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。     

添加奶粉对土壤中铬、镍、锰、铜生物可给性的影响

为了探究不同成分的奶粉对土壤中Cr、Ni、Mn、Cu生物可给性的影响,本文通过in vitro实验研究了添加全脂或脱脂奶粉后,胃肠阶段土壤中Cr、Ni、Mn、Cu的生物可给性的变化.结果表明,胃阶段,土壤中Cr、Ni、Mn、Cu的生物可给性分别为3.9%—46.2%、4.5%—64.0%、21.2%—72.5%、4.5%—69.5%;添加奶粉后,4种金属的生物可给性均有升高,是未加奶粉的1.1—1.5倍、1.3—2.2倍、1.1—2.1倍、1.0—3.6倍(全脂奶粉)和1.1—1.4倍、1.4—2.4倍、1.2—2.5倍、1.0—4.2倍(脱脂奶粉).小肠阶段,土壤中Cr、Ni、Cu的生物可给性有一定上升,但Mn的生物可给性相比胃阶段降低了;奶粉的添加使Cr、Ni、Mn、Cu等4种金属的溶出量增加,分别是未添加的1.2—1.3倍、1.3—2.3倍、2.0—4.5倍、1.0—1.5倍(全脂奶粉)和1.1—1.5倍、1.6—2.5倍、2.5—6.9倍、1.2—1.8倍(脱脂奶粉),其中Ni、Mn的生物可给性增加显著,且Ni、Mn的生物可给性的增加率高于胃阶段.由此可见,奶粉的添加,尤其是脱脂奶粉,促进了土壤中Cr、Ni、Mn、Cu的溶出释放,可能增大了其对人体的健康风险.     

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.     

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。     

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.     

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。     

基于RIVM模型评估湘江干流铜锈环棱螺重金属生物可给性及食用健康风险

重金属污染已成为水产品质量安全存在的主要问题之一.本研究通过测定湘江干流铜锈环棱螺肉中重金属(Cu、Zn、Cr、Cd、Pb)含量,并基于荷兰RIVM(the Dutch National Institute for Public Health and the Environment)体外消化模型模拟口腔、胃及肠道消化,计算螺肉中Cu、Zn、Cr、Cd、Pb的生物可给性,评估其食用健康风险.结果表明,螺肉中Cu、Zn、Cr、Cd、Pb的含量范围分别为35.68—116.96、202.51—323.20、4.41—95.93、0.29—16.08、0.12—17.35 mg·kg^-1,且大多高于水产品重金属限量标准.螺肉中不同重金属的生物可给性差异较大,Zn、Cd和Pb在胃阶段的生物可给性高于口腔和肠阶段,Cu和Cr在肠阶段的生物可给性高于口腔和胃阶段.基于生物可给性的食用健康风险显示,螺肉中5种重金属的目标危害系数(THQ)和综合危害系数(HI)均小于1,不存在非致癌健康风险;但其综合致癌风险指数(TCR)均大于1×10^-4,存在致癌风险. C...     

利用体外实验方法评估稻米中镉的生物可给性和健康风险

为了研究稻米中镉(Cd)的生物可给性与稻米理化性质之间的相互关系以及稻米摄入而导致的Cd健康风险,从湖南某些地区采集了16个稻米样品,利用in vitro方法研究了这些稻米中Cd的生物可给性及其人体健康风险。结果表明:在16个样品中,有13个样品的Cd含量超过稻米中Cd的限量标准(0.2 mg·kg-1)。稻米中Cd的溶解态含量及其生物可给性变化较大,胃阶段和肠阶段Cd的溶解态含量范围分别为0.102~1.70 mg·kg-1和0.015~0.249 mg·kg-1,平均值分别为0.698 mg·kg-1和0.103 mg·kg-1,胃阶段和肠阶段Cd的生物可给性的范围分别为56.8%~82.0%和6.62%~15.9%,平均值分别为70.9%和11.1%。模拟肠液中Cd的溶解态含量与稻米的纤维含量之间有显著的相关性。如果不考虑稻米中Cd的生物可给性,所采集的所有稻米样品的摄入都将导致成人和儿童健康风险。如果我们考虑了稻米中的生物可给性,只有31%的稻米样品会对成人产生健康风险,将有50%的稻米样品会对儿童产生健康风险。     

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。     

Ecological and human health risks from metal(loid)s in peri-urban soil in Nanjing,China

In order to investigate the ecological and human health risks of metal(loid)s (Cu, Pb, Zn, Ni, Cd, Mn, Cr, and As) in peri-urban soils, 43 surface soil samples were collected from the peri-urban area around Nanjing, a megacity in China. The average contents were 1.19, 67.8, 37.6, 105, 167, 44.6, 722, and 50.8 mg kg^?1 for Cd, Cr, Ni, Pb, Zn, Cu, Mn, and As, respectively. A significant positive correlation was found between Cu, Pb, Zn, Cd, Mn, and As (p < 0.01), and Cr had a significant positive correlation with Ni (p < 0.01). Geoaccumulation indices indicate the presence of Cd and As contamination in all of the peri-urban soil samples. Potential ecological risk indices show that the metal(loid)s in the soil could result in higher ecological risks. Cd is the main contributor to the risk, followed by As. The levels of Cu, Pb, Zn, Cd, Mn, and As in stomach and intestinal phases show a positive linear correlation with their total contents. Mn, Zn, Ni, Cd, and Pb in stomach phase showed higher bioaccessibility, while in intestinal phase, Cu, Cr, and As had the higher bioaccessibility. The carcinogenic risk in children and adults posed by As, Pb, and Cr via ingestion was deemed acceptable. The non-carcinogenic risks posed by these metal(loid)s via ingestion to children are higher than to adults and mainly result from As.     

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.     

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.     

The importance of solid-phase distribution on the oral bioaccessibility of Ni and Cr in soils overlying Palaeogene basalt lavas, Northern Ireland

Potentially toxic elements (PTEs) including nickel and chromium are often present in soils overlying basalt at concentrations above regulatory guidance values due to the presence of these elements in underlying geology. Oral bioaccessibility testing allows the risk posed by PTEs to human health to be assessed; however, bioaccessibility is controlled by factors including mineralogy, particle size, solid-phase speciation and encapsulation. X-ray diffraction was used to characterise the mineralogy of 12 soil samples overlying Palaeogene basalt lavas in Northern Ireland, and non-specific sequential extraction coupled with chemometric analysis was used to determine the distribution of elements amongst soil components in 3 of these samples. The data obtained were related to total concentration and oral bioaccessible concentration to determine whether a relationship exists between the overall concentrations of PTEs, their bioaccessibility and the soils mineralogy and geochemistry. Gastric phase bioaccessible fraction (BAF %) ranged from 0.4 to 5.4 % for chromium in soils overlying basalt and bioaccessible and total chromium concentrations are positively correlated. In contrast, the range of gastric phase BAF for nickel was greater (1.4–43.8 %), while no significant correlation was observed between bioaccessible and total nickel concentrations. However, nickel BAF was inversely correlated with total concentration. Solid-phase fractionation information showed that bioaccessible nickel was associated with calcium carbonate, aluminium oxide, iron oxide and clay-related components, while bioaccessible chromium was associated with clay-related components. This suggests that weathering significantly affects nickel bioaccessibility, but does not have the same effect on the bioaccessibility of chromium.     

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.     

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.     

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.