Geochemistry,mineralogy, solid-phase fractionation and oral bioaccessibility of lead in urban soils of Lisbon

An urban survey of Lisbon, the largest city in Portugal, was carried out to investigate its environmental burden, emphasizing metallic elements and their public health impacts. This paper examines the geochemistry of lead (Pb) and its influence on human health data. A total of 51 soil samples were collected from urban recreational areas used by children to play outdoors. The semi-quantitative analysis of Pb was carried out by inductively coupled plasma mass spectrometry after an acid digestion. X-ray diffraction was used to characterize the soil mineralogy. The solid-phase distribution of Pb in the urban soils was investigated on a subset of 7 soils, out of a total of 51 samples, using a non-specific sequential extraction method coupled with chemometric analysis. Oral bioaccessibility measurements were obtained using the Unified BARGE Method developed by the Bioaccessibility Research Group of Europe. The objectives of the study are as follows: (1) investigation of Pb solid-phase distribution; (2) interpretation of Pb oral bioaccessibility measurements; (3) integration of metal geochemistry with human health data; and (4) understanding the influence of geochemistry and mineralogy on oral bioaccessibility. The results show that the bioaccessible fraction of Pb is lower when major metal fractions are associated with less soluble soil phases such as Fe oxyhydroxides, and more increased when the metal is in the highly soluble carbonate phase. However, there is some evidence that the proportion of carbonates in the soil environment is also a key control over the oral bioaccessibility of Pb, irrespective of its solid-phase fractionation.     

Correlation analysis as a tool to investigate the bioaccessibility of nickel, vanadium and zinc in Northern Ireland soils

Correlation analyses were conducted on nickel (Ni), vanadium (V) and zinc (Zn) oral bioaccessible fractions (BAFs) and selected geochemistry parameters to identify specific controls exerted over trace element bioaccessibility. BAFs were determined by previous research using the unified BARGE method. Total trace element concentrations and soil geochemical parameters were analysed as part of the Geological Survey of Northern Ireland Tellus Project. Correlation analysis included Ni, V and Zn BAFs against their total concentrations, pH, estimated soil organic carbon (SOC) and a further eight element oxides. BAF data were divided into three separate generic bedrock classifications of basalt, lithic arenite and mudstone prior to analysis, resulting in an increase in average correlation coefficients between BAFs and geochemical parameters. Sulphur trioxide and SOC, spatially correlated with upland peat soils, exhibited significant positive correlations with all BAFs in gastric and gastro-intestinal digestion phases, with such effects being strongest in the lithic arenite bedrock group. Significant negative relationships with bioaccessible Ni, V and Zn and their associated total concentrations were observed for the basalt group. Major element oxides were associated with reduced oral trace element bioaccessibility, with Al₂O₃ resulting in the highest number of significant negative correlations followed by Fe₂O₃. spatial mapping showed that metal oxides were present at reduced levels in peat soils. The findings illustrate how specific geology and soil geochemistry exert controls over trace element bioaccessibility, with soil chemical factors having a stronger influence on BAF results than relative geogenic abundance. In general, higher Ni, V and Zn bioaccessibility is expected in peat soil types.     

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.     

珠江三角洲典型区域农业土壤中镍的含量分布特征

对珠江三角洲典型区域农业土壤取样调查表明:研究区农业土壤中镍的含量范围在2.29～112.00mg·kg-1之间,平均值(27.79±18.39)mg·kg-1,有24.9%土壤样品的镍含量超过国家土壤环境质量标准(GB15618—1995)的二级标准;土壤中镍的含量主要受成土母质的影响,滨海沉积物和三角洲冲积物发育的土壤中镍含量明显高于其它成土母质的土壤;可能受到富含镍的西江和北江沉积物质的影响,西江和北江三角洲沉积区土壤中镍含量明显高于东江三角洲沉积区。调查结果为研究区域的土壤环境质量调查、评价和治理提供重要的基础资料和决策依据。     

Spatial distribution of potentially bioavailable metals in surface soils of a contaminated sports ground in Galway, Ireland

Assessing the environmental risk of metal contamination in soils requires the determination of both total (TCs) and bioavailable (BCs) element concentrations. A total of 200 surface (0–10 cm) soil samples were collected from an urban sports ground (South Park) in Galway, Ireland, a former landfill and dumping site, which is currently under remediation. The potential BCs of metals were measured using ethylene-diamine-tetra-acetic acid (EDTA) extraction followed by inductively coupled plasma-optical emission spectrometry analysis, while the TCs were determined using portable X-ray fluorescence spectrometry. It was found that Zn was primarily present in the insoluble residue (EDTA un-extractable) fraction in soils, with the median ratio of BCs/TCs 0.27. However, Pb and Cu had higher ratios of BCs/TCs (median values of 0.60 and 0.39, respectively) suggesting that they are potentially more bioavailable in the soils. The spatial distribution maps showed that both TCs and BCs for Cu, Pb and Zn in the study area were spatially heterogeneous. It was found that the BCs exhibited generally similar spatial patterns as their TCs of Cu, Pb and Zn: high values were mainly located in the west, north-east and south-east portions of the study area, where only a thin layer of topsoil existed. It was recommended that the current remediation action for this site needs to be carried out on an urgent basis.     

Cu Ni As Cr对萝卜出苗的影响

利用盆栽试验研究Ｃｕ、Ｎｉ、Ａｓ、Ｃｒ４个元素不同浓度对萝卜出苗的影响．结果表明，土壤含Ｃｕ５０ｍｇ／ｋｇ以上时，随着含Ｃｕ量的增加，出苗数随之减少．在酸性土壤上发生Ｃｕ和Ｎｉ危害时，可用提高土壤ｐＨ至中性的办法来消除．在中性土壤上，含Ｎｉ５０ｍｇ／ｋｇ以上对萝卜出苗有害．Ｃｕ、Ｎｉ复合污染比单一元素污染的危害大，且毒性Ｎｉ＞Ｃｕ．土壤Ｃｒ、Ａｓ含量越大，对萝卜出苗的危害也越大，并且毒性Ｃｒ（６＋）＞Ｃｒ（３＋）．     

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.     

电镀废水中铜锌铬镍对农业环境的影响

电镀废水排入河涌会污染农业环境。以广东省南 海市平洲地区为例,农田灌溉水中Ｃｕ、Ｚｎ、Ｎｉ的含量超过允许限值１ ～１４ 倍,河涌底泥Ｃｕ、Ｚｎ、Ｃｒ、Ｎｉ超标１２ ～３７倍,土壤超标０．５ ～２．９倍,作物超标０．３ ～８ 倍。进入河涌的Ｃｕ、Ｚｎ、Ｃｒ、Ｎｉ能较快沉积于底泥中。进入土壤的Ｃｕ、Ｚｎ、Ｃｒ、Ｎｉ主要累积在耕作层中。作物对Ｃｕ、Ｚｎ 的吸收能力远远高于对Ｃｒ、Ｎｉ的吸收能力,作物吸收系数是Ｚｎ ＞ Ｃｕ ＞ Ｎｉ＞ Ｃｒ     

Environmental impact of heavy metals (Fe, Ni, Cr, Co) in soils waters and plants of triada in euboea from ultrabasic rocks and nickeliferous mineralisation

Soil, water and vegetation samples were collected from the Triada area of Central Euboea and analysed for heavy metals in order to evaluate their environmental impact. The geology of the area studied includes ultrabasic rocks that are overlaid by Upper Cretaceous limestones whereas Fe–Ni mineralisation is intercalated between either the ultrabasic parent rocks or the karstified Jurassic/Triassic carbonates and the transgessive Upper Cretaceous limestones. All the samples were analysed for heavy metals by using atomic absorption spectroscopy. The heavy metal ranges (in g g^–1) for soils samples are: Ni 480–4000, Cr 240–2720, Co 40–208, Fe 24,000–380,000, Mn 46–1680, Pb 16–56, Zn 40–144, Cu 2–82. The values of soil samples of the Triada area are much higher than the values found for Ni, Cr, Co and Fe, in normal soils of the world. The heavy metal ranges (in g L^–1) for water samples are: Ni 19–24, Cr 19–476, Co <5, Fe <100, Mn <100, Mg 5.7–220.5, As 30–69, Cd <2, Pd <10, Zn 5–11, Cu 2–7. The water samples of the Triada area have Cr and Mg concentrations higher than the permittable values. The heavy metal ranges (in g g^–1) for vegetation samples are: Ni 1–135, Cr 0–24, Co 1–21.5, Fe 20–680, Mn 10–206, Cd 0–10, Pb 0–14, Zn 14–70, Cu 0–10.5. The vegetation samples of the Triada area have so high values of Ni, Cr and Co that are considered toxic. The intercorrelated elements Fe, Ni, Cr, Co of the Triada soils, waters and vegetation reflect their association with the ultrabasic rocks and with the Fe–Ni mineralisation.     

Uptake,distribution and loss of Cr in the crab Xantho hydrophilus

Uptake of ⁵¹Cr(III) is faster than uptake of ⁵¹Cr(VI), but it occurs mainly on the surface of the animals. Steady state is attained after 28 d. The resulting concentration factor is about 200. Although the uptake of ⁵¹Cr(VI) is slower, it is more intensively distributed into the organs and tissues of the animals. Steady state was not attained during the experiments (35 d); the highest concentration factor reached was about 10. The uptake of both ⁵¹Cr(III) and ⁵¹Cr(VI) seems to be passive. For both chemical forms of chromium, the loss rate is inversely proportional to the exposure time. When the uptake lasted longer, owing to the distribution of Cr(VI) into the organs and tissues, the loss rate of Cr(III) is somewhat faster relative to the loss rate of ⁵¹Cr(VI). The opposite is the case when the uptake of both forms lasts only two days. On the basis of the distribution and loss experiments, we argue that hexavalent chromium in living organisms is reduced to the trivalent form and then complexed with organic molecules.     

Influences of traffic on Pb,Cu and Zn concentrations in roadside soils of an urban park in Dublin,Ireland

Soils in the vicinity of roads are recipients of contaminants from traffic emissions. In order to obtain a better understanding of the impacts of traffic on soils, a total of 225 surface soil samples were collected from an urban park (Phoenix Park, Dublin, Ireland) in a grid system. Metal (Pb, Cu and Zn) concentrations were determined using a portable X-ray fluorescence analyzer. Strong spatial variations for the concentrations of Pb, Cu and Zn were observed. The spatial distribution maps created using geographical information system techniques revealed elevated metal concentrations close to the main traffic route in the park. The relationships between the accumulation of Pb, Cu and Zn in the roadside soils and the distance from the road were well fitted with an exponential model. Elevated metal concentrations from traffic pollution extended to a distance of approximately 40 m from the roadside. The results of this study provide useful information for the management of urban parks particularly in relation to policies aimed at reducing the impact of traffic related pollution on soils.     

植物吸收修复对土壤镍及其主要化学性质的影响

采用室内盆栽试验方法,研究了外源镍污染土壤的植物吸收修复对土壤镍形态和土壤主要化学性质的影响。试验用水稻土添加NiSO4·6H2O(100～1600mgkg-1)经过12周的驯化培养后,种植了镍超累积植物Alyssu mmurale,110 d后收获植物并进行了试验土壤镍的形态和主要化学性质的分析,采用再分配系数和结合强度系数对植物修复效果进行了定量分析。结果表明,根区土壤中DTPA提取态镍的数量明显减少,根区土壤DTPA-Ni与非根区土壤DTPA-Ni之比的范围在0.33～0.61之间。每盆植物提取镍量为6.61～31.18mg,植物提取量随着添加镍量增加而增加,地上部分最大镍含量达到12454.1mgkg-1。根区的再分配系数在2.17～4.19之间,而非根区的再分配系数在6.87～15.91之间,再分配系数随着镍添加量的增加而增大;根区的结合强度系数为0.84～0.39,而非根区的则为0.88～0.26,随着土壤中镍添加量的增加,结合强度系数逐渐减小。植物吸收修复后,根区土壤镍的再分配系数降低、结合强度系数增大,表明土壤镍各形态之间的稳定性增加,因此植物修复可以加快外源镍在土壤中的稳定。试验结果也表明,根区土壤中pH随着镍添加量的增加呈下降趋势、但较非根区土壤的高;根区土壤有机碳亦较非根区的高。     

Enrichment and exposure assessment of As,Cr and Pb of the soils in the vicinity of Stawell,Victoria, Australia

Stawell Gold Mine in NW Victoria, Australia, mines ores that contain large concentrations of As and significant quantities of the metals Pb and Cr. The aim of this research was to understand the dispersion, enrichment and probable exposure of these potentially hazardous elements around the mine site. Fifty-five surface soil samples were collected near the mine (<15 km) and analysed by ICP-MS/OES following bioavailable and four-acid extractions. Soils near the mine show greater concentrations of As, Cr and Pb than those near a regionally determined background. This is attributed to the combination of a natural geochemical halo around mineralization and anthropogenic dispersion due to mining and urbanization. Total As concentrations were between 16 and 946 mg kg⁻¹ near the mine in a regional background of 1–16 mg kg⁻¹. Total Cr concentrations were between 18 and 740 mg kg⁻¹ near the mine in a regional background of 26–143 mg kg⁻¹. Total Pb concentrations were between 12 and 430 mg kg⁻¹ near the mine in a regional background of 9–23 mg kg⁻¹. Dispersion of contaminant elements from the present ore processing is <500 m. The most enriched soils occur close to the town and are unrelated to present mining practices. The bioavailable As, Cr and Pb, soil ingestion rates and Risk Reference Doses were used to estimate health risks. An average toddler (12 kg) would need to consume at least 1.5 g, and most likely 12 g, of soil per day to show some symptoms of As toxicity. The maximum measured bioavailable As would pose a risk at average ingestion rates of 200 mg per day. Individuals with soil-eating disorders would exceed the safe daily consumption limits for As, and potentially Cr and Pb. Small children are not typically exposed to soil everyday, very few have soil eating disorders, and, therefore, the health risk from the soils around the mine is minimal.     

Tissue distribution of Cd,Cu, Zn,Ni, Cr,Pb and Hg in striated heron,Butorides striatus (Aves: Ardeidae), in a fluvial ecosystem

In this study, the striated heron (Butorides striatus), a species that reproduces in the Middle Paraná River floodplain, was examined for lead, cadmium, chromium, zinc, nickel, mercury and copper concentrations, using liver, kidney, muscle, vertebra and feathers. The results showed low exposure to chromium because all tissue samples had concentrations below the limit of detection. Similar results were obtained for nickel and lead, with the exception of vertebra. This might be associated with either long-term exposure to these metals, or it may be that both nesting and wintering areas are non-polluted. Zinc and copper, both essential metals, were found in all tissues and their concentrations were within the ranges reported in the literature. Mercury was also found in all tissues, but at very low concentrations and even at concentrations below those that produce negative effects in several species of birds (e.g. reproductive success, food intake). Studies of this type are needed to interpret the role of organisms within environments impacted by different human activities.     

生物源提取液与工业废水对土壤中Ni、Co的活化研究

研究了酢浆草提取液(OX)、猪粪提取液(PM)以及味精厂废水(MGW)对土壤中Ni、Co的作用。结果表明，OX提取液原液对土壤中的Ni、Co有较好的活化作用，其活化比例分别达到4．8％和14．6％，但稀释后效果大幅度下降；MGW原液可活化土壤中的1．6％的Ni，但对Co的活化效果较差；PM提取液则对土壤中的重金属起到一定的固定作用。OX提取液的pH值与Ni、Co总活化比例之间呈显著幂相关，可能是由于受到多种酸性活性成分的影响所致。     

复合污染下Cu、Cr、Ni和Cd在水稻植株中的富集特征

掌握水稻对污染土壤中重金属的吸收和富集特征,为科学认识水稻中重金属的残留问题、健康风险提供理论依据。采用田间试验,研究了4个不同处理量Cu、Cr、Ni、Cd复合污染下水稻的富集特征及其随生育期的变化规律。结果表明,重金属在水稻植株各部位中吸收富集系数的大小依次为：Cd〉Cu〉Ni〉Cr,根部重金属吸收富集系数是地上各部位的吸收富集系数的2~100倍。各重金属在水稻植株不同部位的积累分布明显不同,成熟期水稻植株中Cu在水稻不同部位的质量分数为根〉茎≥叶〉米粒〉谷壳,Ni的分布规律为根〉叶〉茎〉米粒〉谷壳,Cr的分布规律为根〉叶〉谷壳≥茎〉米粒,Cd的分布规律为根〉茎〉叶〉米粒〉谷壳;且随着重金属处理量的增加,水稻植株不同部位的重金属质量分数也呈上升趋势。成熟期米粒中Cu、Ni、Cr和Cd的质量分数范围分别为：4.50~6.19、1.86~4.63、0.72~0.76和0.08~0.39 mg·kg-1,与无公害食品标准（GB15199-94、GBT2762-2005）相比,米粒中Cu和Cr的质量分数均未超标,而Ni和Cd（Cd高剂量处理时）的质量分数均超标,存在食用安全风险。重金属在水稻植株不同部位的质量分数随生育期均呈现先升后降的趋势,灌浆中期达到最大,而到成熟期又明显降低。不同重金属在水稻植株中的富集能力和分布规律均呈现明显差异,不同生育期水稻植株中重金属的质量分数明显不同但其质量分数变化呈明显规律性。     

Trace element distribution in the superficial deposits of Northern Derbyshire,England

In an area of marginal farming, trace element distribution associated with lead, fluorite and baryte mineralization is important to the farmer because of the high infertility rate of the livestock and contamination of plant produce leading to the subsequent failure of the farming economy. Therefore sampling of superficial sediments was undertaken over the mineralized Carboniferous Limestone of North Derbyshire above the medieval lead and the modern fluorite workings. Twenty-seven elements were analyzed using emission spectrophotometry and subsequently compared with the geochemistry of the underlying bedrock. Discrepancies which occur are attributed to the glacial and periglacial action during the Wolstonian and Devensian glacial episodes.