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Lead (Pb) contamination continues to contribute to world-wide morbidity in all countries, particularly low- and middle-income countries. Despite its continued widespread adverse effects on global populations, particularly children, accurate prediction of elevated household dust Pb and the potential implications of simple, low-cost household interventions at national and global scales have been lacking. A global dataset (∼40 countries, n = 1951) of community sourced household dust samples were used to predict whether indoor dust was elevated in Pb, expanding on recent work in the United States (U.S.). Binned housing age category alone was a significant (p < 0.01) predictor of elevated dust Pb, but only generated effective predictive accuracy for England and Australia (sensitivity of ∼80%), similar to previous results in the U.S. This likely reflects comparable Pb pollution legacies between these three countries, particularly with residential Pb paint. The heterogeneity associated with Pb pollution at a global scale complicates the predictive accuracy of our model, which is lower for countries outside England, the U.S., and Australia. This is likely due to differing environmental Pb regulations, sources, and the paucity of dust samples available outside of these three countries. In England, the U.S., and Australia, simple, low-cost household intervention strategies such as vacuuming and wet mopping could conservatively save 70 billion USD within a four-year period based on our model. Globally, up to 1.68 trillion USD could be saved with improved predictive modeling and primary intervention to reduce harmful exposure to Pb dust sources., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

In this study, the predominant Pb minerals prior to and after Pb relative bioavailability (Pb-RBA) and Pb bioaccessibility (Pb-BAc) tests were identified using SEM (scanning electron microscopy), XANES (X-ray absorption near edge structure) and XRD (X-ray diffraction). The correlations between in vitro Pb-BAc (using the UBM (Unified BARGE Method) and RBALP (Relative BioAccessibility Leaching Procedure) models) and in vivo Pb-RBA (using endpoints of kidney and liver in an mice model) were determined. The results demonstrated that both RBALP and UBM (gastric phase) reliably indicate Pb-RBA (Pb-RBA). However, raising the solid:liquid ratio of the gastric phase of UBM is necessary to determine Pb-BAc if the soils contain total Pb >10,000 mg/kg. The comparison of Pb minerals prior to and after in vitro extractions demonstrated that the relatively soluble forms of Pb (PbSO 4 , PbO 2 and MgO Pb) start to dissolve than other forms of Pb minerals, suggesting there was no difference in Pb 2+ release between chemical-based (RBALP) and physiologically-based (UBM) models. The identification of the Pb minerals of Pb 5 (PO 4 ) 3 Cl and organically-complexed Pb in mice excreta demonstrated that a portion of Pb 2+ combined with food and humic acid to generate organically-complexed Pb in mice excreta, and that Pb 5 (PO 4 ) 3 Cl is not bioavailable., Competing Interests: Declaration of Competing Interest None., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Whilst advanced electrochemical oxidation can break down per- and polyfluoroalkyl substances (PFAS), the requirement for expensive electrode materials usually prevents its widespread application. Here we use an industrial material of lead peroxide (PbO 2 ) from a lead-acid battery to break down PFAS including perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS), and 1H,1H,2H,2H-perfluorooctanesulfonic acid (6:2 FTS). By optimising the PbO 2 panel (activating and doping) and working conditions including supporting electrolyte (1 L 10 mM Na 2 SO 4 ), initial concentration (10 μM), temperature (room temperature), current density (5 A for a 10 cm × 10 cm PbO 2 panel) etc., we successfully remove > 99% PFAS (individual PFAS monitored via HPLC-MS) whilst mineralising ∼59% PFOA (defluorination, F - released and monitored via F-ISE, fluoride-ion selective electrode). By studying the pseudo-first-order kinetics of the PFAS breakdown (0.0028-0.007 min -1 ) and defluorination (0.84-5.9 × 10 -8 min -1 ), we assign the difference to the adsorption of PFAS on the PbO 2 panel and the appearance of intermediates before the full defluorination. The leaked HF gas (∼10 -5  M, collected using 0.25 L 0.1 M NaOH) and Pb 2+ (∼12 μM, or ∼ 2.5 ppm) are also confirmed. This study employs an economic industrial material, highlights the contribution of adsorption towards the PFAS removal and breakdown, and identifies the possible leakage of secondary contaminants., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Lead (Pb) contaminated soil is of particular concern for infants and children due to their susceptibility to exposure, fast metabolic rates and rapidly developing neuronal systems. Determining the bioaccessibility of Pb in soils is critical in human health risk assessments, which can vary due to different soil properties and sources of Pb contamination. In this study, the potential relationships between soil properties and Pb bioaccessibility from various Pb sources including Pb contamination from mining (specifically, Broken Hill), three shooting ranges, a smelter and two industry sites (pottery and battery), were investigated using the Relative Bioavailability Leaching Procedure (RBALP). We found the following: (1) CEC, TOC, sand and silt content, and total Pb were significantly different (p < 0.05) between the two particle size fractions of < 2 mm and < 250 μm; (2) EC, CEC and total Pb were significantly correlated to Pb bioaccessibility (p < 0.05); and (3) soil analyses based on source of Pb demonstrated a strongly significant relationship between Pb bioaccessibility and soil properties (CEC, EC, clay content and total Pb) for mining soils from Broken Hill (r 2  = 0.86, p < 0.05, n = 18). These results demonstrated the influences of Pb contamination sources, soil properties and particle size fractions on Pb bioaccessibility as well as the prediction of Pb bioaccessibility using soil properties. The findings documented here will help in developing a predictive tool for human health risk assessment and the remediation of Pb contaminated soils., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

A palygorskite-iron oxide nanocomposite (Pal-IO) was synthesized in situ by embedding magnetite into the palygorskite structure through co-precipitation method. The physico-chemical characteristics of Pal-IO and their pristine components were examined through various spectroscopic and micro-analytical techniques. Batch adsorption experiments were conducted to evaluate the performance of Pal-IO in removing Pb(II) from aqueous solution. The surface morphology, magnetic recyclability and adsorption efficiency of regenerated Pal-IO using desorbing agents HCl (Pal-IO-HCl) and ethylenediaminetetraacetic acid disodium salt (EDTA-Na 2 ) (Pal-IO-EDTA) were compared. The nanocomposite showed a superparamagnetic property (magnetic susceptibility: 20.2 emu g -1 ) with higher specific surface area (99.8 m 2  g -1 ) than the pristine palygorskite (49.4 m 2  g -1 ) and iron oxide (72.6 m 2  g -1 ). Pal-IO showed a maximum Pb(II) adsorption capacity of 26.6 mg g -1 (experimental condition: 5 g L -1 adsorbent loading, 150 agitations min -1 , initial Pb(II) concentration from 20 to 500 mg L -1 , at 25 °C) with easy separation of the spent adsorbent. The adsorption data best fitted to the Langmuir isotherm model (R 2  = 0.9995) and pseudo-second order kinetic model (R 2  = 0.9945). Pb(II) desorption using EDTA as the complexing agent produced no disaggregation of Pal-IO crystal bundles, and was able to preserve the composite's magnetic recyclability. Pal-IO-EDTA exhibited almost 64% removal capacity after three cycles of regeneration and preserved the nanocomposite's structural integrity and magnetic properties (15.6 emu g -1 ). The nanocomposite holds advantages as a sustainable material (easily separable and recyclable) for potential application in purifying heavy metal contaminated wastewaters., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Lead (Pb) is a widespread heavy metal which is harmful to human health, especially to young children. To provide a human health risk assessment that is more relevant to real conditions, Pb bioavailability in soils is increasingly employed in the assessment procedure. Both in vivo and in vitro measurements for lead bioavailability are available. In vivo models are time- consuming and expensive, while in vitro models are rapid, economic, reproducible, and reliable while involving more uncertainties. Uncertainties in various measurements create difficulties in accurately predicting Pb bioavailability, resulting in the unnecessary remediation of sites. In this critical review, we utilised available data from in vivo and in vitro studies to identify the key parameters influencing the in vitro measurements, and presented uncertainties existing in Pb bioavailability measurements. Soil type, properties and metal content are reported to influence lead bioavailability; however, the differences in methods for assessing bioavailability and the differences in Pb source limit one's ability to conduct statistical analyses on influences of soil factors on Pb bioavailability. The information provided in the review is fundamentally useful for the measurement of bioavailability and risk assessment practices., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Lead (Pb) bioaccessibility measurements have been the subject of much research in recent years, given the desire to develop a cost-effective and reliable alternative method to estimate its bioavailability from soils and dusts. This study investigates the relationship between Pb bioaccessibility estimated using the Relative Bioavailability Leaching Procedure (RBALP) and solid phase speciation of Pb using mining impacted soils and associated dusts. Solid phase speciation was conducted prior to and after RBALP extractions. The average Pb concentrations were 59, 67, and 385 mg/kg for top soil, sub-soil, and house dust samples, respectively. Lead bioaccessibility in selected top soils and dusts ranged from 16.7 to 57.3% and 8.9 to 98.1%, respectively. Solid phase speciation of Pb in <250 μm residues prior to and after RBALP extraction revealed 83% decrease in Pb bound to carbonate fraction after RBALP extraction. This accounts for 69% of RBALP-extractable Pb. Besides contribution from carbonate bound Pb, 76.6 and 53.2% of Pb bound to Mn oxyhydroxides and amorphous Fe and Al oxyhydroxides contributed to bioaccessible Pb, respectively. However, Pb bound to Mn oxyhydroxides and amorphous Fe and Al oxyhydroxides account for only 13.8 and 20.0% of total RBALP-extractable Pb, respectively. Both non-specifically bound and easily exchangeable fractions and strongly bound inner-sphere complexes were also part of bioaccessible Pb. The present study demonstrates that bioaccessible Pb is released from both soil solution phase Pb as well as that from all soil solid phase with the most contribution being from Pb bound to carbonate mineral phase.

Regulatory assessment of lead (Pb) in contaminated soils is still expressed primarily as total Pb concentrations in soil. In this study, we estimated effective concentrations (ECx) of Pb to Cucumis sativa L. (cucumber) focusing primarily on pore-water Pb data from 10 different soils after 12 weeks ageing. Phytotoxicity expressed in terms of Pb(2+) was observed to occur in the nanomolar range in neutral to alkaline soils (EC50 values 90 to 853 nM) and micromolar levels for acidic soils (EC50 values 7.35 to 9.66 μM). Internal Pb concentrations relating to toxicity (PT50) in roots and shoots also decreased with increasing pore-water pH (R (2) = 0.52 to 0.53). From a series of dose-response studies, we developed transfer functions predicting Pb uptake in C. sativa and we validated these functions with long-term Pb contaminated soils. The significant independent parameters were pore-water Pb(2+) and dissolved Pb plus dissolved organic carbon (DOC). The observed RMSE for the Pb-DOC model and Pb(2+) were 2.6 and 8.8, respectively. The Pb-DOC model tended to under-predict Pb, whilst Pb(2+) tended to over-predict accumulation despite reasonable RMSE values. Further validation is needed in soils with higher pore-water Pb solubility.

The bioaccessibility of lead (Pb) in contaminated soils has been extensively studied, including the influence of soil properties on Pb bioaccessibility. However, little is known about the effects of other metals/metalloid, such as arsenic (As), cadmium (Cd) on the bioaccessibility of Pb, i.e. whether As or Cd could increase or decrease the solubility of Pb in human gastrointestinal tract when Pb-contaminated soil and As-contaminated (or Cd-contaminated) soil are ingested simultaneously. Furthermore, it is far from clear that if soil property could make a difference to these effects. In this study, seven types of soils were collected in Australia and spiked with As, Cd or Pb. Gastric bioaccessibility of Pb ranged from 44 ± 0.9% to 100 ± 6.7% whilst intestinal bioaccessibility dropped to 1 ± 0.2% to 36 ± 1.7%. Statistical analysis shows total Pb in soil was the most significant controller for bioaccessible Pb. Effects of As and Cd on the bioaccessibility of Pb in simulated human digestive system were studied by mixing As-spiked soil (or Cd-spiked soil) with Pb-spiked soil of the same type during bioaccessibility test. Results reveal that neither As nor Cd had impact on Pb bioaccessibility, which indicates when As, Cd and Pb aged in soils separately, they may behave independently in the bioaccessibility measuring system. This finding can be part of evidence to assume additive effect when it comes to estimate the bioaccessibility of mixtures of independently-aged As and Pb (or Cd and Pb) in soils., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Defining the precise clean-up goals for lead (Pb) contaminated sites requires site-specific information on relative bioavailability data (RBA). While in vivo measurement is reliable but resource insensitive, in vitro approaches promise to provide high-throughput RBA predictions. One challenge on using in vitro bioaccessibility (BAc) to predict in vivo RBA is how to minimize the heterogeneities associated with in vivo-in vitro correlations (IVIVCs) stemming from various biomarkers (kidney, blood, liver, urinary and femur), in vitro approaches and studies. In this study, 252 paired RBA-BAc data were retrieved from 9 publications, and then a Bayesian hierarchical model was implemented to address these random effects. A generic linear model (RBA (%)=(0.87±0.16)×BAc+(4.70±2.47)) of the IVIVCs was identified. While the differences of the IVIVCs among the in vitro approaches were significant, the differences among biomarkers were relatively small. The established IVIVCs were then applied to predict Pb RBA of which an overall Pb RBA estimation was 0.49±0.25. In particular the RBA in the residential land was the highest (0.58±0.19), followed by house dust (0.46±0.20) and mining/smelting soils (0.45±0.31). This is a new attempt to: firstly, use a meta-analysis to correlate Pb RBA and BAc; and secondly, estimate Pb RBA in relation to soil types., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Bioaccessibility to assess potential risks resulting from exposure to Pb-contaminated soils is commonly estimated using various in vitro methods. However, existing in vitro methods yield different results depending on the composition of the extractant as well as the contaminated soils. For this reason, the relationships between the five commonly used in vitro methods, the Relative Bioavailability Leaching Procedure (RBALP), the unified BioAccessibility Research Group Europe (BARGE) method (UBM), the Solubility Bioaccessibility Research Consortium assay (SBRC), a Physiologically Based Extraction Test (PBET), and the in vitro Digestion Model (RIVM) were quantified statistically using 10 soils from long-term Pb-contaminated mining and smelter sites located in Western Australia and South Australia. For all 10 soils, the measured Pb bioaccessibility regarding all in vitro methods varied from 1.9 to 106% for gastric phase, which is higher than that for intestinal phase: 0.2 ∼ 78.6%. The variations in Pb bioaccessibility depend on the in vitro models being used, suggesting that the method chosen for bioaccessibility assessment must be validated against in vivo studies prior to use for predicting risk. Regression studies between RBALP and SRBC, RBALP and RIVM (0.06) (0.06 g of soil in each tube, S:L ratios for gastric phase and intestinal phase are 1:375 and 1:958, respectively) showed that Pb bioaccessibility based on the three methods were comparable. Meanwhile, the slopes between RBALP and UBM, RBALP and RIVM (0.6) (0.6 g soil in each tube, S:L ratios for gastric phase and intestinal phase are 1:37.5 and 1:96, respectively) were 1.21 and 1.02, respectively. The findings presented in this study could help standardize in vitro bioaccessibility measurements and provide a scientific basis for further relating Pb bioavailability and soil properties.

The stabilisation of Pb in the soil by phosphate is influenced by environmental conditions and physicochemical properties of the soils to which it is applied. Stabilisation of Pb by phosphate was examined in four soils under different environmental conditions. The effect of soil moisture and temperature on stabilisation of Pb by phosphate was examined by measurement of water extractable and bioaccessible Pb, sequential fractionation and X-ray absorption spectroscopy. The addition of humic acid, ammonium nitrate and chloride was also examined for inhibition or improvement of Pb stability with phosphate treatment. The effect of moisture level varied between soils. In soil MB and DA a soil moisture level of 50% water holding capacity was sufficient to maximise stabilisation of Pb, but in soil TV and PE reduction in bioaccessible Pb was inhibited at this moisture level. Providing moisture at twice the soil water holding capacity did not enhance the effect of phosphate on Pb stabilisation. The difference of Pb stability as a result of incubating phosphate treated soils at 18 °C and 37 °C was relatively small. However wet-dry cycles decreased the effectiveness of phosphate treatment. The reduction in bioaccessible Pb obtained was between 20 and 40% with the most optimal treatment conditions. The reduction in water extractable Pb by phosphate was substantial regardless of incubation conditions and the effect of different temperature and soil moisture regimes was not significant. Selective sequential extraction showed phosphate treatment converted Pb in fraction 1 (exchangeable, acid and water soluble) to fraction 2 (reducible). There were small difference in fraction 4 (residual) Pb and fraction 1 as a result of treatment conditions. X-ray absorption spectroscopy of stabilised PE soil revealed small differences in Pb speciation under varying soil moisture and temperature treatments. The addition of humic acid and chloride produced the greatest effect on Pb speciation in phosphate treated soils., (Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.)

To reduce cost and enhance reactivity, bimetallic Fe/Pd nanoparticles (NPs) were firstly synthesized using grape leaf aqueous extract to remove Orange II. Green synthesized bimetallic Fe/Pd NPs (98.0%) demonstrated a far higher ability to remove Orange II in 12h compared to Fe NPs (16.0%). Meanwhile, all precursors, e.g., grape leaf extract, Fe(2+) and Pd(2+), had no obvious effect on removing Orange II since less than 2.0% was removed. Kinetics study revealed that the removal rate fitted well to the pseudo-first-order reduction and pseudo-second-order adsorption model, meaning that removing Orange II via Fe/Pd NPs involved both adsorption and catalytic reduction. The remarkable stability of Fe/Pd NPs showed the potential application for removing azo dyes. Furthermore, Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR) confirmed the changes in Fe/Pd NPs before and after reaction with Orange II. High Performance Liquid Chromatography-Mass Spectrum (HPLC-MS) identified the degraded products in the removal of Orange II, and finally a removal mechanism was proposed. This one-step strategy using grape leaf aqueous extract to synthesize Fe/Pd NPs is simple, cost-effective and environmentally benign, making possible the large-scale production of Fe/Pd NPs for field remediation., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Lead (Pb) poisoning in children is a major public health catastrophe worldwide. This report summarises both exposure pathways and blood Pb levels in children below 7 years of age and adults (above 18 years) from the Adudu community living near a lead-zinc mine in Nasawara, Nigeria. The average and median blood Pb levels in children and adults were 2.1 and 1.3 μg/dL, 3.1 and 1.8 μg/dL, respectively. However, Pb in 14% of adults' blood exceeded 5 μg/dL, which is the recommended threshold blood Pb concentration in adults as established by the Centers for Disease Control and Prevention (CDC). Furthermore 68% of adults' blood exceeded blood Pb action level of 2 μg/dL. For children, 11.4% and 31% of the blood samples exceeded 5 μg/dL and 2 μg/dL, respectively, while no safe blood Pb level in children has been recommended. In Nasawara, a significant difference (p<0.05) was observed between the various age groups in children with 2-4 years old having the highest levels and 6 year old children having the lowest Pb levels. Although this study did not detect elevated levels of Pb in children's blood in regions such as Zamfara, Nigeria and Kabwe, Zambia, a high percentage of samples exceeded 2 μg/dL. Soils, floor dusts, water and crops also reveal that Pb contamination in the study area could potentially be the major cause of blood Pb in the community exposed to mining. This study also observed a significant correlation between water Pb levels of adults and blood Pb levels, suggesting that water is the major exposure pathway. This analysis highlights the need to properly manage mining activities so that the health of communities living in the vicinity of a Pb-Zn mine is not compromised., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Complementary medicines have associated risks which include toxic heavy metal(loid) and pesticide contamination. The objective of this study was to examine the speciation and bioavailability of lead (Pb) in selected complementary medicines. Six herbal and six ayurvedic medicines were analysed for: (i) total heavy metal(loid) contents including arsenic (As), cadmium (Cd), Pb and mercury (Hg); (ii) speciation of Pb using sequential fractionation and extended x-ray absorption fine structure (EXAFS) techniques; and (iii) bioavailability of Pb using a physiologically-based in vitro extraction test (PBET). The daily intake of Pb through the uptake of these medicines was compared with the safety guidelines for Pb. The results indicated that generally ayurvedic medicines contained higher levels of heavy metal(loid)s than herbal medicines with the amount of Pb much higher than the other metal(loid)s. Sequential fractionation indicated that while organic-bound Pb species dominated the herbal medicines, inorganic-bound Pb species dominated the ayurvedic medicines. EXAFS data indicated the presence of various Pb species in ayurvedic medicines. This implies that Pb is derived from plant uptake and inorganic mineral input in herbal and ayurvedic medicines, respectively. Bioavailability of Pb was higher in ayurvedic than herbal medicines, indicating that Pb added as a mineral therapeutic input is more bioavailable than that derived from plant uptake. There was a positive relationship between soluble Pb fraction and bioavailability indicating that solubility is an important factor controlling bioavailability. The daily intake values for Pb as estimated by total and bioavailable metal(loid) contents are likely to exceed the safe threshold level in certain ayurvedic medicines. This research demonstrated that Pb toxicity is likely to result from the regular intake of these medicines which requires further investigation., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Three Australian shooting range soils were treated with phosphate and magnesium oxide, or a combination of both to chemically stabilize Pb. Lead speciation was determined after 1 month ageing by X-ray absorption spectroscopy combined with linear combination fitting in control and treated soils. The predominant Pb species in untreated soils were iron oxide bound Pb, humic acid bound Pb and the mineral litharge. Treatment with phosphate resulted in substantial pyromorphite formation in two of the soils (TV and PE), accounting for up to 38% of Pb species present, despite the addition of excess phosphate. In MgO treated soils only, up to 43% of Pb was associated with MgO. Litharge and Pb hydroxide also formed as a result of MgO addition in the soils. Application of MgO after P treatment increased hydroxypyromorphite/pyromorphite formation relative to soils teated with phosphate only. X-ray diffraction and Scanning electron microscopy revealed PbO precipitate on the surface of MgO. Soil pH, (5.3-9.3) was an important parameter, as was the solubility of existing Pb species. The use of direct means of determination of the stabilisation of metals such as by X-ray absorption spectroscopy is desirable, particularly in relation to understanding long term stability of the immobilised contaminants., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Soil plays a significant role in controlling the potential bioavailability of contaminants in the environment. In this study, eleven soils were used to investigate the relationship between soil properties and relative bioavailability (RB) of lead (Pb). To minimise the effect of source of Pb on in vivo bioavailability, uncontaminated study soils were spiked with 1500 mg Pb/kg soil and aged for 10-12 months prior to investigating the relationships between soil properties and in vivo RB of Pb using swine model. The biological responses to oral administration of Pb in aqueous phase or as spiked soils were compared by applying a two-compartment pharmacokinetic model to blood Pb concentration. The study revealed that RB of Pb from aged soils ranged from 30±9% to 83±7%. The very different RB of Pb in these soils was attributed to variations in the soils' physico-chemical properties. This was established using sorption studies showing: firstly, Freundlich partition coefficients that ranged from 21 to 234; and secondly, a strongly significant (R(2)=0.94, P<0.001) exponential relationship between RB and Freundlich partition coefficient (Kd). This simple exponential model can be used to predict relative bioavailability of Pb in contaminated soils. To the best of our knowledge, this is the first such model derived using sorption partition coefficient to predict the relative bioavailability of Pb., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Aging is a time-dependent process that causes metal bioavailability to decrease with time. The current study investigated the bioavailability change of Pb in four contrasting soils over a time period until the Pb relative bioavailability (RB) levels achieved a steady state to assess the extent of the following: firstly, bioavailability change in each soil and secondly, correlation of these changes with the soil properties. Relative bioavailability of soils spiked with 1500 mg Pb/kg were measured in swine that were fed these soils, throughout an aging period (56 days) to investigate relationships between soil properties and in vivo bioavailability of Pb. Spiked soils were used to minimize the effect of varying sources of Pb on RB. The RB of Pb in GTA, IWA, and MLA decreased from their initial Pb RB values until a steady state RB of 34, 45, and 59 % was reached, respectively, by the 56th day. In contrast, however, to these RB decreases, NTA soil indicated no change in RB over the whole aging period of the experiment. The lack of change in RB in the NTA soil over time was attributed to it achieving a steady state RB within a very short time due to its comparatively high sorptive capacity (K d = 112).

This study aims to examine the effectiveness of amendments for risk-based land management of shooting range soils and to explore the effectiveness of amendments applied to sites with differing soil physiochemical parameters. A series of amendments with differing mechanisms for stabilisation were applied to four shooting range soils and aged for 1 year. Chemical stabilisation was monitored by pore water extraction, toxicity characteristic leaching procedure (TCLP) and the physiologically based extraction test (PBET) over 1 year. The performance of amendments when applied in conditions reflecting field application did not match the performance in the batch studies. Pore water-extractable metals were not greatly affected by amendment addition. TCLP-extractable Pb was reduced significantly by amendments, particularly lime and magnesium oxide. Antimony leaching was reduced by red mud but mobilised by some of the other amendments. Bioaccessible Pb measured by PBET shows that bioaccessible Pb increased with time after an initial decrease due to the presence of metallic fragments in the soil. Amendments were able to reduce bioaccessible Pb by up to 50 %. Bioaccessible Sb was not readily reduced by soil amendments. Soil amendments were not equally effective across the four soils.

In this study, lead (Pb) bioaccessibility was assessed in peri-urban contaminated soils using a variety of established in vitro assays. Bioaccessibility data was then used to predict Pb relative bioavailability (RBA) using published in vivo-in vitro regression models in order to compare calculated estimates and measured values. Lead bioaccessibility varied depending on the in vitro methodology employed with the relative bioavailability leaching procedure (RBALP) and in vitro gastrointestinal (IVG) assays providing more conservative Pb bioaccessibility values compared to those determined using PBET, UBM and Rel-SBRC-I assays. When Pb RBA was calculated, predicted values using PBET-G and UBM-G data were similar to measured Pb RBA values. However, Pb RBA was over-estimated by 1.6-5.5- and 2.6-6.6-fold when data and regression models from RBALP and IVG-G assays were employed.

Purpose: This study aims to examine whether addition of immobilising agents to a sandy, alkaline (pH = 8.1) soil, which had been contaminated with Pb and Zn by airborne particles from a Pb/Zn smelter, would substantially reduce metal bioavailability., Methods: The effectiveness of five waste materials (blast furnace (BF) slag, alum water treatment (WT) sludge, red mud, sugar mill mud and green waste compost) as metal immobilising agents was evaluated by incubating them with a contaminated soil for a period of 12 months at rates of 5% and 10% (w/w), after which, Rhodes grass was grown in the soils in a greenhouse study., Results: Additions of WT sludge, BF slag and red mud reduced CaCl(2), CH(3)COOH, HCl and EDTA-extractable Zn but compost and mill mud had no appreciable immobilising effects. Additions of all amendments reduced levels of CaCl(2), CH(3)COOH and HCl-extractable Pb although concentrations of EDTA-extractable Pb remained unchanged. A sequential extraction procedure showed that additions of mill mud and compost increased the percentage of total Pb and Zn present in the oxidisable fraction whilst additions of the other materials increased the percentage present in the residual fraction. Rhodes grass yields were promoted greatly by additions of red mud, compost and particularly mill mud, and yields were negatively correlated with tissue Pb concentrations and extractable Pb., Conclusions: Red mud was the most effective material for lowering extractable Pb and Zn levels simultaneously while mill mud and compost were notably effective for Pb. A field evaluation in the study area is justified.

Long-term lead (Pb) contaminated soils from two lead-zinc smelters and a shooting range, along with freshly spiked control soil, were studied by means of chemical, biological or a physiological method to examine the effect of ageing on Pb bioavailability. The freshly Pb spiked control soil was subjected to an earthworm toxicity test to observe the avoidance and mortality response of the earthworms. Meanwhile, an extractable fraction of Pb on the spiked soil as a result of ageing was examined and further compared with physiologically based in vitro bioaccessibility extraction tests. Their differences in lethal concentration, LC(50), to the earthworm population from spiked soils varied substantially as a function of soil pH. The strong effect of ageing on toxicity was also reflected in the extractability of Pb which was far greater in acidic soil, labelled AC, compared to the alkaline soil, labelled BC. This demonstrates that the bioavailable fraction causing toxicity to earthworms was achieved at a much lower total Pb content for acidic soils relative to alkaline soils. Moreover, the effect of ageing also exhibits that a marked decline in bioavailable Pb results in lowering toxicity. Significant amounts of weight loss in earthworms during an acute toxicity test in long-term contaminated soils at a relatively low Pb concentration suggested that other metal or combined metal toxicity may also play a significant role. This study demonstrates that the soil characteristics and ageing period greatly influence the bioavailable fraction of Pb which is related to the bioreceptor., (Copyright © 2011 Elsevier Inc. All rights reserved.)

Lead is a highly toxic element and forms stable compounds with phosphate, which is commonly used to immobilize Pb in soils. However, few studies have monitored the long-term stability of immobilized Pb, which is a critical factor in determining the effectiveness of the in situ stabilization technique. Both soluble and insoluble phosphate compounds were tested for Pb immobilization, and its subsequent mobility and bioavailability in a contaminated soil from a shooting range. Adding tricalcium phosphate, hydroxyapatite, rock phosphate and potassium dihydrogen phosphate reduced the concentration of ammonium-nitrate-extractable Pb in the contaminated soil by 78.6%, 48.3%, 40.5% and 80.1%, respectively. Insoluble phosphate amendments significantly reduced leached Pb concentration from the column while soluble potassium dihydrogen phosphate compound increased P and Pb concentrations in the leachate. Rock phosphate reduced Pb accumulation in earthworms by 21.9% compared to earthworms in the control treatment. The long-term stability of immobilized Pb was evaluated after 2 years' incubation of the contaminated soil with rock phosphate or soluble phosphate compounds. Bioavailable Pb concentration as measured by simple bioavailability extraction test (SBET) showed the long-term stability of immobilized Pb by P amendments. Therefore, Pb immobilization using phosphate compounds is an effective remediation technique for Pb-contaminated soils.

Lead (Pb) bioaccessibility was assessed using 2 in vitro methods in 12 Pb-contaminated soils and compared to relative Pb bioavailability using an in vivo mouse model. In vitro Pb bioaccessibility, determined using the intestinal phase of the Solubility Bioaccessibility Research Consortium (SBRC) assay, strongly correlated with in vivo relative Pb bioavailability (R(2) = 0.88) following adjustment of Pb dissolution in the intestinal phase with the solubility of Pb acetate at pH 6.5 (i.e., relative Pb bioaccessibility). A strong correlation (R(2) = 0.78) was also observed for the relative bioaccessibility leaching procedure (RBALP), although the method overpredicted in vivo relative Pb bioavailability for soils where values were <40%. Statistical analysis of fit results from X-ray absorption near-edge structure (XANES) data for selected soils (n = 3) showed that Pb was strongly associated with Fe oxyhydroxide minerals or the soil organic fraction prior to in vitro analysis. XANES analysis of Pb speciation during the in vitro procedure demonstrated that Pb associated with Fe minerals and the organic fraction was predominantly solubilized in the gastric phase. However, during the intestinal phase of the in vitro procedure, Pb was strongly associated with formation of ferrihydrite which precipitated due to the pH (6.5) of the SBRC intestinal phase. Soils where Fe dissolution was limited had markedly higher concentrations of Pb in solution and hence exhibited greater relative bioavailability in the mouse model. This data suggests that coexistence of Fe in the intestinal phase plays an important role in reducing Pb bioaccessibility and relative bioavailability.

The use of nanoscale zero-valent iron (nZVI) to remediate contaminated groundwater is limited due to its lack of durability and mechanical strength. To address this issue, 20% (w/w) nZVI was loaded onto kaolinite as a support material (K-nZVI). More than 96% of Pb(2+) was removed from aqueous solution using K-nZVI at an initial condition of 500 mg/L Pb(2+) within 30 min under the conditions of 10 g/L of K-nZVI, pH 5.10 and a temperature of 30 °C. To understand the mechanism of removal of Pb(2+), various techniques were implemented to characterize K-nZVI. Scanning electron microscopy (SEM) indicated that K-nZVI had a suitable dispersive state with a lower aggregation, where the mean specific surface area and average particle size as determined by the BET-N(2) method and X-ray diffraction (XRD), were 26.11 m(2)/g and 44.3 nm, respectively. The results obtained from XRD, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) indicated that a small number of iron oxides formed on the surface of K-nZVI, suggesting that free Pb(2+) was adsorbed onto K-nZVI and subsequently reduced to Pb(0)., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

This paper examines the potential value of phosphate solubilizing bacteria (Enterobacter cloacae) in the dissolution of rock phosphate (RP) and subsequent immobilization of lead (Pb) in both bacterial growth medium and soils. Enterobacter sp. showed resistance to Pb and the bacterium solubilized 17.5% of RP in the growth medium. Enterobacter sp. did not enhance Pb immobilization in solution because of acidification of bacterial medium, thereby inhibiting the formation of P-induced Pb precipitation. However, in the case of soil, Enterobacter sp. increased Pb immobilization by 6.98, 25.6 and 32.0% with the RP level of 200, 800 and 1600 mg P/kg, respectively. The immobilization of Pb in Pb-spiked soils was attributed to pyromorphite formation as indicated by XRD analysis. Inoculation of phosphate solubilizing bacteria with RP in soil can be used as an alternative technique to soluble P compounds which can cause eutrophication of surface water., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

Lead (Pb) bioaccessibility was assessed in a range of peri-urban soils (n=31) with differing sources of Pb contamination, including shooting range soils, and soils affected by incinerator, historical fill, mining/smelting, and gasworks activities. A gossan soil sample was also included. Lead bioaccessibility was determined using both gastric and intestinal phases of the SBRC in vitro assay and in vitro data was then incorporated into in vivo-in vitro regression equations to calculate Pb relative bioavailability. Lead bioaccessibility ranged from 26.8-105.2% to 5.5-102.6% for gastric and intestinal phase extractions respectively. Generally, Pb bioaccessibility was highest in the shooting range soils and lowest in the gossan soil. Predictions of relative Pb bioavailability derived from in vitro data were comparable for shooting ranges soils, but highly variable for the other soils examined. For incinerator, historical fill, gasworks and gossan soils, incorporating in vitro gastric data into the in vivo-in vitro regression equation resulting in more conservative Pb relative bioavailability values than those derived using the intestinal in vitro data., (Copyright © 2010 Elsevier B.V. All rights reserved.)

Lead (Pb), a highly toxic heavy metal forms stable compounds with phosphate (P). The potential of phosphate solubilizing bacteria (PSB) to immobilize Pb by enhancing solubilization of insoluble P compounds was tested in this research. Eighteen different PSB strains isolated from P amended and Pb contaminated soils were screened for their efficiency in P solubilization. The PSB isolated from P amended soils solubilized 217-479 mg/L of P while the PSB from Pb contaminated soil solubilized 31-293 mg/L of P. Stepwise multiple regression analysis and P solubility kinetics indicated that the major mechanism of P solubilization by PSB is the pH reduction through the release of organic acids. From the isolated bacteria, two PSB were chosen for Pb immobilization and these bacteria were identified as Pantoea sp. and Enterobacter sp., respectively. The PSB significantly increased P solubilization by 25.0% and 49.9% in the case of Pantoea sp., and 63.3% and 88.6% in the case of Enterobacter sp. for 200 and 800 mg/kg of rock phosphate (RP) addition, respectively, thereby enhancing the immobilization of Pb by 8.25-13.7% in the case of Pantoea sp. and 14.7-26.4% in the case of Enterobacter sp. The ability of PSB to solubilize P, promote plant growth, and immobilize Pb can be used for phytostabilization of Pb contaminated soils., (Copyright © 2010 Elsevier B.V. All rights reserved.)

The mobility and bioavailability of lead (Pb) in soils can be mitigated by its immobilization using both soluble and insoluble phosphate (P) compounds. The effectiveness of insoluble P sources on Pb immobilization depends on their rate of dissolution which can be enhanced by phosphate solubilizing bacteria (PSB). In this study, the effect of soluble (potassium dihydrogen phosphate) and insoluble (rock phosphate in the presence and absence of PSB) P compounds on the immobilization of Pb, and leaching of Pb and P was examined using both naturally contaminated (SR soil: NH₄NO₃ extractable Pb: 28.7 mg/kg, pH: 5.88, organic matter: 0.7%) and Pb spiked (AH soil: NH(4)NO(3) extractable Pb: 42.7 mg/kg, pH: 5.23, organic matter: 10.9%) soils. Phosphate compounds were added at the rate of 200 mg P/kg and 800 mg P/kg for SR and AH soils, respectively. Soluble P treatment immobilized 80% and 57% of Pb in SR and AH soils, respectively. Insoluble rock phosphate immobilized 40% and 9% of Pb without PSB, and 60% and 17% with PSB in SR and AH soils, respectively. Lead leaching was the lowest when soils were amended with rock phosphate in the presence of PSB, which reduced Pb leaching by 36% for SR soil and 18% for AH soil compared to the control. The leaching of Pb increased when the soils were amended with soluble P because soluble P treatment increased dissolved organic carbon (DOC) concentration of soil, thereby increasing Pb mobility. Soluble P treatment significantly increased P leaching and 9% of total added P was leached from low P retaining AH soil. The optimum level of P amendment is a critical issue when soluble P is used as a Pb immobilizing agent because of eutrophication resulting from excessive P leaching to surface and ground water. While the soluble P compound was effective in the immobilization of Pb, it resulted in P leaching which increased with increasing levels of P addition. However, rock phosphate amendment with PSB achieved the immobilization of Pb with a minimum effect on both Pb and P leaching., (Copyright © 2010 Elsevier B.V. All rights reserved.)

Lead (Pb) is a wide spread contaminant in the terrestrial landscape. It is highly detrimental to plant and animal life and possesses no known biologic function. Yet there is a paucity of reliable information available on the response of Australian and other plant species to Pb exposure at phytotoxic doses. In this study, the response of three Australian native grass species and two tree species to Pb in nutrient solution culture was investigated. Plants were exposed to average Pb concentrations ranging from 0.020 to 15.2 microM. The plant species included Acacia decurrens, Austrodanthonia richardsonii, Bothriochloa macra, Eucalyptus camaldulensis, and Dichanthium sericeum. Few foliar symptoms were evident in any plant species, although some discolouration in young leaves of E. camaldulensis was evident from 1 microM, and B. macra showed pronounced reddening at the highest treatments. The most tolerant plant species studied based on solution EC(50, roots) (microM) results was B. macra (7.0 +/- 0.2), followed by A. decurrens (3.9 +/- 0.2), D. sericeum (2.9 +/- 0.3), E. camaldulensis (1.1 +/- 0.3), and A. richardsonii (0.4). A hazardous concentration value (HC(5)) (n = 9) for soil solution was estimated to be 0.16 microM. A. richardsonii was highly sensitive to Pb and possessed little ability to restrict Pb translocation to its shoots. B. macra was able to tolerate high root (3924 mg kg(-1)) and shoot (743.0 mg kg(-1)) Pb concentrations. A. decurrens excluded Pb from it shoots. The high tolerance of A. decurrens to Pb and limited translocation to shoots indicates it may be useful in revegetation of Pb-contaminated soils.

We investigated the pore-water content and speciation of copper (Cu), zinc (Zn), cadmium (Cd) and lead (Pb) in a range of uncontaminated and long-term contaminated soils in order to establish their potential bioaccessibility to soil biota, plants and humans. Among the samples, soil pH (0.01 M CaCl(2)) ranged from 4.9 to 8.2. The total metal content of the uncontaminated soils ranged from 3.8 to 93.8 mg Cu kg(-1), 10.3 to 95 mg kg(-1) Zn, 0.1 to 1.8 mg Cd kg(-1) and 5.2 to 183 mg kg(-1) Pb, while metal content in the contaminated soils ranged from 104 to 6841 mg Cu kg(-1), 312 to 39,000 mg kg(-1) Zn, 6 to 302 mg Cd kg(-1) and 609 to 12,000 mg kg(-1) Pb. Our analysis of pore-water found the Cu concentrations to be much higher in contaminated soils than in uncontaminated soils, with the distribution coefficients (K(d)) correlating significantly with the log of dissolved organic carbon concentrations. Despite the high total metal content of the contaminated soil, Zn, Cd and Pb were not generally found at elevated levels in the pore-water with the exception of a single contaminated soil. A long period of ageing and soil weathering may have led to a substantial reduction in heavy metal concentrations in the pore-water of contaminated soils. On the other hand, Pb bioaccessibility was found to be comparatively high in Pb contaminated soils, where it tended to exceed the total Pb values by more than 80%. We conclude that, despite the extensive ageing of some contaminated soils, the bioaccessibility of Pb remains relatively high.

In this study, lead (Pb) bioaccessibility in contaminated soils was assessed using an in vitro method (SBRC) encompassing gastric (SBRC-G) and intestinal (SBRC-I) phases. Initially, bioaccessibility studies were performed with a Pb reference material (Pb acetate, 1-10 mg L(-1)) in order to determine the influence of pH on Pb solubility. In the gastric phase (pH 1.5), Pb solubility was 100% (100 +/- 2.9%, n = 16) irrespective of the Pb concentration added, however, when the pH of the intestinal phase was increased to near neutral, Pb solubility decreased to 14.3 +/- 7.2%. In contaminated soils, Pb bioaccessibility varied from 35.7 to 64.1% and 1.2 to 2.7% for SBRC-G and SBRC-I phases, respectively. When relative bioaccessibility (Rel-SBRC-I) was calculated by adjusting the dissolution of Pb from contaminated soils by the solubility of Pb acetate at pH 6.5 (intestinal phase pH); Rel-SBRC-I values ranged from 11.7-26.1%. A stepwise regression model based on Pearson correlation factors was used to determine the suitability of in vitro assays for predicting in vivo (swine assay) relative Pb bioavailability. Rel-SBRC-I provided the best estimate of in vivo relative Pb bioavailability for soils used in this study (in vive relative Pb bioavailability [%] = Rel-SBRC-I [pH 6.5%] x 0.58 + 1.98, P = 0.53). The versatility of Rel-SBRC-I was demonstrated by accurately predicting relative Pb bioavailability from other reported in vivo studies.

Mouse models have been employed by many scientific research groups worldwide to predict the bioavailability of metal (loid)s and other chemicals in humans. Their suitability for predicting mixed metal (loid) bioavailability has been questioned and debated for decades by many research teams. In this study soils contaminated by lead (Pb) and arsenic (As), either in the field or by spiking in the laboratory, were used in bioavailability and bioaccessibility tests. The spiked soils were aged for more than a year prior to testing to achieve steady state and eliminate soil ageing effects, as reported in previous research. The bioavailability of, firstly, Pb in the presence of As and secondly, As in the presence of Pb was determined using mice. Furthermore, bioaccessibility was determined using a range of in vitro methods: relative bioaccessibility leaching procedure (RBALP), the Unified Bioaccessibility Research Group Europe (BARGE) method (UBM) gastric and intestinal phases, and the National Institute for Public Health and the Environment (RIVM) gastric and intestinal phases. The correlations between Pb and As bioavailability and their in vitro bioaccessibility when they were present in mixtures were analysed. The results indicated that the bioavailability of Pb in mice kidney tissues significantly correlated with bioaccessibility of Pb in RBALP (p < 0.01) , UBM gastric (p < 0.01) and intestinal phases (p < 0.01) and RIVM gastric phases when Pb is present in metal (loid) mixtures. Results of the current study reveal that the RBALP, and UBM gastric and intestinal phase were by far the best methods for predicting the RB of Pb when it is present in metal (loid) mixtures. Consequently, the mouse model can successfully explain the in vivo in vitro correlation (IVIVC) of Pb when it is present in metal (loid) mixtures. However, we did find that a mouse model may not be the best one to explain the IVIVC of As when it is present in metal (loid) mixtures. [Display omitted] • RBALP, & UBM gastric and intestinal phases best predicted RB of Pb. • RB of Pb in mixtures correlates well with RBALP test results. • UBM gastric and intestinal phases reliably predict RB of Pb in mixtures. • Mouse model did not to explain the IVIVC relationship of As in metal (loid) mixtures. • Suitability of mouse model to predict the RB of As in mixtures was questioned. [ABSTRACT FROM AUTHOR]