Simple Bioaccessibility Extraction Test Research Articles

Bioaccessibility of heavy metals in soils cannot be predicted by a single model in two adjacent areas.

The objective of this study was to examine whether a single model could be used to predict the bioaccessibility of heavy metals in soils in two adjacent areas and to determine the feasibility of using existing data sets of total metal concentrations and soil property parameters (e.g., pH, total organic carbon, and soil texture) when predicting heavy metal bioaccessibility. A total of 103 topsoil samples were collected from two adjacent areas (Baotou and Bayan Obo). A total of 76 samples were collected from Baotou, and 27 were collected from Bayan Obo. The total and bioaccessible concentrations of arsenic (As), copper (Cu), lead (Pb), and zinc (Zn) were measured following complete composite acid digestion and a simple bioaccessibility extraction test. The average total concentrations of As, Cu, Pb, and Zn were 8.95, 27.53, 28.40, and 79.50mg/kg, respectively, in Baotou and 18.12, 30.75, 38.09, and 87.62mg/kg in Bayan Obo. Except for As, these values were similar in both areas. The average bioaccessible heavy metal concentrations (Bio-HMs) for each target HM were also similar. In Baotou, the average Bio-HM values for As, Cu, Pb, and Zn were 1.16, 3.76, 16.31, and 16.10mg/kg, respectively, and 1.26, 2.51, 14.31, and 8.68mg/kg in Bayan Obo. However, the relative bioaccessibilities for each HM in Baotou were greater than those in Bayan Obo, with mean values for Pb, Zn, Cu, and As of 57, 20, 17, and 12%, respectively, in Baotou and 40, 11, 9, and 8% in Bayan Obo. In both areas, prediction models were successfully created using heavy metal concentrations and soil physicochemical parameters; however, models of the same target element differed between the areas, which indicated that a common model for both sites does not exist. Bio-HMs were highly affected by soil properties, which were found to differ between the adjacent areas. In addition, soil properties with large variations played major roles in the predictive models. This study highlights the importance of incorporating physical and chemical parameters that vary greatly when building predictive models of heavy metal bioaccessibility in soil. A similarity in soil properties between areas might be a prerequisite for the creation of a common predictive model for soil Bio-HMs.

Testing single extraction methods and in vitro tests to assess the geochemical reactivity and human bioaccessibility of silver in urban soils amended with silver nanoparticles

To assess if the geochemical reactivity and human bioaccessibility of silver nanoparticles (AgNPs) in soils can be determined by routine soil tests commonly applied to other metals in soil, colloidal Ag was introduced to five pots containing urban soils (equivalent to 6.8mgAgkg−1 soil). Following a 45days stabilization period, the geochemical reactivity was determined by extraction using 0.43M and 2M HNO3. The bioaccessibility of AgNPs was evaluated using the Simplified Bioaccessibility Extraction Test (SBET) the “Unified BARGE Method” (UBM), and two simulated lung fluids (modified Gamble’s solution (MGS) and artificial lysosomal fluid (ALF)).The amount of Ag extracted by 0.43M and 2M HNO3 soil tests was <8% and <50%, respectively of the total amount of Ag added to soils suggesting that the reactivity of Ag present in the soil can be relatively low. The bioaccessibility of Ag as determined by the four in vitro tests ranged from 17% (ALF extraction) to 99% (SBET) indicating that almost all Ag can be released from soil due to specific interactions with the organic ligands present in the simulated body fluids.This study shows that to develop sound soil risk evaluations regarding soil contamination with AgNPs, aspects of Ag biochemistry need to be considered, particularly when linking commonly applied soil tests to human risk assessment.

Factors influencing the heavy metal bioaccessibility in soils were site dependent from different geographical locations.

A soil survey was conducted in urban areas from five sites, including Beijing, Baotou, Datong, Fuyang, and Xiantao in China. The objective was to explore the most significant factors that may impact the bioaccessibility of heavy metals (Bio-HMs), including As, Cr, Cu, Pb, and Zn, in soils. Twenty to 30 composite soil samples were collected at each site. The various soil properties, including pH, particle size, Fe/Mn, and organic matter contents, were analyzed. The chemical operated forms of HMs in soils were measured by the Bureau of Reference (BCR) sequential extraction scheme, while the Bio-HMs were determined by the simple bioaccessibility extraction test (SBET) procedure. The concentrations of total heavy metals (T-HMs) in soils from different sites (cities) were in the range as As (5.69-9.86), Cr (77.42-230.20), Cu (15.68-36.54), Pb (14.12-58.93), and Zn (38.66-183.46) mg/kg. Cu and Pb had higher relative bioaccessibilities (48-70%) than those of As and Cr (6-15%), indicating higher health risks of the former than the latter two HMs. The Bio-HMs for various HMs were comparable to the first two or three combined BCR extracted fractions, with an exception of Cu, whose Bio-HMs were larger than the combined three BCR fractions, indicating that Cu was highly accessible in soils as compared with other HMs. Factor analysis showed that all variables, including soil property parameters and BCR extracted fractions, could be represented by three common factors extracted with higher than 0.5 loadings and ∼80% cumulative contribution to the total variance. Among the three common factors, factor 1, containing mainly pH, texture, and Fe/Mn variables, and factor 3, containing mainly organic matter variable, could be attributed to geographical regions, while factor 2, containing mainly BCR extracted fractions, could be ascribed to relative bioaccessibility of HMs (R-Bio-HMs). Interactive mapping of the main factors and cluster analysis were consistent, which supported the "site gathering" of the soil sample pools, suggesting that the Bio-HMs in soils in different geographical localities were site dependent.

In Vitro Health Risk Assessment of Ingesting Metal-Enriched Soils and Dusts in a Chinese Mining City

ABSTRACTTo evaluate the potential health hazards caused by extensive vanadium–titanium magnetite mining, bioavailability and bioaccessibility of metals were assessed in the pluralistic mining–agriculture–residential city of Panzhihua, China. Intensive mining and related heavy traffic may have contributed to Ni, Cr, and Zn contamination and Mn and V accumulation in soils and road dusts. The metal bioavailability estimated by water extraction was significantly lower than metal bioaccessibility on the basis of the simple bioaccessibility extraction test. The bioaccessible metal concentrations were significantly and positively correlated with soil/dust total metal concentrations (p < .05). However, bioavailable metal concentrations exhibited no relationship with total metal concentrations except for V. The bioaccessibility of metals significantly varied and exhibited the following order: Pb > Zn > Mn > Ni > V > Cr. Health risk assessment indicated that the carcinogenic and non-carcinogenic risks posed by these metals were at an acceptable level, but Cr in soils of the mining area and V in surface soils along the Jinsha River were close to the safe level for children. Therefore, the potential health risk attributed to the exposure of children to metals in surface soils and road dusts in such areas should not be overlooked.

Bioaccessibility of antimony and arsenic in highly polluted soils of the mine area and health risk assessment associated with oral ingestion exposure

In this study, the bioaccessibility and the human health risks of Sb and As in soils from Xikuangshan (XKS) Sb mine, Hunan, China were investigated using two commonly used in vitro extraction methods, Simplified Bioaccessibility Extraction Test (SBET) and Physiologically Based Extraction Test (PBET). Soils in the XKS Sb mine area were mainly co-contaminated by Sb (74.2–16,389; mean: 3061mgkg−1) and As (7.40–596; mean: 216mgkg−1). The bioaccessibility values of Sb and As in most cases were less than 30%, and the average bioaccessibility values of Sb and As were 5.89±6.44% and 2.13±2.55% for the SBET extraction; 7.83±9.82% and 6.62±6.37% for the PBET (Gastric) extraction; and 3.03±3.53% and 2.40±2.01% for the PBET (Intestinal) extraction, respectively. The bioaccessible Sb and As were significantly positively correlated with the total concentrations, but negatively correlated with the Fe, Al, Mn and organic matter (OM) contents in soils. Risk assessment results based on total concentrations might overestimate the risk existing in the studied area. After considering the bioaccessibility, the Hazard Quotient (HQ) values of Sb for most of the sampling sites and of As for all of the sampling sites became lower than 1. The Carcinogenic Risk (CR) values of As were also significantly reduced, 8.77E−06 and 1.74E−05 on average for the SBET and PBET methods, respectively. Considering the bioaccessibility can provide more applicable guidelines for risk assessments and more rational suggestions in the management of the soils contaminated with Sb and As.

In situ stabilization of As and Sb with naturally occurring Mn, Al and Fe oxides in a calcareous soil: Bioaccessibility, bioavailability and speciation studies

This study investigated the effectiveness of 6 different types of naturally occurring manganese, aluminum and iron oxides for stabilization of As and Sb in a calcareous soil spiked with 50mgkg−1 of As or Sb and two dosages of treatments (2% and 5%). The resulting contaminated soils were subjected to a series of chemical extraction studies including sequential extraction, single step extraction with DTPA and Simplified Bioaccessibility Extraction Test (SBET) for estimation of bioaccessible fraction of As and Sb in soil and a greenhouse experiment using barley as the test crop. The results showed that Fe-associated and carbonate-bound fraction of As and Sb were predominant fractions. However, the amounts of labile fractions were higher in As contaminated soils, whereas the percentage of Sb associated with crystalline Fe-oxide and residual fractions were higher. The results revealed that application of natural metal oxides reduced DTPA and SBET extractable amounts and plant uptake of As and Sb. After application of amendments, the exchangeable fraction of As decreased dramatically by up to 82% while Sb exchangeable fraction decreased by up to 60% depending upon the additive. The results of chemical extractions and plant uptake confirmed that Sb had lower bioavailability, compared with As.

Human Health Risk Assessment Based on Toxicity Characteristic Leaching Procedure and Simple Bioaccessibility Extraction Test of Toxic Metals in Urban Street Dust of Tianjin, China

The potential ecological and human health risk related with urban street dust from urban areas of Tianjin, China was quantitatively analyzed using the method of toxicity characteristic leaching procedure (TCLP) and simple bioaccessibility extraction test (SBET). In the study, Hakason index, Nemerow index (P), the hazard index (HI) and the cancer risk index (RI) were calculated to assess the potential risk. The sequence of potential ecological risk based on Hakason index was arsenic (As) > cadmium (Cd) > lead (Pb) > copper (Cu) > chromium (Cr), in particular, As and Cd were regarded as high polluted metals. While the results of extraction of TCLP were assessed using P, the sequence was As > Pb > Cd > Cr > Cu, which mean that As and Pb should be low polluted, and Cd, Cr and Cu would barely not polluted. For human health, total carcinogenic risk for children and adults was 2.01×10−3 and 1.05×10−3, respectively. This could be considered to be intolerable in urban street dust exposure. The sequence in the hazard quotient (HQ) of each element was As > Cr > Pb > Cu > Cd. The HI value of these toxic metals in urban street dust for children and adults was 5.88×10−1 and 2.80×10−1, respectively. According to the characters of chemistry, mobility, and bioavailability of metals in urban street dust, we estimated the hazards on the environment and human health, which will help us to get more reasonable information for risk management of metals in urban environment.

Immobilization Efficiency Evaluation by Using Tessier, TCLP and SBET Method for As, Cu and Pb Contaminated Soils

In this paper, Tessier sequence extract procedure (SEP), toxicity leaching procedure (TCLP) and simple bioaccessibility extraction test (SBET) were employed to evaluate the immobile efficiencies for As, Cu and Pb contaminated soils. Experimental results indicated that the TCLP was efficient to extract the most active part heavy metal and evaluate the risk of the samples; the Tessier method divided heavy metals in soils to different fractions. Monitoring the changes of different fractions during the immobilizing procedure could help fully understand the mechanism of stabilization. The SBET method simulated the human digest system, thus it could be used to evaluate the risk changes to human during the immobilizing process; and to reveal the potential risk of chemical stability. In our project, these three evaluate method should be utilized properly to help accessing the risk, electing suitable immobilizing method and evaluating the efficiency of stabilization.

Food crop accumulation and bioavailability assessment for antimony (Sb) compared with arsenic (As) in contaminated soils

Field samples and a 9-week glasshouse growth trial were used to investigate the accumulation of mining derived arsenic (As) and antimony (Sb) in vegetable crops growing on the Macleay River Floodplain in Northern New South Wales, Australia. The soils were also extracted using EDTA to assess the potential for this extractant to be used as a predictor of As and Sb uptake in vegetables, and a simplified bioaccessibility extraction test (SBET) to understand potential for uptake in the human gut with soil ingestion. Metalloids were not detected in any field vegetables sampled. Antimony was not detected in the growth trial vegetable crops over the 9-week greenhouse trial. Arsenic accumulation in edible vegetable parts was <10 % total soil-borne As with concentrations less than the current Australian maximum residue concentration for cereals. The results indicate that risk of exposure through short-term vegetable crops is low. The data also demonstrate that uptake pathways for Sb and As in the vegetables were different with uptake strongly impacted by soil properties. A fraction of soil-borne metalloid was soluble in the different soils resulting in Sb soil solution concentration (10.75 ± 0.52 μg L(-1)) that could present concern for contamination of water resources. EDTA proved a poor predictor of As and Sb phytoavailability. Oral bioaccessibility, as measured by SBET, was <7 % for total As and <3 % total Sb which is important to consider when estimating the real risk from soil borne As and Sb in the floodplain environment.

Evaluation of the As, Cu and Pb Immobilizing Efficiency by Tessier, TCLP and SBET Method

Utilize of property evaluation method for an immobilizing procedure is very important. In this paper, an immobilizing procedure was used to stabilize heavy metals in tested soils. Tessier sequence extract procedure (SEP), toxicity leaching procedure (TCLP) and simple bioaccessibility extraction test (SBET) were used to evaluate the efficiency of the stabilization procedure. The leachability, bioaccessibility and speciation of As, Cu and Pb in the tested soils were analyzed using Tessier SEP, TCLP and SBET method separately. The results indicated that the most active part of the heavy metals could be extracted out by TCLP method and it could be used to evaluate the risk of the tested soils. Tessier method divided heavy metals in soils to different fractions. Monitoring the changes of different fractions during the immobilizing procedure could help fully understand the mechanism of stabilization. The SBET method simulated the human digest system and evaluated the risk changes to human during the immobilizing procedure. And it helped to reveal the potential risk of chemical stability. In our project, these three evaluation method should be utilized properly to help accessing the risk, electing suitable immobilizing method and evaluating the efficiency of stabilization.

Leachability, bioaccessibility and plant availability of trace elements in contaminated soils treated with industrial by-products and subjected to oxidative/reductive conditions

Two industrial by products, red mud (RM) and aluminum-rich water treatment residue (Al-WTR) were used (2%w/w) for the immobilization of As, Cu and Pb in two polluted soils. Soil-1 was a mine contaminated soil (2428 As, 234 Cu and 559 Pbmgkg−1); Soil-2 was a chromated copper arsenate contaminated soil (860 and 1500mgkg−1 of As and Cu respectively). Two different redox conditions (aerobic and 3 repeated reduction/oxidation cycles) were also applied. The immobilization of trace elements and their bioaccessibility were evaluated through a leaching test and simplified bioaccessibility extraction test (SBRC) respectively, whereas phytoavailability was assessed in pot trials with Lolium perenne.The RM addition increased the solubility of As and Pb, under both redox conditions, in Soil-1 with respect to untreated soil (i.e., +40 and 38% respectively in RMsw-Soil-1 in aerobic condition). In Soil-2 Al-WTR was the amendment most efficient at decreasing As mobility (<50% with respect to untreated soil). The high correlations detected between trace element mobility and dissolved organic carbon (DOC) suggests that As, Cu and Pb formed soluble organic complexes. The SBRC results suggested that this test was mainly affected by physical and chemical characteristics of soils, whereas trial pot showed that the treatments with RMsw and Al-WTR in aerobic condition were able to decrease the plant uptake of As by 34 and 57% in Soil-1, and by 88 and 87% in Soil-2. These treatments also reduced uptake of Cu from Soil-2 (by 68 and 86%) and of Pb from Soil-1 (by 52 and 34%).The results of this study show that the efficacy of the soil amendments is a complex function of soil conditions, source of contamination, and perhaps most importantly the environmental endpoint considered.

Bioaccessibility and health risk assessment of arsenic in arsenic-enriched soils, Central India

Incidental soil ingestion is expected to be a significant exposure route to arsenic for children because of the potentially high arsenic contents found in certain soils. Therefore, it is prudent to get information on oral bioaccessibility of arsenic following incidental soil ingestion and its relevance in health risk assessment for future remediation strategies. Soil samples were collected from eight villages of Ambagarh Chauki block, Chhattisgarh, Central India. The soils from seven villages had total arsenic content more than the background level of 10mgkg−1 (ranged from 16 to 417mgkg−1), whereas the total arsenic content of soil from Hauditola was 7mgkg−1. Bioaccessible arsenic assessed by the simplified bioaccessibility extraction test (SBET) ranged from 5.7 to 46.3%. Arsenic bioaccessibility was significantly influenced by clay content (R2=0.53, p<0.05, n=8), TOC (R2=0.50, p<0.05, n=8), Fe content (R2=0.47, p<0.05, n=8) and soil pH (R2=0.75, p<0.01, n=8). Risk assessment of the study sites showed that hazard index of arsenic under incidental soil ingestion was below 1 in all the study sites, except Kaudikasa. However, carcinogenic risk probability for arsenic to children from the villages Meregaon, Thailitola, Joratarai and Kaudikasa was below acceptable level (<1×10−4), suggesting potential health risk for children from these sites could not be overlooked. With high carcinogenic risk value (3.8E−05) and HI index (>1) for arsenic in soils of Kaudikasa, attention should be paid for development of remediation measure.

The function of digestive enzymes on Cu, Zn, and Pb release from soil in in vitro digestion tests

The bioaccessibility of soil heavy metals is the solubility of soil heavy metals in synthetic human digestive juice, which is usually determined using in vitro digestion test. To reveal the effects of digestive enzymes on soil heavy metals bioaccessibility, three representative in vitro digestion tests, Simple Bioaccessibility Extraction Test (SBET), Physiologically Based Extraction Test (PBET), and Simple Gastrointestinal Extraction Test (SGET), were chosen. The bioaccessibility of soil Cu, Zn, and Pb in each method were respectively evaluated with and without digestive enzymes, and the differences were compared. The results showed that the effects of digestive enzymes varied with different methods and elements. Because of digestive enzymes addition, the environmental change from acid gastric phase to neutral intestinal phase of PBET did not result in apparently decrease of the bioaccessibility of soil Cu. However, the solubility of soil Zn and Pb were pH-dependent. For SGET, when digestive enzymes were added, its results reflected more variations resulting from soil and element types. The impacts of digestive enzymes on heavy metal dissolution are mostly seen in the intestinal phase. Therefore, digestive enzyme addition is indispensable to the gastrointestinal digestion methods (PBET and SGET), while the pepsin addition is not important for the methods only comprised of gastric digestion (SBET).

Bioaccessibility and health risk of arsenic and heavy metals (Cd, Co, Cr, Cu, Ni, Pb, Zn and Mn) in TSP and PM2.5 in Nanjing, China

The bioaccessibility and human health risks of As and heavy metals (Cu, Pb, Zn, Ni, Co, Cr, Cd and Mn) in total suspended particulates (TSP) and fine particulate matter (PM2.5) in Nanjing, China were investigated. The average mass concentration ratios of PM2.5 to TSP were 0.61 for Gulou sampling site and 0.50 for Pukou sampling site, respectively. Zn, Pb, Mn and Cu were the most abundant elements among the studied metal(loid)s in both TSP and PM2.5. The results of a simple bioaccessibility extraction test of the studied metal(loid)s varied among elements, with Cd, Zn, Mn, Pb and As showing the higher bioaccessibility. The carcinogenic risks of As, Cd, Co, Cr and Ni in both TSP and PM2.5 via dermal contact and inhalation exposure were within the acceptable level (<1 × 10−4) for both children and adults, but there was potential carcinogenic risk posed by Pb via ingestion to children and adults. The hazard index values for all of the studied elements suggested no non-carcinogenic health risks via ingestion and dermal contact, but a potential non-carcinogenic health risk via inhalation to adults. Values of hazard quotient and hazard index indicated the non-carcinogenic risks from the studied metal(loid)s to children via ingestion, dermal contact and inhalation pathways in Nanjing given the present air quality.

Assessment of oral bioaccessibility of arsenic in playground soil in Madrid (Spain): A three-method comparison and implications for risk assessment

Three methodologies to assess As bioaccessibility were evaluated using playground soil collected from 16 playgrounds in Madrid, Spain: two (Simplified Bioaccessibility Extraction Test: SBET, and hydrochloric acid-extraction: HCl) assess gastric-only bioaccessibility and the third (Physiologically Based Extraction Test: PBET) evaluates mouth–gastric–intestinal bioaccessibility. Aqua regia-extractable (pseudo total) As contents, which are routinely employed in risk assessments, were used as the reference to establish the following percentages of bioaccessibility: SBET – 63.1; HCl – 51.8; PBET – 41.6, the highest values associated with the gastric-only extractions. For Madrid playground soils – characterised by a very uniform, weakly alkaline pH, and low Fe oxide and organic matter contents – the statistical analysis of the results indicates that, in contrast with other studies, the highest percentage of As in the samples was bound to carbonates and/or present as calcium arsenate. As opposed to the As bound to Fe oxides, this As is readily released in the gastric environment as the carbonate matrix is decomposed and calcium arsenate is dissolved, but some of it is subsequently sequestered in unavailable forms as the pH is raised to 5.5 to mimic intestinal conditions. The HCl extraction can be used as a simple and reliable (i.e. low residual standard error) proxy for the more expensive, time consuming, and error-prone PBET methodology. The HCl method would essentially halve the estimate of carcinogenic risk for children playing in Madrid playground soils, providing a more representative value of associated risk than the pseudo-total concentrations used at present.

Bioaccessibility and health risk of arsenic, mercury and other metals in urban street dusts from a mega-city, Nanjing, China

The oral bioaccessibility and the human health risks of As, Hg and other metals (Cu, Pb, Zn, Ni, Co, Cd, Cr, Mn, V and Fe) in urban street dusts from different land use districts in Nanjing (a mega-city), China were investigated. Both the total contents and the oral bioaccessibility estimated by the Simple Bioaccessibility Extraction Test (SBET) of the studied elements varied with street dusts from different land use districts. Cd, Zn, Mn, Pb, Hg and As showed high bioaccessibility. SBET-extractable contents of elements were significantly correlated with their total contents and the dust properties (pH, organic matter contents). The carcinogenic risk probability for As and Cr to children and adults were under the acceptable level (<1 × 10 −4). Hazard Quotient values for single elements and Hazard Index values for all studied elements suggested potential non-carcinogenic health risk to children, but not to adults.

Pediatric Lead Exposure From Imported Indian Spices and Cultural Powders

Significant lead poisoning has been associated with imported nonpaint products. To describe cases of pediatric lead intoxication from imported Indian spices and cultural powders, determine lead concentrations in these products, and predict effects of ingestion on pediatric blood lead levels (BLLs). Cases and case-study information were obtained from patients followed by the Pediatric Environmental Health Center (Children's Hospital Boston). Imported spices (n = 86) and cultural powders (n = 71) were analyzed for lead by using x-ray fluorescence spectroscopy. The simple bioaccessibility extraction test was used to estimate oral bioavailability. The integrated exposure uptake biokinetic model for lead in children was used to predict population-wide geometric mean BLLs and the probability of elevated BLLs (>10 microg/dL). Four cases of pediatric lead poisoning from Indian spices or cultural powders are described. Twenty-two of 86 spices and foodstuff products contained >1 microg/g lead (for these 22 samples, mean: 2.6 microg/g [95% confidence interval: 1.9-3.3]; maximum: 7.6 microg/g). Forty-six of 71 cultural products contained >1 microg/g lead (for 43 of these samples, mean: 8.0 microg/g [95% confidence interval: 5.2-10.8]; maximum: 41.4 microg/g). Three sindoor products contained >47% lead. With a fixed ingestion of 5 microg/day and 50% bioavailability, predicted geometric mean BLLs for children aged 0 to 4 years increased from 3.2 to 4.1 microg/dL, and predicted prevalence of children with a BLL of >10 microg/dL increased more than threefold (0.8%-2.8%). Chronic exposure to spices and cultural powders may cause elevated BLLs. A majority of cultural products contained >1 microg/g lead, and some sindoor contained extremely high bioaccessible lead levels. Clinicians should routinely screen for exposure to these products.

Immobilization of Zn, Cu, and Pb in contaminated soils using phosphate rock and phosphoric acid

Considerable research has been done on P-induced Pb immobilization in Pb-contaminated soils. However, application of P to soils contaminated with multiple heavy metals is limited. The present study examined effectiveness of phosphoric acid (PA) and/or phosphate rock (PR) in immobilizing Pb, Cu, and Zn in two contaminated soils. The effectiveness was evaluated using water extraction, plant uptake, and a simple bioaccessibility extraction test (SBET) mimicking metal uptake in the acidic environment of human stomach. The possible mechanisms for metal immobilization were elucidated using X-ray diffraction, scanning electron microscopy, and chemical speciation program Visual MINTEQ. Compared to the control, all P amendments significantly reduced Pb water solubility, phytoavailability, and bioaccessibility by 72–100%, 15–86%, and 28–92%, respectively. The Pb immobilization was probably attributed to the formation of insoluble Pb phosphate minerals. Phosphorus significantly reduced Cu and Zn water solubility by 31–80% and 40–69%, respectively, presumably due to their sorption on minerals (e.g., calcite and phosphate phases) following CaO addition. However, P had little effect on the Cu and Zn phytoavailability; while the acid extractability of Cu and Zn induced by SBET (pH 2) were even elevated by up to 48% and 40%, respectively, in the H 3PO 4 treatments (PA and PR + PA). Our results indicate that phosphate was effective in reducing Pb availability in terms of water solubility, bioaccessibility, and phytoavailability. Caution should be exercised when H 3PO 4 was amended to the soil co-contaminated with Cu and Zn since the acidic condition of SBET increased Cu and Zn bioaccessibility though their water solubility was reduced.

Inorganic Amendments to Decrease metal Availability in Soils of Recreational Urban Areas: Limitations to their Efficiency and Possible Drawbacks

The use of three inorganic materials as potential immobilizers of metals in soils has been studied by monitoring metal availability by EDTA extraction, the Simple Bioaccessibility Extraction Test (SBET) and extraction with a mixture of organic acids (OA). The SBET test was the most suitable for risk assessment in soils of recreational areas. The materials were a 4A-type zeolite, tri-calcium phosphate and ‘slovakite’, a synthetic sorbent developed for remediation of metal-polluted soils. Adsorption/desorption experiments of metals by the isolated materials showed that all materials caused a strong retention of metals from solutions, with negligible release by dilution. When added to soils of three parks, zeolite and, to a much lesser extent, slovakite caused some increase in soil pH. Despite this increase of pH, zeolite is often the least effective amendment for decreasing metal availability estimated by any method, and even sometimes seems to cause some increase, as well as an increase of soil electrical conductivity. In contrast, slovakite causes a decrease of available metals as estimated by EDTA and SBET, but by SBET the effect seems to be steadily reduced after the first samplings, so that after 300 days the metals extracted by this method are very similar to the data for the blanks. Despite the differences in pseudo-total metal contents, few differences are noticeable among parks. In general, these amendments are scarcely efficient in the case of neutral urban soils like those studied here. Other techniques are needed for controlling and, eventually, decreasing metal pollution hazard in soils of recreational areas.

Availability and Bioaccessibility of Metals in Fine Particles of Some Urban Soils

Metals in urban soils might be transferred to humans via ingestion, dermal contact, or breathing, especially to children due to the "hand to mouth" activity during outdoor activities in playground and recreational areas. This involuntary soil ingestion depends on soil adherence to skin; it is known that the adhesion process tends to exclude particles greater than 50 microm, so the fraction below this diameter would be the most dangerous for health. The aim of this work was to study the "availability", estimated by the EDTA extraction, and "oral bioaccessibility", estimated by the Simple Bioaccessibility Extraction Test (SBET), of several metals in urban soils of two European cities (Sevilla and Torino), as related to the soil particle size distribution. Torino and Sevilla showed different levels of metal contents, availability, and bioaccessibility. In Torino, the finer particles showed metal enrichment of Cu, Zn, and, to a lesser extent, Pb, whereas in Sevilla, all of the studied metals showed this enrichment compared to the whole soils. The whole soil cannot be used as a good general indicator of the bioaccessibility of metals in the finest fractions of the soil. Metal availability was higher in the clay fraction (<2 microm) than in other fractions or whole soils in both cities, and principal component analysis shows that availability is especially due to this fraction. In contrast, Cu and Pb bioaccessibility in the clay fraction seems to be slightly lower than, or comparable to, all of the other fractions and the whole soil. Bioaccessibility of Cr and Ni is clearly greater in the coarser fractions of Sevilla than those of Torino, despite the considerably greater total contents of both metals in the latter city. Adsorbed metal forms are assumed to be preferentially responsible for metals released by EDTA. A different origin is attributed to bioaccessible metal forms. Anthropic influence seems more important in determining metal availability and bioaccessibility in urban soils of both cities than the different geological or industrial characteristics.