approach that aims at assessing the genotoxicity of bioaccessible PHEs following ingestion of contaminated house dust. A multidisciplinary methodology associating chemical characterization of five house dust samples, extraction of the bioaccessible PHEs in gastric extracts by the unified BARGE method, determination of the bioaccessible fraction and in vitro genotoxicity of gastric extracts in adenocarcinoma gastric human (AGS) cells was developed. The five gastric extracts induced dose-dependent genotoxicity in AGS cells. Copper (bioaccessible concentration up to 111 mg/kg) was probably the prevalent PHE inducing primary DNA damage (up to 5.1-fold increase in tail DNA at 0.53 g/l of gastric extract). Lead (bioaccessible concentration up to 245 mg/kg) was the most prevalent PHE inducing chromosome-damaging effects (r = 0.55; p < 0.001 for micronucleated cells induction). The association of principal component analysis and Spearman’s correlations was decisive to understand the chromosome-damaging properties of the bioaccessible PHEs in AGS cells. This methodology could be used on a larger-scale study to provide useful information for science-based decision-making in regulatory policies, and a better estimation of human exposure and associated health risks.     

Oral bioaccessibility of metals in an urban catchment,Newcastle upon Tyne

The metal content was determined in soils from a former, historic, contaminated land site and now a ‘green’ public open space in N.E. England. Using a systematic sampling grid approach, 32 soil samples were taken from locations across the site and analyzed for six potentially toxic elements (Cd, Cr, Cu, Ni, Pb, and Zn). Initially, the pseudo-total metal content of the soils was determined using acid digestion followed by inductively coupled plasma mass spectrometry analysis. This data was evaluated against published soil guideline value (SGV) and generic assessment criteria (GAC) values; it was found that 21% (i.e., 41 samples) exceeded the stated lower values. The data was then compared to the oral bioaccessibility of the soils, which was assessed by an in-vitro gastrointestinal extraction procedure. The results, determined as the % BAF, indicated that overall bioaccessibility was low (<10% BAF) for all the elements studied; the exception was Cd. Given that SGV/GAC values are based on generic land-use categories and not a public open space, as investigated in this work, further work is recommended on developing a qualitative risk assessment at the site to estimate the risks posed to human health via the direct and indirect soil ingestion pathway.     

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.     

Arsenic distribution and bioaccessibility across particle fractions in historically contaminated soils

Incidental soil ingestion is a common contaminant exposure pathway for humans, notably children. It is widely accepted that the inclusion of total soil metal concentrations greatly overestimates the risk through soil ingestion for people due to contaminant bioavailability constraints. The assumption also assumes that the contaminant distribution and the bioaccessible fraction is consistent across all particle sizes. In this study, we investigated the distribution of arsenic across five particle size fractions as well as arsenic bioaccessibility in the <250-, <100-, <10- and 2.5-μm soil particle fractions in 50 contaminated soils. The distribution of arsenic was generally uniform across the larger particle size fractions but increased markedly in the <2.5-μm soil particle fraction. The marked increase in arsenic concentration in the <2.5-μm fraction was associated with a marked increase in the iron content. Arsenic bioaccessibility, in contrast, increased with decreasing particle size. The mean arsenic bioaccessibility increased from 25 ± 16% in the <250-μm soil particle fraction to 42 ± 23% in the <10-μm soil particle fraction. These results indicate that the assumption of static arsenic bioaccessibility values across particle size fractions should be reconsidered if the ingested material is enriched with small particle fractions such as those found in household dust.