Effect of biogeochemical interactions on bioaccessibility of arsenic in soils of a former smelter site in Republic of Korea

The total concentration-based regulations for soil remediation do not consider the possible changes in bioaccessibility of remaining arsenic (As) in soils due to biogeochemical interactions after remediation. This study used As-contaminated soil and pore water samples that were collected from the rice paddy and forest/farmland located in the vicinity of a former smelter site in Republic of Korea to elucidate the changes in As bioaccessibility due to biogeochemical interactions. Bioaccessibility and chemical forms of As in soils were determined by using an in vitro method and sequential extraction, respectively, and soil microbial community was evaluated. Bioaccessibility of As in the rice paddy soil samples was higher than that in the forest/farmland soil samples. This could be attributed to relatively higher dependence of bioaccessible As in the rice paddy soils on the soil concentration of iron (Fe), aluminum, or manganese, which could lead to greater changes in bioaccessible As via reductive dissolution. The strong linear relationship (R ² = 0.90, p value ≤0.001) between the pore water As and Fe concentrations, and the greater portion of bacterial species related to reductive dissolution of Fe oxides in the rice paddies can support the higher As bioaccessibility promoted by reductive dissolution. Therefore, it is necessary to consider the potential changes in the bioaccessible As due to biogeochemical interactions in remediation of As-contaminated soils, particularly when soils are likely to be reused under reductive dissolution-promoting conditions (e.g., flooded conditions).     

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.     

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。     

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.     

Dust from Zambian smelters: mineralogy and contaminant bioaccessibility

Metal smelting is often responsible for local contamination of environmental compartments. Dust materials escaping from the smelting facilities not only settle in the soil, but can also have direct effects on populations living close to these operations (by ingestion or inhalation). In this particular study, we investigate dusts from Cu–Co metal smelters in the Zambian Copperbelt, using a combination of mineralogical techniques (XRD, SEM/EDS, and TEM/EDS), in order to understand the solid speciation of the contaminants, as well as their bioaccessibility using in vitro tests in simulated gastric and lung fluids to assess the exposure risk for humans. The leaching of metals was mainly dependent on the contaminant mineralogy. Based on our results, a potential risk can be recognized, particularly from ingestion of the dust, with bioaccessible fractions ranging from 21 to 89 % of the total contaminant concentrations. In contrast, relatively low bioaccessible fractions were observed for simulated lung fluid extracts, with values ranging from 0.01 % (Pb) up to 16.5 % (Co) of total contaminant concentrations. Daily intakes via oral exposure, calculated for an adult (70 kg, ingestion rate 50 mg dust per day), slightly exceeded the tolerable daily intake limits for Co (1.66× for fly ash and 1.19× for slag dust) and occasionally also for Pb (1.49×, fly ash) and As (1.64×, electrostatic precipitator dust). Cobalt has been suggested as the most important pollutant, and the direct pathways of the population’s exposures to dust particles in the industrial parts of the Zambian Copperbelt should be further studied in interdisciplinary investigations.     

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.     

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.     

Assessing human exposure to aluminium,chromium and vanadium through outdoor dust ingestion in the Bassin Minier de Provence,France

The Western part of the “Bassin Minier de Provence”, a former coal mining area, is still occupied by old polluting industries such as a coal-fired power plant and an alumina factory. The identified pollution sources that raise more concern in the population are the emission of gases and dusts, as well as the storage of raw and transformed materials. In 2011, a preliminary survey was carried out in the area as the first step to an exposure and health risk-assessment study. This first survey intends to assess human exposure through ingestion and health risk associated with potentially harmful elements (PHEs) in ground-level dusts collected in recreational areas used by children. Dust samples were taken at 19 sites distributed across the study area, depending on the location of public parks, public gardens, playgrounds and schools. Pseudo-total concentrations of 53 elements were determined by ICP-MS. Bioaccessible concentrations were estimated using the unified bioaccessibility method. This study presents the results obtained for Al, V and Cr, which seem to be related with industry and show similar distribution patterns. PHEs presumably related to traffic or other urban pollution sources are not discussed in this study. The highest total concentrations occur in dusts near the alumina plant that have significant amounts of Al mineral phases (gibbsite and alumina). However, in these dusts only small fractions of the elements under study are in bioaccessible forms. The highest bioaccessible fractions occur in dusts collected near the coal-fired power plant. Further investigation is required to assess potential pathways of exposure and health risk in this area.     

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.     

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.     

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.     

The influence of physicochemical parameters on bioaccessibility-adjusted hazard quotients for copper,lead and zinc in different grain size fractions of urban street dusts and soils

When the hazard quotient for ingestion (HQI) of a trace element in soil and dust particles is adjusted for the element’s bioaccessibility, the HQI is typically reduced as compared to its calculation using pseudo-total element concentration. However, those studies have mostly used bulk particles (<2 mm or <250 µm), and the reduction in HQI when expressed as bioaccessible metal may not be similar among particle size fractions, the possibility probed by the present study of street dusts and soils collected in Tehran. The highest Cu, Pb and Zn near-total concentrations occurred in the finest particles of dusts and soils. Bioaccessible concentrations of Cu, Pb and Zn in the particles (mg kg^?1) were obtained using simple bioaccessibility extraction test (SBET). The bioaccessibility (%) did not vary much among near-total concentrations. In the bulk (<250 µm) sample, the bioaccessible concentration of Cu and Pb increased as the pH of sample increased, while Zn bioaccessibility (%) in the bulk particles was influenced by organic matter and cation exchange capacity. X-ray diffraction identified sulfide and sulfate minerals in all of the size-fractionated particles, which are insoluble to slightly soluble in acidic conditions and included most of the Cu and Pb in the samples. The only Zn-bearing mineral identified was hemimorphite, which would be highly soluble in the SBET conditions. The calculated HQI suggested potential non-carcinogenic health risk to children and adults from ingestions of soils and dusts regardless of particle size consideration, in the order of Zn > Pb ≥ Cu. The HQI calculated from near-total metal was not much different for particle size classes relative to bulk particles; however, the bioaccessibility percent-adjusted HQI for Pb was higher for the smaller particles than the bulk. This work is novel in its approach to compare HQI for a bulk sample of particles with its composite particle size fractions.     

Bioaccessibility of Cd and Pb in tailings from a zinc smelting in Brazil: implications for human health

Soils and wastes enriched with heavy metals may present ecological and human health risks. A considerable number of mining areas exist in Brazil, where high levels of metals have been found. However, studies of bioaccessibility of metals in soils/tailings from these areas are scarce, despite their potential informational contribution concerning exposure risks of residents near these areas. This study evaluated tailings collected from four sites of a zinc smelting area located in Brazil with aims to: (1) evaluate the presence of metals of potential concern; (2) investigate Cd and Pb bioaccessibility; and (3) determine the desorption kinetics of Cd and Pb. High concentrations of total Cd and Pb (up to 1743 mg Cd kg^?1 and 8675 mg Pb kg^–1) and great variability were found in the tailings, indicating the importance of adequate planning for their final disposal, in order to avoid contamination in the surrounding environment. Cadmium and Pb bioaccessibility percentages in the intestinal phase were less than 47 and 4 %, respectively, which represents significant fractions not available for absorption in the intestinal tract. However, this material has to be monitored since its bioaccessibility may increase with eventual physicochemical changes, releasing Cd and Pb. Desorption kinetics experiments revealed that Pb in the samples remained in less labile fractions, whereas Cd was found in more labile fractions, which is in accordance with the bioaccessibility results.     

Site-Specific Characterization of Castromil Brownfield Area Related to Gold Mining Activities

Castromil is one of the gold mining areas in Portugal that has been abandoned since 1940. This area, which was first mined in Roman times, is located within a Hercynian granite body near the contact with Silurian metasediments. Gold is essentially disseminated along veins in the silicified granite, running NW-SE, related with a shear zone and frequently associated with sulphides (arsenopyrite and basically pyrite). In paragenetic terms, three stages of mineralization are considered: ferro-arseniferous (quartz + arsenopyrite I + pyrite I + pyrrhotite + bismuth), zinciferous (sphalerite + chalcopyrite), and remobilization (arsenopyrite II + galena + gold). Due to the lack of laws and environmental education, Castromil is today a gold mining heritage site where we can detect the consequences of an incautious exploration (tailings, wells and adits located in the old explored zone) and where a residential area is located. In order to characterize the actual state of the old mining area the trace metal contamination of soils and waters by mining activities was investigated. In the studied area 106 soil samples, 15 waters and 20 plants were sampled and analysed. The soil samples were analysed for 32 elements by ICP-AES. Waters were analysed by ionic chromatography and ICP-MS for major and trace elements. Plants were analysed for As, Fe and Pb by AAS. The results are discussed taking into account the risk-based standards for soils and groundwater's (target and intervention values) proposed by Swartjes (1999). The results show elevated concentration of As and Pb which were found in soils collected from agricultural areas. Foodstuff plants species collected in the Castromil agricultural area show high concentrations of As in the leaves (cabbage and lettuce) and in the tubers (potatoes). Groundwaters in the mining area contain high concentrations of As that exceeds the intervention values. The area must to be subject to a remediation process, considering the actual risks to humans and ecosystems and the risks due to contaminant migration.     

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.     

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.     

Geochemical investigation of potentially harmful elements in household dust from a mercury-contaminated site,the town of Idrija (Slovenia)

A comprehensive geochemical investigation of potentially harmful elements (PHEs) in household dust from the town of Idrija (Slovenia), once a world-famous Hg mining town that is now seriously polluted, was performed for the first time. After aqua regia digestion, the content of mercury (Hg), arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), molybdenum (Mo), nickel (Ni), lead (Pb) and zinc (Zn) was measured. PHE-bearing particles were recognised and observed by scanning electron microscopy and energy-dispersive spectrometry before and after exposure to simulated stomach acid (SSA). Mercury binding forms were identified by Hg thermal desorption technique and gastric bioaccessible Hg was estimated after SSA extraction by ICP-MS. With regard to rural and urban background values for Slovenia, high Hg content (6–120 mg/kg) and slightly elevated As content (1–13 mg/kg) were found. Mercury pollution is a result of past mining and ore processing activities. Arsenic content is potentially associated with As enrichment in local soils. Four Hg binding forms were identified: all samples contained Hg bound to the dust matrix, 14 samples contained cinnabar, two samples contained metallic Hg (Hg⁰), and one sample assumingly contained mercury oxide. After exposure to SSA, Hg-bearing phases showed no signs of dissolution, while other PHE-bearing phases were significantly morphologically and/or chemically altered. Estimated gastric Hg bioaccessibility was low (<0.006–0.09 %), which is in accordance with identified Hg binding forms and high organic carbon content (15.9–31.5 %) in the dust samples.     

Evaluating the respiratory bioaccessibility of nickel in soil through the use of a simulated lung fluid

Simulated lung fluids are solutions designed to mimic the composition of human interstitial lung fluid as closely as possible. Analysis of mineral dusts using such solutions has been used to evaluate the respiratory bioaccessibility of various elements for which solubility in the lungs is a primary determinant of reactivity. The objective of this study was to employ simulated lung fluid analysis to investigate the respiratory bioaccessibility of nickel in soils. Current occupational guidelines in Australia regulate nickel compounds in terms of water solubility, though this may not be an accurate estimation of the total nickel that will dissociate in the lungs. Surface soils were collected from the city of Kalgoorlie in Western Australia, the site of an operational nickel smelter and metal mining activities. The fraction of the samples less than 10 μm was extracted from the soil, and it was this sub-10-μm fraction that was found to hold most of the total nickel present in the soil. The fine fraction was analyzed using a simulated lung fluid (modified Gamble’s solution) to isolate the nickel phases soluble in the lungs. In addition, a sequential extraction was employed to compare the bioaccessible fraction to those dissolved from different binding forms in the soil. In all samples, the simulated lung fluid extracted more nickel than the two weakest leaches of the sequential extraction combined, providing a more representative nickel bioaccessibility value than the current water leach method.     

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.