Oral bioaccessibility of trace metals in household dust: a review

Because household dust is a heterogeneous assortment of particles derived from a multitude of diverse sources, concentrations of toxicants, like trace metals, vary widely among sample populations. For risk assessment purposes, the bioaccessibility of a trace metal, or its degree of solubilization in the human lung or digestive environment, provides a better metric of its potential health impact than its total concentration. In this paper, the relatively little direct information that exists on the in vitro oral bioaccessibilities of metals in household dust is reviewed. Data and mechanisms from studies involving better characterized geosolids, like soil and street dust, or metal-rich components thereof, such as paints, are also extrapolated to the household setting, although use of these solids as surrogates of household dust is not recommended. The bioaccessibility of a given metal is highly variable in the household setting; for instance, reported accessibilities of Pb in fluids that mimic the human stomach range from 25 to 80%, and accessibility is usually, but not always, reduced when conditions are altered to mimic the intestine. While part of this variation reflects the inherent heterogeneity of samples arising from local to regional differences in geology, industrial emissions, and domestic (and cultural) practices, considerable variation results from the precise means by which bioaccessibility is determined in vitro. It is recommended, therefore, that the effects of physicochemical variables, and in particular, the solid to fluid ratio and the pH of the stomach phase, are studied systematically such that appropriate algorithms or corrections may be factored into measures of bioaccessibility obtained under operationally defined default conditions.     

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.     

城市小集水区降雨径流污染来源解析

利用深圳市王家庄集水区的降雨径流水质监测数据,运用正定矩阵因子分解法（PMF）定量解析了单个城市小集水区降雨径流污染的主要来源。结果表明：研究区降雨径流的主要污染源为城市污水、管内沉积物和地表径流。其中城市污水以输出氨氮（NH3-N）和总氮（TN）为主,管内沉积物是化学需氧量（CODCr）、总磷（TP）和生化需氧量（BOD5）的主要来源,地表径流为固体悬浮物（SS）的主要来源。PMF模型可作为土地利用方式均一的单个城市小集水区降雨径流污染源解析的有效方法之一,主要污染源的廓线能否保持相对稳定是该模型在降雨径流污染源解析时的主要约束条件。     

Chemical speciation and bioaccessibility of lead in surface soil and house dust,Lavrion urban area,Attiki, Hellas

In the Lavrion urban area study, Hellas, a five-step sequential extraction method was applied on samples of ‘soil’ (n = 224), affected by long-term mining and metallurgical activities, and house dust (n = 127), for the purpose of studying the potential bioaccessibility of lead and other metals to humans. In this paper, the Pb concentrations in soil and house dust samples are discussed, together with those in rocks and children’s blood. Lead is mainly associated with the carbonate, Fe–Mn oxides and residual fractions in soil and house dust. Considering the very low pH of gastric fluids (1–3), a high amount of metals, present in soil (810–152,000 mg/kg Pb) and house dust (418–18,600 mg/kg Pb), could be potentially bioaccessible. Consequently, children in the neighbourhoods with a large amount of metallurgical processing wastes have high blood-Pb concentrations (5.98–60.49 μg/100 ml; median 17.83 μg/100 ml; n = 235). It is concluded that the Lavrion urban and sub-urban environment is extremely hazardous to human health, and the Hellenic State authorities should urgently tackle this health-related hazard in order to improve the living conditions of local residents.     

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.     

Oral and inhalation bioaccessibility of potentially toxic elements in household dust from former Hg mining district,Idrija, Slovenia

Environmental Geochemistry and Health - One of the main sources of potential chronic exposure to potentially toxic elements is household dust, especially in an environment with known point sources...     

Bioavailability of trace metals in brownfield soils in an urban area in the UK

Thirty-two brownfield sites from the city of Wolverhampton were selected from those with a former industrial use, wasteland or areas adjacent to industrial processes. Samples (<2 mm powdered soil fraction) were analysed, using inductively coupled plasma–atomic emission spectrometry (ICP–AES) for 20 elements. Loss on ignition and pH were also determined. A five-step chemical sequential extraction technique was carried out. Single leach extraction with 0.12 M hydrochloric acid of Pb, Cu and Zn in soil was determined as a first approximation of the bioavailability in the human stomach. Some of the sites were found to have high concentrations of the potentially toxic elements Pb, Zn, Cu and Ni. The partitioning of metals showed a high variability, however a number of trends were determined. The majority of Zn was partitioned into the least chemically stable phases (steps 1, 2 and 3). The majority of Cu was associated with the organic phase (step 4) and the majority of Ni was fractionated into the residue phase (step 5). The majority of Pb was associated with the residue fraction (step 5) followed by Fe–Mn oxide fraction (step 3). The variability reflects the heterogeneous and complex nature of metal speciation in urban soils with varied historic histories. There was a strong inverse linear relationship between the metals Ni, Zn and Pb in the readily exchangeable phase (step 1) and soil pH, significant at P < 0.01 level. There was a significant increase (P < 0.05) in the partitioning of Cu, Ni and Zn into step 4 (the organic phase) in soils with a higher organic carbon content (estimated by loss on ignition). Copper was highly partitioned into step 4 as it has a strong association with organics in soil but this phase was not important for the partitioning of Ni or Zn. The fractionation of Ni, Cu and Zn increased significantly in step 3 when the total metal concentration increases (P < 0.01). The Fe–Mn oxide fraction becomes more important in soils elevated in these metals, possibly due to the scavenging of metals by oxides. Cu and Pb extracted by HCl was statistically similar to the sum of the metals in steps 1 to 4 (P < 0.01) and HCl available Zn was statistically similar to the sum of Zn in steps 1 to 3 (P < 0.01). Step 4 (the organic phase) was not an important phase for Zn, so it was concluded that any Cu, Zn and Pb present in soil in a nonresidue phase would be potentially available for uptake into the human system once soil has been ingested.     

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.     

Oral bioaccessibility of inorganic contaminants in waste dusts generated by laterite Ni ore smelting

The laterite Ni ore smelting operations in Niquelândia and Barro Alto (Goiás State, Brazil) have produced large amounts of fine-grained smelting wastes, which have been stockpiled on dumps and in settling ponds. We investigated granulated slag dusts (n = 5) and fly ash samples (n = 4) with a special focus on their leaching behaviour in deionised water and on the in vitro bioaccessibility in a simulated gastric fluid, to assess the potential exposure risk for humans. Bulk chemical analyses indicated that both wastes contained significant amounts of contaminants: up to 2.6 wt% Ni, 7580 mg/kg Cr, and 508 mg/kg Co. In only one fly ash sample, after 24 h of leaching in deionised water, the concentrations of leached Ni exceeded the limit for hazardous waste according to EU legislation, whereas the other dusts were classified as inert wastes. Bioaccessible fractions (BAF) of the major contaminants (Ni, Co, and Cr) were quite low for the slag dusts and accounted for less than 2 % of total concentrations. In contrast, BAF values were significantly higher for fly ash materials, which reached 13 % for Ni and 19 % for Co. Daily intakes via oral exposure, calculated for an adult (70 kg, dust ingestion rate of 50 mg/day), exceeded neither the tolerable daily intake (TDI) nor the background exposure limits for all of the studied contaminants. Only if a higher ingestion rate is assumed (e.g. 100 mg dust per day for workers in the smelter), the TDI limit for Ni recently defined by European Food Safety Authority (196 µg/day) was exceeded (324 µg/day) for one fly ash sample. Our data indicate that there is only a limited risk to human health related to the ingestion of dust materials generated by laterite Ni ore smelting operations if appropriate safety measures are adopted at the waste disposal sites and within the smelter facility.     

Distribution of metals in mechanical fractions of soils from a lake catchment in Venezuela

Soil samples were collected from both the surface and at depth from the lowlands around Lake Valencia and from the adjacent mountains. This paper reports results for Al, Ca, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb and Zn in mechanical fractions of the soils. Lowland soils, developed on lacustrine sediments, show a predominance of medium- to fine-grain size fractions whereas the shallow mountain soils show the highest percentage of particles in the coarse to medium fractions. Concentrations of most of the elements investigated increased toward finer particle sizes. The generally higher metal concentrations in lowland soils compared with mountain soils are consistent with release by weathering in the uplands and accumulation in the lowlands. The presence of carbonates derived from ubiquitous shelly material in the lowland soils may explain increases of Ca and Mg in labile fractions. In the lowland area, there is little evidence for the translocation of metals in the soil profiles, despite the high rainfall of a tropical climate, and the calcareous nature of these soils could account for the immobility of metals.     

The distribution of heavy metals in deposited urban dusts and sediments, Coventry, England

Samples of urban dusts and sediments have been collected and categorised into three compartment those which act mainly as sources, those undergoing transport and those which have been deposited. The sediments were fractionated into <63m to match similar sized lacustrine sediments and <2mm to represent natural and anthropogenic fluvially transported sediments. Preliminary results of total heavy metals analysis show that the <2mm fraction of the source group exhibits the greatest variabilty in metal concentrations. Overall, however, the <63m fraction dominates regardless of compartment. Some heavy metal concentrations decrease through the sourcetransportdeposit process, possibly due to selective onward transport of finer material or other anthropogenic processes unique to the urban environment (e.g. street cleansing). Sitespecificity is indicated in a comparison with other similar studies.     

Analysis of rainfall runoff characteristics from a subtropical urban lawn catchment in South-east China

Characteristics of rainfall runoff from a 3.26 hm² urban catchment with predominant land-use as lawn in Xiamen City, South-east China were investigated and analyzed. Water quality and quantity measurements of rainfall runoff were conducted for ten rainfall events over the period March, 2008 to April, 2009. The results indicated that chemical oxygen demand (COD) and total phosphorus (TP) were the major pollutants with event mean concentrations of 56.09 and 0.44 mg·L^?1. From hydrograph and pollutograph analysis of two typical rainfall events, it was clear that the peak rainfall preceded the peak flowrate by about 15?C20 min. Meanwhile, concentrations of major pollutants showed multiple peaks and these peaks usually preceded peak flowrate. There were no distinctive first-flush effects except for the rainfall events with the longest rainfall duration and largest runoff volume, which was verified by the fact that the first 30% runoff volume (FF30) carried 39.36% of the total suspended solids (TSS) load, 35.17% of the COD load, 28.13% of the TP load and 39.03% of the nitrate nitrogen load. Multivariate regression analysis further demonstrated that the total runoff volume had a positive correlation with the FF30 of TSS and COD.     

Occurrence and distribution of organochlorine residues and metals in sediment,water and fish in the catchment area of lake baiyangdian,china

The occurrence and distribution of metals (Al, Cd, Cr, Cu, Pb, Zn), organochlorine residues (HCH, DDT and metabolites, PCBs) and EOC1 (extractable organic bound chlorine) were monitored in 1993 and 1996 in sediment, water and fish in the catchment area of Lake Baiyangdian, China. The levels of the metals, especially Cd and Zn, were significantly higher in the sediment than those in non‐polluted areas. PCBs and chlorinated pesticides constituted only a minor part (< 8.4%) of the extractable organic bound chlorine, indicating the presence of additional, unknown, organochlorine residues. Among the pesticides, DDT was widely distributed and high levels occurred in fish despite a ban of its production and use in 1983. The low quotient of pp‐DDT/pp‐DDE in sediment and fish indicated that the input of DDT to the catchment area was not of recent origin.     

Some characteristics of the distribution of heavy metals in urban topsoil of Xuzhou,China

An assessment is presented of distribution characteristics of heavy metals in the urban topsoil from the city of Xuzhou. The concentrations of Ag, Al, As, Au, Ba, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, Hg, Li, Mn, Mo, Ni, Pb, Pd, Pt, Sb, Sc, Se, Sn, V and Zn have been determined from 21 soil samples. Examination of lognormal distribution plots indicates that the diagrams of Al, Be, Fe, Ga, Li, and V are almost linear suggesting that these metals are almost unaffected by anthropogenic activities while the plots for As, Cd, Cu, Pb, Pd, Pt, Se, Zn and others are not linear probably due to anthropogenic activities from which these metals are delivered to the soils. Al is used for mineralogical normalization of these data. An evaluation of background values for topsoil is also carried out by means of lognormal distribution plots. The results show our background values obtained from the lognormal distribution plots are comparable to those values of uncontaminated soils of Xuzhou obtained by previous work except for Cd and Hg. At present, no explanation for the exceptions Cd and Hg can be given.     

Heavy metals accumulation in tree leaves from urban areas

Higher plants may be used as biomonitors for the assessment of atmospheric heavy metal pollution by means of their bioaccumulative properties. We evaluated the reliability of biomonitoring heavy metal pollution by horse chestnut and linden leaves, common species found in Belgrade city parks. The results show that the highest concentrations of heavy metals were found in horse chestnut leaves at Studentski Park site, amounting to 110.2, 20.3 and 4.9 g g^–1 dry weight for Cu, Pb and Cd, respectively, which are considered above toxic levels for plants.Selected article from the Regional Symposium on Chemistry and Environment, Krusevac, Serbia, June 2003, organised by Dr. Branimir Jovancicevic.     

贵阳市区地表灰尘重金属污染分析与评价

以贵阳市区为研究地点,采集了贵阳城区工业区、交通区、商业区、居民区、文教区、公园广场、对照区7个类别共80个采样点的地表灰尘,分析了地表灰尘重金属在不同区域的分布特征,并分析其可能来源。最后,应用潜在生态危害指数法对6个功能区（工业区、交通区、商业区、居民区、文教区、公共区）样品中重金属的潜在生态危害进行评价。结果表明：贵阳市地表灰尘重金属的平均质量分数均高于贵州省土壤环境背景值,Cd、As、Cu污染质量分数都超过4倍以上背景值水平,其余重金属污染水平大多处于1~3倍背景值水平。就单个重金属潜在生态危害系数平均值来看,地表灰尘的潜在生态危害最大的是Hg,其次是Cd,生态危害最低的是Cr。6个功能区生态危害水平均属于强生态危害水平,其中工业区和公共区生态危害水平最高。     

Reduction of availability of trace metals in urban soils using inorganic amendments

Urban soils in medium- and large-sized cities generally have shown elevated contents of environmentally important trace metals (e.g. lead, copper, zinc). Such high concentrations in soils of green areas, mainly recreational areas, can be a source of potentially toxic elements and pose a risk for human health. Thus the availability of these contaminants is an essential control parameter, as it indicates potential plant uptake and their transfer to humans via inhalation of suspended dust, or direct ingestion (i.e. hand to mouth pathway), or consumption of contaminated foodstuff. Young children are the most sensitive segment of the population. Addition of amendments to the soil is a feasible technique to reduce the availability of trace metals. Accordingly, four urban soils of green areas of Seville (Spain), with relatively high lead contents and moderate copper and zinc contents, were amended in the laboratory with four inorganic materials [acid zeolite (AZ), sodium zeolite (SZ), Slovakite (SL), apatite (AP)], at two rates (1%, 5% w/w) and incubated for 1 year. Significant decreases in EDTA-extractable metal contents were observed in some of the treatments after adding the amendments even before the incubation begun, mainly for SL treatments. The amendment that produced the longest lasting immobilisation effect, compared to control treatments, was AZ at the higher rate. The effects of SZ and SL tended to decrease with time, while the AP effect was almost negligible after 3 months of ageing. This study confirms the feasibility of using certain inexpensive soil amendments to at least temporarily immobilise metals in urban soils for the purpose of protecting human health, especially that of young children.     

Relative bioaccessibility of Pb-based paint in soil

The threat posed by lead (Pb) in soil for pediatric populations continues to be a public health issue. In long-established residential areas, a principal source of Pb in soil is likely to be old Pb-based paint originating from building surfaces. The health hazard posed by Pb from paint in soil will likely depend on quantity of paint incorporated, its Pb-mineral composition, whether the Pb is locked in some other material and the paint residence time in the soil (degree of aging). Here the relative bioavailability (RBA) of Pb in different types of Pb-bearing paint has been assessed. Tests were performed with individual paints, with paints mixed with a low-Pb soil, and with paints mixed with soil and the biogenic phosphate apatite II. Thirteen Pb-bearing paint samples were ground and passed through 250- and 100-µm screens. Samples nominally <100 µm from all the paints were analyzed, and six of the paints for which there was sufficient material in the 100- to 250-µm-size range were also tested. RBA extraction of Pb employed a simulated gastric fluid (SGF) of HCl and glycine adjusted to a pH of 1.5 in which samples were agitated (in an end-over-end rotator) for 2 h. Original paints were examined by SEM/EDX, and by XRD, residues collected after RBA extraction were examined by SEM/EDX. The concentration of Pb in the extraction fluid was measured by AAS. The quantity of Pb mobilized in each test batch was approximately an order of magnitude less in the paint–soil mix compared to the corresponding paint-only sample. The difference in the amount of Pb extracted from the paint–soil mix compared to the paint–soil–phosphate mix was minimal. However, in the post-RBA residues of the paint–soil mix, a PbCl precipitate was observed, and in the extraction residues of the paint–soil–apatite II mixes PbClP phases were recorded. Precipitation of these secondary phases obviously modified the amount of Pb in the extraction fluid, and this may need to be considered, i.e., under-reporting of extractable Pb, when this form of in vitro extraction is used to determine the RBA of Pb in environmental media.     

Use of a physiologically based extraction test to estimate the human bioaccessibility of potentially toxic elements in urban soils from the city of Glasgow,UK

A simple, two-stage, physiologically based extraction has been applied to assess the human bioaccessibility of potentially toxic elements (PTE) in 20 urban soils from a major UK city. Chromium and iron bioaccessibilities were found to be markedly higher in the intestinal phase, whilst lead and zinc bioaccessibilities were higher in the stomach. Copper and manganese bioaccessibilities were generally similar under both extraction conditions. Principal component analysis was used to study relationships amongst bioaccessible element concentrations and land use. Distinctions could be observed between the distributions of the urban metals—copper, lead and zinc—and metals predominantly of geogenic origin, such as iron. There was no clear delineation between roadside soils and soils obtained from public parks. Bioaccessible analyte concentrations were found to be correlated with pseudototal (aqua regia soluble) analyte concentrations for all elements except iron. Results of the BCR sequential extraction did not, in general, provide a good indication of human bioaccessibility. Comparison of bioaccessible PTE concentrations with toxicological data indicated that lead is the element of greatest concern in these soils but that levels are unlikely to pose a health risk to children with average soil intake.