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Toxic heavy metals pollution in urban soil has become a major global issue due to its adverse effects on the environment and human health. In this paper, 26 soil samples were analyzed to assess the speciation, bioavailability and human health risk of Arsenic (As), Mercury (Hg), Lead (Pb) and Cadmium (Cd) in urban soils of a heavy industrial city in NE China by using a Monte Carlo simulation approach. The results showed that As, Hg, Pb and Cd concentrations in the soil all exceed the corresponding background value of study area. Mercury displays the highest value of geo-accumulation index (Igeo), followed by Cd, Pb and As. The pollution load index (PLI) value (>2) indicates a moderate pollution level in the study area. The chemical speciation of HMs mainly exists in residual fraction except Cd. The probabilistic health risk assessment demonstrated that the mean values of Total Carcinogenic Risk (TCR) and Hazard Index (HI) calculated with total concentration are at the unacceptable level, with a higher risk to children than adults. However, the mean values calculated with bioavailable fraction are all within the acceptable level. The mean value of TCR and HI obtained by bioavailable fraction is about 96% and 95% lower than that obtained by total concentration, respectively. Thus, this study suggested that the bioavailable fraction of HMs is a more reliable parameter for health risk assessment, while the total concentration of HMs can overestimate the true risk. The results of this study provide some insight into the speciation, bioavailability and health risks of toxic heavy metals in urban soils in those heavy industrial cities., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Animal bioassays have been developed to estimate oral relative bioavailability (RBA) of metals in soil, dust, or food for accurate health risk assessment. However, the comparability in RBA estimates from different labs remains largely unclear. Using 12 soil and soil-like standard reference materials (SRMs), this study investigated variability in lead (Pb) and arsenic (As) RBA estimates employing a mouse bioassay in 3 labs at Nanjing University, University of Jinan, and Shandong Normal University. Two performances of the bioassay at Nanjing University in 2019 and 2020 showed reproducible Pb and As RBA estimates, but increasing the number of mouse replicates in 2020 produced more precise RBA measurements. Although there were inter-lab variations in diet consumption rate and metal accumulation in mouse liver and kidneys following SRM ingestion due to differences in diet composition, bioassays at 3 labs in 2019 yielded overall similar Pb and As RBA estimates for the 12 SRMs with strong linear correlations between each 2 of the 3 labs for Pb (R 2  = 0.95-0.98 and slope = 0.85-1.02) and As RBA outcomes (R 2  = 0.46-0.86 and slope = 0.56-0.79). The consistency in RBA estimates was attributed to the relative nature of the final bioavailability outcome, which might overcome the inter-lab variation in diet consumption and metal uptake in mice. These results increased the confidence of use of mouse bioassays in bioavailability studies.

The dispersion of mine tailings affects ecosystems due to their high content of potentially toxic elements. Environmental risk increases when the soil impacted by tailings is used for agriculture; this use may result in health impacts. This study analyzes the feasibility of remediating a calcareous soil (used for maize cultivation) polluted with lead in the semiarid zone of Zimapán, México, by using EDTA as an extractant. Total geoavailable and bioaccessible concentrations in the gastric and intestinal phases were determined to evaluate lead availability and health risk. The soil was then washed with EDTA, and the geochemical fractionation (interchangeable, carbonates, Fe/Mn oxy-hydroxides, organic matter-sulfides, and residual) and impact on the mesophile bacteria and fungi/yeast populations were analyzed. The results showed total Pb concentrations up to 647 ± 3.50 mg/kg, a 46% bioaccessible fraction (297 ± 9.90 mg/kg) in the gastric phase and a 12.2% (80 ± 5 mg/kg) bioaccessible fraction in the intestinal phase, indicating a health and environmental risk. Meanwhile, the geochemical fractionation before washing showed a Pb fraction mainly consisting of Fe/Mn oxy-hydroxides (69.6%); this reducible fraction may progressively increase its bioaccessibility. Geochemical fractionation performed in the washed soil showed differences from that determined before the treatment; however, the iron and manganese fraction, at 42.4%, accounted for most of the Pb. The soil microbiology was also modified by EDTA, with an increase in aerobic bacteria and a decrease in fungi/yeast populations. Although 44% total lead removal was achieved, corresponding to a final concentration of 363.50 ± 43.50 mg/kg (below national and USEPA standards), washing with EDTA increased the soluble and interchangeable lead concentrations. Statistical analysis indicated a significant effect (p < 0.05) of EDTA on the soil's geochemical fractionation of lead.

Metal(loid) contamination of soil, resulting from the mining activities, is a major issue worldwide, due to its negative effects on the environment and health. Therefore, these contaminated soils need to be remediated. One realistic method is the assisted phytostabilization, which aims at establishing a vegetation cover on the soil that will reduce metal(loid) bioavailability and spreading through the prevention of wind erosion and water leaching. In addition, amendments are applied to improve soil conditions and ameliorate plant growth. In this goal, biochar and compost showed good results in terms of amelioration of soil fertility and reduction in lead bioavailability. However, they usually have a negative effect on arsenic. On the contrary, iron sulfate showed capacity to reduce arsenic mobility through interaction with its iron hydroxides. Finally, the choice of the appropriate plant species is crucial for the success of assisted phytostabilization. One good option is to use endemic species, adapted to the metal(loid) stress, with a fast growth and large shoot and root systems. The aims of this study were to (1) evaluate the effects of applying biochar, compost and iron sulfate, alone or combined, to a former mine soil on the soil properties and Agrostis capillaris growth, and (2) assess the difference between two Agrostis capillaris ecotypes, an endemic metallicolous ecotype and a non-metallicolous ecotype. Results of the mesocosm experiment showed that amendment application improved soil properties, i.e., reduced soil acidity, increased nutrient availability and lower metal(loid) stress, the best being the combination biochar-compost-iron sulfate. These ameliorations allowed a better plant growth. Finally, the metallicolous ecotype performed better in terms of growth than the non-metallicolous one and could thus be used in an assisted phytostabilization process on the former mine site.

Combining biochar (BR) with other immobilizing amendments has additive effects on Pb immobilization and been recognized to be effective for the restoration of Pb polluted soils. However, the impacts of different proportions between BR and a highly efficient Pb immobilizing agent called "magnesium potassium phosphate cement (MC)" have never been earlier investigated. This work aimed to investigate the consequences of BR and MC alone and their mixtures of 25:75, 50:50, and 75:25 ratios on Pb bioavailability, Pb immobilization index (Pb-IMMi), and enzymatic activities in Pb polluted soil. Furthermore, amendments effects on Pb distribution in spinach, growth, antioxidant capacity, biochemical, and nutritional spectrum were also investigated. We found that MC alone performed well to immobilize Pb in soil and reducing its distribution in shoots, but was less efficient to improve soil enzymatic activities and plant attributes. Conversely, the application of BR alone stimulated soil enzymatic activities, plant growth, and quality but was less effective to immobilize Pb in soil and reducing shoot Pb concentrations. The combinations of BR and MC of various ratios showed variable results. Interestingly, the most promising outcomes were obtained with BR50%+MC50% treatment which resulted in enhanced Pb-IMMi (73%), activities of soil enzymes, plant growth and quality, and antioxidant capacity, compared to control. Likewise, significant reductions in Pb concentrations in shoots (85%), roots (78%), extractable Pb (73%) were also obtained with BR50%+MC50% treatment, compared to control. Such outcomes point towards a cost-effective approach for reducing Pb uptake by the plants via using MC and BR at a 50:50 ratio., (Copyright © 2020. Published by Elsevier Inc.)

A soil microcosm experiment was carried out to quantify the transfer of cadmium (Cd) and lead (Pb) in a multi-species soil system (MS·3). Red earth from Jiangxi (S1), fluvo-aquic soil from Henan (S2), fluvo-aquic soil from Beijing (S3), and black soil from Heilongjiang (S4) were used for soil column packing with S1, S3, or S4 as the 20-50 cm layer and S2, which was Cd- and Pb-contaminated, as the top 0-20 cm layer. For each soil combination, four treatments were set up: CK (no wheat and no earthworm), W (only wheat), E (only earthworm), and E + W (earthworm and wheat). The results showed that the coexistence of earthworm with wheat reduced Cd and Pb contents in wheat plants and earthworms, and increased plant biomass, but had no significant effect on the survival rate and mean weight change rate of earthworms. Total Cd and Pb decreased remarkably in the 0-20 cm layer while increased in the 20-50 cm layer, and approximately 32.8%-51.1% of Cd and 0.35%-7.0% of Pb migrated down into the 20-50 cm soil layers from the 0-20 cm soil layers. The migration varied between the treatments from S2 to S1, S2, and S3. In S2-S1 and S2-S4 columns, the amount of Cd migration decreased when the earthworms coexisted with wheat, while in S2-S3 column, there was no significant difference on such amount regardless of the coexistence of earthworms with wheat. Taken together, the results indicated that the migration of Cd and Pb was not only associated with wheat and earthworm, but also depended on soil types., 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 © 2020 Elsevier Ltd. All rights reserved.)

Organisms employ various enzymatic and non-enzymatic detoxification mechanisms to minimize the harmful effects of metal pollution in the terrestrial environment. We examined the effects of copper (Cu), lead (Pb) and their mixture (Cu + Pb) on glutathione (GSH), metallothionein (MTs), cytochrome P450 (CYP 450), carboxylesterase (CarbE), acetylcholinesterase (AchE) and glutathione S-transferase (GST) in Lycosa terrestris and Pardosa birmanica via two exposure routes, i.e., soil and food for 10, 20 and 40 days. The present results revealed that the accumulation of Cu and Pb in both spiders' species increase with exposure duration and depend on the route of exposure and type of metal. The activities of CarbE, GST, and MTs significantly increased with increasing metal body burden for all experimental treatments. The CYP 450 activity exhibited a significant time-dependent decrease with increasing Cu concentration in both species. The AchE activity was significantly inhibited on Pb exposure via soil and Cu + Pb exposure via both routes. The decrease in the level of GSH was measured on Cu + Pb exposure via both routes. Thus, all these enzymatic and non-enzymatic responses are sensitive to the metals tested and could serve as early warning indicators for assessing the effects of metal pollution in these species., (Copyright © 2020. Published by Elsevier B.V.)

Tomato is the most widespread vegetable crop in the world. In Italy, tomatoes are mainly cultivated in the South and in the Campania region, precisely in the area called Agro Nocerino-Sarnese. This flatland is affected by an extreme level of environmental degradation, especially related to the Sarno River, where concentrations of Potential Toxic Elements (PTEs) have been found to be higher than the maximum permitted level. The aim of this study was to determine the PTEs uptake by roots and their translocation to the aerial parts of the plants of two cultivars of tomatoes (Pomodoro Giallo and San Marzano Cirio 3). To the purpose, samples of the two cultivars were grown both in pots with experimentally contaminated soil containing: Cr or Cd or Pb at extremely high concentrations and in pots with uncontaminated soils (control). Additionally, the antioxidant properties of the cultivars selected grown on uncontaminated/contaminated soils were assessed. The results showed that Cd was the contaminant that most significantly interfered with the growth of both cultivars of tomato plants, whereas Pb caused lower phenotypical damage. Cd translocation from root to the organs of tomato plants was observed in both cultivars. Specifically, the total amount of Cd found in stems and leaves was higher in the Pomodoro Giallo (254.4 mg/kg dry weight) than in the San Marzano Cirio 3 (165.8 mg/kg dry weight). Cd was the only PTE found in the fruits of both cultivars, with values of 6.1 and 3.9 mg/kg dry weight of Pomodoro Giallo and San Marzano Cirio 3, respectively. The fruits of tomato plants grown in PTEs-contaminated soil showed inhibition or stimulations of the radical scavenging activity compared to the fruits grown in uncontaminated soil. This study highlighted that, despite the relatively high experimental concentrations of PTEs, their translocation to the edible part was comparatively low or absent., Competing Interests: The authors have declared that no competing interests exist.

Trace metals are found naturally in soil. However, the increase in industrial and agricultural polluting activities has increased trace metal contamination and raised high concerns in the public health sector. The study was conducted on Origanum syriacum, one of the most consumed herbs in the Middle East, and was divided into three parts. (1) Pot experiment: to study the effect of Cd, Pb, or Ni levels in soil on their uptake by O. syriacum. (2) Field samples: collected from major agricultural regions in Lebanon to analyze Cd, Pb, and Ni concentrations in soil and leaves. (3) Sale outlets samples: to measure the levels of Cd, Pb, and Ni in O. syriacum tissues in the market. Results showed that there was a positive correlation between levels of Cd, Pb, and Ni in soil and those in O. syriacum tissues. None of the field samples contained Pb or Ni that exceeded the maximum allowable limits (MAL). Three samples collected from heavily poultry-manured soil contained Cd higher than the MAL. Samples collected from sale outlets did not exceed the MAL for Ni but two exceeded the MAL for Cd and one for Pb. Trace metal contamination is not a major concern in O. syriacum produced in Lebanon. Only one mixture sample from a sale outlet was higher in Pb than the MAL and three samples from heavily manured fields exceeded the MAL for Cd.

Sodium sulfide (Na 2 S) is usually used as an amendment in industrial sewage treatment. To evaluate the effects of Na 2 S on the growth of Robinia pseudoacacia (black locust), heavy metal immobilization, and soil microbial activity, the R. pseudoacacia biomass and nutrient content and the soil heavy metal bioavailability, enzyme activity, and arbuscular mycorrhizal (AM) fungal community were measured by a single-factor pot experiment. The Pb-Zn-contaminated soil was collected from a Pb-Zn mine that had been remediated by R. pseudoacacia for five years. Three pollution levels (unpolluted, mildly polluted, and severely polluted) were evaluated by the pollution load index. Na 2 S application increased the shoot biomass under severe and mild contamination. In soil, Na 2 S application decreased the bioavailable Pb and Zn contents under severe and mild contamination, which resulted in a decrease in the Pb and Zn content in R. pseudoacacia. However, Na 2 S application did not affect the total Pb content per plant and enhanced the total Zn content per plant because of the higher biomass of the plants under Na 2 S application. Increased phosphatase activity and increased available phosphorous content may promote the uptake of phosphorus in R. pseudoacacia. Moreover, Na 2 S application is beneficial to the diversity of AM fungi under mild and severe pollution. Overall, Na 2 S application has great potential for enhancing soil heavy metal immobilization, enhancing soil microbial activity, and improving the growth of R. pseudoacacia in polluted soils. Therefore, Na 2 S is suitable for use in Pb-Zn remediation to ameliorate environmental heavy metal pollution., 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 © 2020 Elsevier Inc. All rights reserved.)

Agricultural production of Ligusticum chuanxiong Hort. is often affected by heavy metal pollution in soil, especially mixtures of cadmium (Cd) and lead (Pb). We assessed metal-induced phytotoxicity in L. chuanxiong by exposing the plants to soil treated with Cd, Pb, or Cd/Pb mixtures. A combined Cd/Pb treatment alleviated the inhibition in plant growth, photosynthesis, and secondary metabolite generation seen in single-metal exposures in three of the four combinations. Most combined Cd/Pb treatments resulted in preferential uptake of magnesium, copper, and nitrogen in underground plant parts and accumulation of phosphorus and calcium in aboveground plant parts, thereby leading to improvements in photosynthetic potential. Compared with single-metal exposures, combined Cd/Pb treatment significantly decreased the contents of Cd by 16.67%-40.12% and Pb by 10.68%-21.70% in the plant, respectively. At the subcellular level, the Pb presence increased the Cd percentage associated with cell wall from 64.79% to 67.93% in rhizomes and from 32.76% to 45.32% in leaves, while Cd reduced Pb contents by 9.36%-46.39% in the subcellular fractions. A combined Cd/Pb treatment decreased the contents of water- and ethanol-extractable metal forms and increased the contents of acetic acid- and hydrochloric acid-extractable forms. The lower toxic effects of the Cd/Pb mixture in L. chuanxiong were associated with photosynthetic potential, subcellular distribution, the chemical forms of Cd and Pb, and synthesis of secondary metabolites. These findings are useful for plant production strategies in soils contaminated by heavy metals., Competing Interests: Declaration of competing interest The authors declare no conflicts of interest., (Copyright © 2020 Elsevier Inc. 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.)

Evaluation of the transportation of heavy metals in food chain has received a great deal of attention. In this study, the mobility of cadmium (Cd) and lead (Pb) in soil-mulberry-silkworm system was assessed. The results showed that bioconcentration factors for Cd and Pb were lower than 1 for all the three mulberry cultivars. Higher translocation factors (TFs) were observed in the levels from branch to leaf, larvae to excrement. The BCFs of Pb in root and silkworm excrement were higher than those in the other parts. Meanwhile, most of Cd accumulated from soils located in the root (48.00-54.40%) and only about 10% was in the leaf. But the Cd and Pb had significant effects on the ratios of cocoon shell with Yuesang 11 under different planting densities. For Yuesang 11 and Qiangsang 1, the Pb percentages were roots > branches > leaves > stems. The rates of ingestion (IR) and digestion (DR) were a little higher than those in the control at first and then decreased gradually with time. The IR reached the lowest values on 8th day while the DR arrived at the highest. Planting mulberry and raising silkworm could be a reasonable method for the utilization of heavy metal contaminated paddy soils., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Despite the global importance of atmospheric heavy metal input into agricultural soils, research has primarily focused on the amount of the depositions with limited attention given to the risk of the newly deposited heavy metals. To understand the remobilization of the newly deposited copper (Cu) and lead (Pb) from the atmosphere and explore the metals' mobility and bioavailability to rice (Oryza sativa L.), a soil transplant experiment was conducted in three areas along a gradient of atmospheric depositions. Approximately 61% of the Cu and 76% of the Pb depositions tended to be present in potentially mobile fractions. The soil retention of newly deposited Cu and Pb presented as higher mobile fractions than these in the original soil. The newly deposited Cu and Pb in soils only accounted for 0.34-8.7% and 0.07-0.29% of the total soil Cu and Pb pools, but they contributed 30-84% and 6-41% in rice tissues, respectively. A major implication of these findings is that once the heavy metal is deposited, it may be reactivated in soils and transported to aerial parts or foliar uptake into plant tissues, emphasizing the important role of the newly deposited Cu and Pb in contributing to the edible parts of crops., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In order to assess and optimize frequently used in vitro inhalation bioaccessibility procedures for heavy metals in the inhalation risk assessment, in vivo inhalation bioavailability of Pb in simulated atmosphere fine particles (PM 2.5 ) from aging soils spiked with lead compounds and field soils in lead-zinc mining areas was investigated via intranasally instilled experiments with these PM 2.5 suspensions to mice and Pb bioaccessibility was extracted by using four frequently used in vitro procedures (Gamble Solution, simulated lung fluid, simulated epithelial lung fluid and artificial lysosomal fluid). Mouse exposure experiments showed that Pb was mainly distributed in the liver, kidneys, blood and spleen. Based on the kidney model, in vitro inhalation bioaccessibility of Pb extracted with optimized Gamble Solution, in which solid to liquid ratio (S/L) was optimized to 1:1000 g ml -1 and DTPA was proved to be the key effective component, showed a strong linear relationship with its in vivo inhalation bioavailability (y = 1.07x - 3.86, R 2  = 0.73). Moreover, in vitro bioaccessible and bioavailable fractions of Pb were mainly from acid exchangeable and reducible fractions of Pb in PM 2.5 . Altogether, optimized Gamble Solution was suggested for the analysis of in vitro bioaccessibility for risk-based assessments., (Copyright © 2019 Elsevier B.V. All rights reserved.)

A greenhouse pot experiment was conducted to evaluate the effect of biochar on the growth and uptake of Pb and Zn by tomato plants ( Solanum lycopersicum, L.) cultivated in two highly contaminated Kosovo soils, A and B. Plants were cultivated in the biochar amended and unamended soils. As expected, the biochar addition to the two polluted soils has contributed to significantly improve the crop yields, in terms of both fresh and dry weight. Further, results indicated that the effect of biochar on metal mobility is closely related, besides its properties, to soil's native characteristics. In fact, the addition of biochar to soil B had also beneficial effects on the uptake of both metals, halving in some cases the values of the biological accumulation and transfer coefficients, while it did not show the same efficacy on soil A.

Pot experiments were conducted under abiotic conditions to investigate the interactive influence of decabromodiphenyl ether (BDE-209) and lead (Pb) on the seed germination, germ length, root exudation and physiological characteristics of tall fescue (Festuca arundinaceae), and the uptake, accumulation of Pb and BDE-209 in the plant tissues. Results show that seed germination and germ length were impacted by Pb but less influenced by BDE-209. BDE-209 spiking (10 and 50 mg/L) could alleviate the toxicity of high Pb concentration on seed germination and growth. The chlorophyll content was significantly increased at 500 mg/kg Pb but declined at 2000 mg/kg Pb. Low-level Pb contamination (500 mg/kg) activated antioxidase activity; however, 2000 mg/kg Pb significantly reduced the antioxidase activity. Plant biomass slightly decreased at 500 mg/kg Pb but significantly declined at 2000 mg/kg Pb. The addition of a moderate dosage of BDE-209 (10-50 mg/kg) lessened Pb phytotoxicity, leading to improved plant growth relative to the case of Pb spiking alone. The exudate secretion was significantly enhanced by Pb addition, but BDE-209 spiking only caused slightly increased secretion. Pb could interfere with BDE-209 adsorption and translocation of tall fescue by affecting physiological behavior of the plant, but BDE-209 exhibited little influence on the Pb fate in the plant. Overall, BDE-209 had slight interference on the impact of Pb towards tall fescue. The results demonstrate the complex interactive effects of organic pollutants and heavy metals in the soil-plant system., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Lead can be immobilized in contaminated soils by phosphate rock (PR) amendment, but its efficiency is generally limited by low solubility of PR. Our study aimed to elucidate whether phosphate solubilizing bacteria (PSB) can promote Pb immobilization through PR solubilization. Results showed that P. ananatis HCR2 and B. thuringiensis GL-1 could effectively solubilize PR by producing citric, glucose, and α-Ketoglutaric acids. In broth assay, phosphate solubilized from PR by PSB rapidly reacted with Pb 2+ and formed insoluble lead compounds, as confirmed by scanning electron microscope, energy dispersive X-ray, and X-ray photoelectron spectroscopy. Pot experiment using lettuce (Lactuca sativa L.) and diffusive gradients in thin films (DGT) verified the effectiveness of soil remediation using PR amendment and PSB inoculation, as plant shoot biomass and net photosynthetic rate as well as soil bioavailable phosphate concentration have significantly increased, while the phytoavailability of Pb, Cd, and Zn greatly reduced. This study suggested that PR amendment combined with PSB inoculation could be applied for remediation of agricultural fields contaminated with multiple heavy metals., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Better understanding of microbial activity in the rhizosphere soils associated with lead (Pb) uptake by plants may help with the phytoremediation of Pb-contaminated soils. In this work, the effects of Pb exposure (0, 200, 400, 600, 800 mg kg -1 ) on Pb accumulation and soil microbial activity in the rhizosphere of the mining ecotype (ME) and corresponding non-mining ecotype (NME) of Athyrium wardii (Hook.) Makino were investigated through a pot experiment. Although the plant growth of the two ecotypes was inhibited under Pb stress, the ME showed a less biomass decrease (12.6-44.0%) for aboveground than the NME, showing a greater tolerance to Pb stress. Pb concentrations as well as Pb accumulation in the two ecotypes showed an increasing trend with increasing soil Pb concentrations. The ME presented greater Pb accumulation ability than the NME, especially in underground parts. Pb availability in the rhizosphere soils of the two ecotypes after harvest decreased compared with those before transplantation. Available Pb in the rhizosphere of the ME was 1.4-4.8 times higher than that of the NME under exposure to 200-800 mg kg -1 Pb. The ME shows a greater ability to mobilize Pb in the rhizosphere soils. Pb exposure resulted in an inhibition of microbial activity in the rhizosphere of the two ecotypes. The ME demonstrated greater soil respiration and microbial biomass carbon (MBC) in the rhizosphere than the NME when treated with 200-800 mg kg -1 Pb. The ME showed a less decrease for MBC and a less increase for metabolic quotient in the rhizosphere soils than the NME when exposed to Pb generally. Microorganisms in the rhizosphere soils of the ME seem to be much more adapted to Pb stress, thus showing a great benefit for Pb accumulation and the phytostabilization of Pb-contaminated soils by the ME.

In this study, an in vitro in vivo correlation (IVIVC) between Pb in vitro bioaccessibility (IVBA) and relative bioavailability (RBA) was explored to determine whether the efficacy of Pb immobilization in phosphate amended soils could be predicted using an in vitro approach. Mining/smelting impacted soil from Broken Hill, Australia (582-3536 mg/kg of Pb in the <250 μm soil particle fraction) was amended with Phosphoric Acid (PA), Mono Ammonium Phosphate (MAP) or Triple Super Phosphate (TSP) at Pb:P molar ratios of 1:1-1:5. Pb speciation in pre- and post-treated soil was assessed using X-ray Absorption Spectroscopy (XAS), Pb IVBA was measured using the Solubility Bioaccessibility Research Consortium (SBRC) assay (gastric and intestinal phases), and Pb RBA was determined in mice using blood Pb concentration as the bioavailability endpoint. XAS analysis revealed a 3.75-6.00 fold increase in the weighted % of Pb phosphates in soil containing >1000 mg/kg Pb while treatment effect ratios of 0.89-0.99 (SBRC-G), 0.09-0.71 (SBRC-I) and 0.27-0.80 (RBA) were observed in PA amended soil (Pb:P = 1:5). Although significant (p < 0.05) correlation were obtained between Pb RBA and IVBA (%) determined using SBRC-G (r = 0.64) and SBRC-I (r = 0.67), the strengths of the relationships were weak (r 2  = 0.41-0.45). This research highlights the complexities associated with the prediction of Pb RBA in phosphate amended soil., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

A study of the impact of an abandoned lead (Pb) mine ("Las Musas"), located in SW Spain, on the contamination of the surface soil and pastures in its vicinity revealed the presence of widely distributed, high levels of Pb contamination. The total Pb concentrations in soils sampled at distances from 3 to 998 m from the mine ranged between 129 and 1053 mg/kg, when it has been reported that non-polluted soils have concentrations of 29-40 mg/kg. These exceed the maximum tolerable levels in agricultural soils for the protection of environmental and human health as established in international and regional regulations. While the concentrations of potentially bioavailable Pb in the soils also surpassed the regulatory levels, the effective bioavailable fractions were low. The Pb concentrations measured in native plants ranged from 1.70 to 129 mg/kg dry weight, with Cynosurus echinatus, Philadelphus coronarius, and Fraxinus angustifolia being the species that bioaccumulated the greatest concentrations of this metal. Estimation of the environmental risk to wildlife and livestock grazing in the studied area showed no potential toxicity for these animals.

Atmospheric deposition of heavy metals is widely documented and has been connected to adverse ecological and health impacts. The influence of atmospheric deposition on the soil-rice system in a typical urban agglomeration region was studied continuously through a field contrast experiment for two years. The results showed that the Cd and Pb in rice grains is mainly from soil, but Cd and Pb from the atmospheric deposition should be a focus of attention. The bioavailable content of heavy metals in atmospheric deposition is higher than that in corresponding surface soil. Atmospheric deposition contributed 10.8-47.7% of the Cd and Pb in brown rice, and 13.7-60.3% of the Cd and Pb in rice leaves was from atmospheric deposition. In the traffic area, a high deposition site, the contributions of atmospheric depositions to heavy metals in rice plants were higher than those from abandoned mine area and suburban area. Atmospheric deposition also consistently decreased the pH (0.17-0.66) and increased the exchangeable Cd (27.1-62.1%) and Pb (3.3-26.1%) in surface soil. In addition, the health risk index (HRI) of rice consumption was also increased as a result of the different atmospheric depositions of heavy metals, which accounted for 40.0% and 35.5% of Cd and Pb at the high deposition site, respectively. These findings demonstrate the potential influences of atmospheric deposition on the soil-crop system and human health, and can also provide a useful reference for developing the emission control strategies., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The robustness of in vitro bioaccessibility assays to predict oral relative bioavailability (RBA) of multiple metals in contaminated soils requires validation using additional soil samples. In this study, 11 contaminated soils from mining/smelting areas were analyzed for As-, Cd-, and Pb-RBA using a mouse bioassay and metal bioaccessibility via the UBM gastric phase assay. Metal-RBA varied considerably among soils, with As-RBA (2.5-23%, mean 12%) being generally lower than Cd-and Pb-RBA (3.4-88 and 3.3-59%, mean 42 and 28%), due to higher proportions of As in the residual fractions. Metal-RBA generally decreased with increasing metal concentrations probably due to reduced labile metal fractions. In addition, strong negative correlations were observed between total Fe with As-, Cd-, and Pb-RBA (R 2  = 0.46-0.77), suggesting the role of Fe in controlling metal-RBA in soils. Like RBA, metal bioaccessibility by the UBM assay also varied among samples. However, strong in vivo-in vitro correlations (IVIVCs) were observed between metal-RBA and bioaccessibility (R 2  = 0.52-0.81). Further, there were little differences when As-, Cd-, and Pb-IVIVCs established using soils from this study and soils pooled from literature were compared, suggesting the robustness of the UBM assay to predict metal-RBA in contaminated soils., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Lead (Pb) is an important pollutant and is released into the environment in many forms. Different lead compounds have a variety of solubilities and so may impact on lead bioavailability and toxicity when added to soil. In this experimental study, we investigated the bioavailability of Pb in soil spiked with 300, 900 and 1500 mg/kg of Pb-acetate, PbCl 2 and PbO using lettuce and wallaby grass. The concentration of Pb in the shoots of both species from control soils (2-3 mg/kg) was similar to previously reported concentrations in plants grown on uncontaminated soils. The Pb concentrations in the plant shoots increased with Pb concentrations in soil for lettuce (R 2  = 0.526, P < 0.001) and wallaby grass (R 2  = 0.776, P < 0.001). This study demonstrated that Pb bioavailability in soil was not affected by the type of Pb compound added to the soil for both plant species up to 1500 mg/kg Pb concentrations. Instead, the Pb concentration in the plant was best predicted by the total concentration of lead in the soil, irrespective of the original lead compound added to the soil. This research suggests that the original Pb compounds that contaminated the soil are unlikely to be an important factor in assessing Pb bioavailability, and hence risk, in soils., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

To our knowledge, this is the first report on exploring the interactive effects of various biochars (BCs) and nanomaterials (NMs) on plant growth and bioavailability of trace elements in soil. This study evaluated the bioavailability and toxicity of arsenic (As), lead (Pb), and NMs to cabbage plants. The BCs were produced from rice husk (RB), sewage sludge, and bamboo wood (WB). The BCs at 2.5 and 5% (w w -1 ), NMs for removing As (NMs-As) and heavy metals (NMs-HM) at 3000 mg kg -1 , and multi-walled carbon nanotubes (CNT) at 1000 mg kg -1 were applied in bioassay and incubation experiments (40 days), along with the unamended soil as the control. Results showed that the NMs-As and NMs-HM decreased seed germination at 3 days after sowing; however, their toxicity was eliminated by BCs. Growth parameters of cabbage revealed that the CNT was the most toxic NMs, as it was translocated in root and leaf cells, which was confirmed by transmission electron microscopic images. Bioavailable Pb was reduced by 1.2-3.8-folds in all amended rhizosphere and bulk soils. Amendments of 2.5% WB + NMs-As and 2.5% RB + NMs-As significantly decreased both bioavailable As and Pb.

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.)

In a previous study, Pb toxicity was found to be delayed compared to Pb bioaccumulation in Enchytraeus crypticus. This study aimed at further investigating the acute and delayed onset of Pb toxicity in E. crypticus by using a combination of toxicokinetics and toxicodynamics approaches. Enchytraeids were exposed to different Pb concentrations (uptake phase) in natural LUFA 2.2 soil for different short-term exposure periods, followed by a 7-d elimination phase in clean soils. Body Pb concentrations and enchytraeid mortality were determined at different time intervals during both the exposure and the elimination phase. Pb uptake kinetics in E. crypticus were well described by a three-stage first-order model with an initial overshoot in body Pb concentrations. At higher exposure concentrations, Pb caused delayed enchytraeid mortality even following short-term exposure. LC50 based on body Pb concentrations appeared no good descriptor of delayed Pb toxicity in E. crypticus. Exposure time had a major impact on Pb bioaccumulation, toxicity and its delayed effects, which argues against relying on ecotoxicity tests for metal toxicity using a fix exposure duration. The presence of delayed toxic effects also suggests that post-exposure observations are necessary to avoid underestimation of metal toxicity., (Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.)

The present study investigated the bioavailability and toxicity of lead to the potworm Enchytraeus crypticus in six soils with different properties. Pb partitioning between the soil solution and solid phase was affected by soil organic matter (OM) content, cation exchange capacity (CEC) and water holding capacity (WHC). After 21 d exposure, Pb bioaccumulation in the enchytraeids was positively correlated with total soil Pb concentration. Bioaccumulation was best predicted by Pb availability (CaCl 2 -extractable and porewater Pb concentrations), and by the Ca concentration in pore water and the CEC of the soils. Toxicity varied greatly among soils, with LC50s and EC50 reproduction s based on total Pb concentrations ranging from 246 to >3092 and from 81 to 1008 mg Pb/kg dry soil, respectively. The variation in LC50s among soils was explained by differences in CaCl 2 -extractable Pb concentrations in soil and internal Pb concentrations in the animals. The differences in EC50 reproduction s could be explained from the CaCl 2 -extractable Pb concentrations in the soils. Although it was also correlated with CEC and porewater Ca concentration, pH CaCl2 was the dominating factor for predicting Pb toxicity based on total soil concentrations. This study demonstrates that soil properties, such as pH, CEC and Ca concentration in pore water, significantly affected the bioavailability and toxicity of Pb and therefore should be taken into account when assessing the ecological risk of metals in contaminated soils., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Biochar, produced by the pyrolysis of biomass under low oxygen conditions, has gathered attention in the last few years due to its capability to reduce metal(loid)s bioavailability and mobility in soils, as well as its beneficial effects on soil fertility. Indeed, biochar amendment to polluted soil induced usually an increase of pH, water holding capacity, and nutrient contents, associated with a decrease of metal(loid)s concentrations in soil pore water, through sorption. However, biochar has been shown efficient in sorbing cation pollutants, like Pb, but present a low sorption capacity towards anions like As. This contrasted behavior poses a problem, as most polluted soils are multi-contaminated, with both cation and anion pollutants. One of the solutions to overcome such problem is to functionalize biochar, by modifying its surface. However, most studies actually focused on functionalization effect on metal(loid)s sorption towards batch experiments, and only a few dealt with modified biochar incorporation to the soil. Therefore, this study aimed (i) to assess the sorption capacity of hardwood biochars, harboring different particle sizes, towards Pb and As; (ii) to evaluate the effect of a Fe-functionalization on Pb and As sorption; and (iii) to validate the results, in a phytotoxicity test using Phaseolus vulgaris as bioindicator plant. The batch experiments showed that all four biochars were able to efficiently sorb Pb, the fine biochars showing higher sorption values than the coarse biochars. As sorption was very low. Fe-coating increased As sorption value, while having no effect on Pb sorption. However, when incorporated in the soil, Fe-coated biochar did not improve soil physico-chemical properties compared to the pristine biochar; especially, it did not reduce As soil pore water concentrations. Finally, bean plant did not show differences in terms of biomass production between the two biochars incorporated into polluted soil, demonstrating that Fe-functionalization did not improve biochar capacity to decrease soil toxicity.

Interactions between heavy metals in soil could affect soil heavy metal availability and plant uptake. Thus, in this study, Cd and Pb accumulation as well as plant growth of the mining ecotype (ME) and non-mining ecotype (NME) of Athyrium wardii (Hook.) in response to the exposure of Cd and Pb was investigated by a pot experiment. Although the exposure of Cd in combination with Pb further inhibited the growth of the two ecotypes in comparison with the exposure of single Cd or Pb, the ME presented lower biomass decline for the whole plant (22.0%-70.0%) than the NME among most treatments. The presence of Pb promoted Cd accumulation both in above-ground and under-ground parts of the ME. Cd concentrations in under-ground parts of the ME decreased when exposed to higher concentrations of Pb (> 600 mg kg -1 ). Meanwhile, the presence of Cd inhibited Pb accumulation in above-ground parts of the ME and promoted Pb accumulation in under-ground parts of the ME. Pb concentrations in under-ground parts of the ME decreased when soil Cd concentrations were more than 25 mg kg -1 . The partial correlation analysis further demonstrated that the interactions between Cd and Pb stimulated Cd accumulation both in above-ground and under-ground parts of the ME and Pb accumulation in under-ground parts of the ME, while inhibited Pb accumulation in above-ground parts of the ME, showing great benefit for Pb phytostabilization by the ME. Among treatments, the bioaccumulation coefficients for Cd and Pb of the ME, varying from 2.71-31.05 and 20.09-78.06, were much higher than those of the NME. The translocation factors for Cd and Pb of the ME, varying from 0.26-0.52 and 0.01-0.10, were lower than those of the NME. These results indicate that the ME presented greater potential for the phytostabilization of soil contamination with Cd and Pb, especially for Pb.

To determine the effects of dietary constituents on soil Pb oral bioavailability, Pb relative bioavailability (RBA) in 3 soils contaminated by zinc smelting (ZS), wire-rope production (WR), and metal mining (MM) was measured under fasted and fed states with 9 foods. Under fasted state, Pb-RBA was 84.4 ± 10.3, 82.6 ± 4.70, and 32.3 ± 1.10% for ZS, WR, and MM soils; however, it decreased by 1.3-3.5 fold to 23.9-58.8, 25.6-49.9, and 14.8-24.2% under fed states with foods excluding Pb-RBA with egg in WR soil (97.3 ± 4.46%), and with cabbage and egg in MM soil (40.0 ± 8.62 and 44.4 ± 0.96%). In the presence of foods, egg and pork with significantly higher protein and fat contents leaded to the highest soil Pb-RBA (44.4-97.3%), while Pb-RBA determined with mineral-rich mouse feed was 1.6-7.9 fold lower (9.41-13.5%), suggesting high fat and protein foods tended to increase soil Pb-RBA, while high mineral diets decreased soil Pb-RBA. The increased Pb-RBA of MM soil with cabbage compared to fasted state was due to high organic content in cabbage, which could increase soil Pb solubility by inhibiting Fe and Pb co-precipitation in the intestine. For accurate assessment of health risks of contaminated soils, dietary influence on soil Pb-RBA should be considered., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Paddy rice (Oryza sativa L.) is a major staple crop in Asia. However, heavy metal accumulation in paddy soil poses a health risk for rice consumption. Although plant uptake of Pb is usually low, Pb concentrations in rice plants have been increasing with Pb contamination in paddy fields. It is known that iron oxide deposits in the rhizosphere influence the absorption of soil Pb by rice plants. In this study, 14 rice cultivars bred in Taiwan, including ten japonica cultivars (HL21, KH145, TC192, TK9, TK14, TK16, TN11, TNG71, TNG84, and TY3) and four indica cultivars (TCS10, TCS17, TCSW2, and TNGS22), were used in a field experiment. We investigated the genotypic variation in rice plant Pb in relation to iron oxides deposited in the rhizosphere, as seen in a suspiciously contaminated site in central Taiwan. The results showed that the cultivars TCSW2, TN11, TNG71, and TNG84 accumulated brown rice Pb exceeding the tolerable level of 0.2mgkg -1 . In contrast, the cultivars TNGS22, TK9, TK14, and TY3 accumulated much lower brown rice Pb (<0.1mgkg -1 ); therefore, they should be prioritized as safe cultivars for sites with potential contamination. Moreover, the iron oxides deposited on the rhizosphere soil show stronger affinity to soil-available Pb than those on the root surface to form iron plaque. The relative tendency of Pb sequestration toward rhizosphere soil was negatively correlated with the Pb concentrations in brown rice. The iron oxides deposited on the rhizosphere soil but not on the root surface to form iron plaque dominate Pb sequestration in the rhizosphere. Therefore, the enhancement of iron oxide deposits on the rhizosphere soil could serve as a barrier preventing soil Pb on the root surface and result in reduced Pb accumulation in brown rice., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Hand-to-mouth activity is an important pathway for children's exposure to contaminated soils, which is often co-contaminated by Pb and As in mining and smelting sites. To reduce soil Pb risk to humans by oral exposure, phosphate amendments have been used to reduce Pb relative bioavailability (RBA), but its efficiency has not been investigated using validated in vitro assays nor its influence on As-RBA. Here, 5 contaminated soils (A-E) were amended with 0.5% phosphoric acid (PA) to study its effect on Pb- and As- RBA using a newly-developed mouse kidney model and bioaccessibility using 4 in vitro assays including UBM, SBRC, IVG, and PBET. Based on the mouse kidney model, Pb-RBA in PA-amended soils decreased from 14.2-62.5% to 10.1-29.8%. In contrast, As-RBA decreased from 26.5% to 15.9% in soil B but increased from 27.5 to 41.2% in soil D, with changes being insignificant in 3 other soils (35.8-58.8 to 28.1-61.1%). When assessing Pb bioaccessibility in PA-amended soils, decreased bioaccessibility were found using PBET and SBRC. For As, its bioaccessibility increased in PA-amended soils, inconsistent with in vivo data. Our results shed light on the importance of method selection to assess risk in Pb- and As-contaminated soils amended with phosphate., (Copyright © 2017 Elsevier B.V. All rights reserved.)

In this study, the influence of sample matrix on the relative bioavailability of arsenic (As), cadmium (Cd) and lead (Pb) was assessed following exposure of C57BL/6 mice to spiked aged (12years) soils. AIN93G mouse chow was amended with individual and tertiary As, Cd and Pb soil combinations which were administered to mice over a 9day exposure period. Contaminant relative bioavailability was calculated by comparing As urinary excretion and Cd-kidney/Pb-liver accumulation to corresponding values for compounds used to derive the respective toxicity reference value. Strong linear dose-responses were observed for mice exposed to AIN93G mouse chow augmented with individually spiked soil with As, Cd and Pb. When mice were exposed to co-contaminants, As relative bioavailability (RBA) decreased similar to results from previous co-contaminant salt experiments presumably due to the influence of Cd on phosphate transport proteins, which are utilized for As absorption. However, a decrease in Cd-kidney and Pb-liver accumulation was also observed following co-co-exposure. It was postulated that this resulted from interactions with other (essential) metals (e.g. iron, aluminium, manganese, magnesium) within the soil matrix and their influence on absorption via divalent metal transporters., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Surface soils in portions of the Sydney (New South Wales, Australia) urban area are contaminated with lead (Pb) primarily from past use of Pb in gasoline, the deterioration of exterior lead-based paints, and industrial activities. Surface soil samples (n=341) were collected from a depth of 0-2.5cm at a density of approximately one sample per square kilometre within the Sydney estuary catchment and analysed for lead. The bioaccessibility of soil Pb was analysed in 18 samples. The blood lead level (BLL) of a hypothetical 24 month old child was predicted at soil sampling sites in residential and open land use using the United States Environmental Protection Agency (US EPA) Integrated Exposure Uptake and Biokinetic (IEUBK) model. Other environmental exposures used the Australian National Environmental Protection Measure (NEPM) default values. The IEUBK model predicted a geometric mean BLL of 2.0±2.1µg/dL using measured soil lead bioavailability measurements (bioavailability =34%) and 2.4±2.8µg/dL using the Australian NEPM default assumption (bioavailability =50%). Assuming children were present and residing at the sampling locations, the IEUBK model incorporating soil Pb bioavailability predicted that 5.6% of the children at the sampling locations could potentially have BLLs exceeding 5µg/dL and 2.1% potentially could have BLLs exceeding 10µg/dL. These estimations are consistent with BLLs previously measured in children in Sydney., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Lead (Pb) contamination in soil represents a threat to human health. Phytoextraction has gained attention as a potential alternative to traditional remediation methods because of lower cost and minimal soil disruption. The North American native switchgrass (Panicum virgatum L.) was targeted due to its ability to produce high biomass and grow across a variety of ecozones. In this study switchgrass was chemically enhanced with applications of the soil-fungicide benomyl, chelates (EDTA and citric acid), and PGR to optimize phytoextraction of Pb and zinc (Zn) from contaminated urban soils in Atlanta, GA. Exogenous application of two plant hormones was compared in multiple concentrations to determine effects on switchgrass growth: indole-3-acetic acid (IAA), and Gibberellic Acid (GA 3 ), and one PGR benzylaminopurine (BAP), The PGR BAP (1.0 μM) was found to generate a 48% increase in biomass compared to Control plants. Chemical application of citric acid, EDTA, benomyl, and BAP were tested separately and in combination in a pot experiment in an environmentally controlled greenhouse to determine the efficacy of phtyoextraction by switchgrass. Soil acidification by citric acid application resulted in highest level of aluminum (Al) and iron (Fe) in plants foliage resulting in severe phytotoxic effects. Total Pb phytoextraction was significantly highest in plants treated with combined chemical application of B + C and B + C + H. Suppression of AMF activities by benomyl application significantly increased concentrations of Al and Fe in roots. Application of benomyl reduced AMF colonization but was also shown to dramatically increase levels of septa fungi infection as compared to Control plants., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The increasing industrial, mining and agricultural activities have intensified the release of potential toxic trace elements (PTEs), which are of great concern to human health and environment. The alarming increase in PTEs concentration, stress the need for biotechnological remediation approaches. In order to assist phytoextraction of PTEs, different combinations of Streptomyces pactum (Act12) with biochar were applied to mining and industrial polluted soils of Shaanxi and Hunan Provinces of China, respectively. Act12 affected soil physico-chemical properties in both soils. Bioavailable Zn and Pb increased due to microbial activities, while Cd decreased by adsorption on biochar surface. Phytoextraction of Zn and Pb occurred in TG and CZ soil, while Cd uptake decreased in iron rich CZ soil by conflicting effect of siderophores. Cd in sorghum shoot was below detection level, but uptake increased in the roots due to minimum available fraction in TG soil. Biochar reduced the shoot and root uptake of Cd. Sorghum shoot, root dry weight and chlorophyll significantly increased after Act12 and biochar application. β-glucosidase, alkaline phosphatase and urease activities were significantly enhanced by Act12. Antioxidant enzymatic activities (POD, PAL and PPO) and lipid peroxidation (MDA) were decreased after the application of Act12 and biochar by reduced PTEs stress. Act12 and biochar can be used for different crops to enumerate the transfer rate of PTEs into the food chain., (Copyright © 2017 Elsevier Inc. All rights reserved.)

The effect of the combined application of nano-hydroxyapatite (NHAP) or nano-carbon black (NCB) on the phytoextraction of Pb by ryegrass was investigated as an enhanced remediation technique for soils by field-scale experiment. After the addition of 0.2% NHAP or NCB to the soil, temporal variation of the uptake of Pb in aboveground parts and roots were observed. Ryegrass shoot concentrations of Pb were lower with nano-materials application than without nano-materials for the first month. However, the shoot concentrations of Pb were significantly increased with nano-materials application, in particular NHAP groups. The ryegrass root concentrations of Pb were lower with nano-materials application for the first month. These results indicated that nano-materials had significant effects on stabilization of lead, especially at the beginning of the experiment. Along with the experimental proceeding, phytotoxicity was alleviated after the incorporation of nano-materials. The ryegrass biomass was significantly higher with nano-materials application. Consequently, the Pb phytoextraction potential of ryegrass significantly increased with nano-materials application compared to the gounps without nano-materials application. The total removal rates of soil Pb were higher after combined application of NHAP than NCB. NHAP is more suitable than NCB for in-situ remediation of Pb-contaminated soils. The ryegrass translocation factor exhibited a marked increase with time. It was thought that the major role of NHP and NBA might be to alleviate the Pb phytotoxicity and increase biomass of plants., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Mouse is an acceptable animal model to measure lead (Pb) relative bioavailability (RBA) in contaminated soils; however, there is a lack of comparisons among Pb-RBA measurements based on different endpoints and dosing approaches. In this study, 12 soils (47.8-8123mg Pbkg -1 ) were assessed for Pb-RBA using Pb accumulation in mouse liver, kidneys, and/or femur following a 10-d steady state soil dose via diet, with 6 soils being measured using mouse bioassays with area under the mouse blood Pb concentration time curve (AUC) following a single gavaged dose as the endpoint. Based on individual endpoints of the steady state method, Pb-RBA in soils was 2.1-83.4%, being generally consistent among liver, kidneys, and femur with strong linear correlations between them (r 2 =0.74-0.89). To compensate variation in Pb distribution among different tissues, Pb-RBA was further calculated using a combined endpoint (e.g., sum of Pb accumulation in liver, kidneys, and femur). Compared to Pb-RBA based on individual tissue showing relative standard deviation (RSD) of 11.9-15.8%, Pb-RBA using the combined endpoint showed lower RSD (10.8%), thereby being more robust. For the 6 soils with Pb-RBA based on both mouse single gavaged and steady state dosing approach, no significant difference was observed; however, steady state approach was more repeatable among animals with lower RSD (11.4% vs. 34.5%). To ensure robustness of in vivo data, the steady state dosing approach with Pb accumulation in combined tissues is recommended., (Published by Elsevier B.V.)

Accidental ingestion of contaminated soil has been recognized as an important pathway of human exposure to lead (Pb), especially for children through hand-to-mouth activities. Intake of food following the soil ingestion may affect the bioaccessibility of Pb in the gastrointestinal tract. In this study, the effect of steamed bread on the transformation and subsequent bioaccessibility of Pb in two soils was determined by the physiologically based extraction test (PBET). Two compounds, Pb(NO 3 ) 2 and PbCO 3 , were included in the evaluation for comparison. In the gastric phase, Pb bioaccessibility decreased as the steamed bread increased due to the sorption of Pb on the undissolved steamed bread, especially in PbCO 3 , Pb bioaccessibility decreased from 95.03% to 85.40%. Whereas in the intestinal phase, Pb bioaccessibility increased from 1.85% to 5.66% and from 0.89% to 1.80% for Pb(NO 3 ) 2 and PbCO 3 , respectively. The increase was attributed to the transformation of formed Pb carbonates into soluble organic-Pb complexes induced by the dissolved steamed bread at neutral pH as indicated by MINTEQ modeling. For the PbCO 3 -contaminated soil, the change in Pb bioaccessibility in both gastric and intestinal phases behaved like that in the pure PbCO 3 compound, the steamed bread increased the bioaccessibility of Pb in the intestinal phase, but the decreased bioaccessibility of Pb was observed in the gastric phase after the steamed bread was added. However, in the soil contaminated with free Pb 2+ or sorbed Pb forms, the steamed bread increased the Pb bioaccessibility in both gastric and intestinal phases. This was probably due to the higher dissolved organic carbon induced transformation of sorbed Pb (Pb sorbed by Fe/Mn oxides) into soluble Pb-organic complex. Results from this study indicated that steamed bread had an influence on the Pb speciation transformation, correspondingly affecting Pb bioaccessibility in the gastrointestinal tract., (Copyright © 2016. Published by Elsevier Inc.)

The mineral body exploited in Salafossa (Eastern Dolomites) was one of the largest lead/zinc-containing mineral deposits in Europe. Both metals were mainly present as sulphides (sphalerite, ZnS and galena, PbS). Mining activity started around 1550, but it was only around 1960 that the richest veins of the minerals were discovered. The mine closed in 1985, and concentrations of several trace metals, such as thallium (Tl), iron (Fe), manganese (Mn), lead (Pb) and zinc (Zn), were detected in the soils and plant samples (Biscutella laevigata L.) that were collected from eighteen sites selected outside the mine. B. laevigata is a pseudometallophyta species, and it often grows near mining areas where the soil's metal concentrations are significantly higher than those of soil with a natural geochemical background. The total metal concentrations in the plant tissue (roots and leaves of Biscutella laevigata) and in the soil samples - both bulk-soil and the B. laevigata root system (rhizo-soil) - were determined through Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES). The metal extractability and leachability of the soil samples were estimated using soil extractions with DTPA (Diethylenetriaminepentaacetic acid). In addition, metal mobility caused by rainwater runoff was estimated by using a leaching test with a dilute solution of H 2 SO 4 and HNO 3 . The results showed that metals were present in a chemical form available for uptake by the plants' roots. In fact, high concentrations of the metals were also found in the plant tissue (roots and leaves) of B. laevigata, and these concentrations were higher than those whose soils present natural geochemical background levels in the corresponding rhizo-soil. Thus, B. laevigata has shown a marked ability to bioaccumulate trace metals, especially Tl and, to a lesser extent, Zn, Pb, Fe and Mn, and it can influence metal mobility in the rhizo-soil. To assess the uptake and translocation processes of the trace metals, resulting in their bioaccumulation, two different indices were calculated: the enrichment factor in roots (EFr), as the ratio between the metal concentration in belowground biomass and in the respective rhizo-soil, and the translocation factor (TF), as the ratio between the metal concentration in the leaves and the corresponding roots. For both indices, values > 1 denoted enrichment of the metal in the roots or its translocation to the upper tissues. The results showed that EFr and TF were considerably high only for Tl, reaching a maximum value of 60 for EFr and 11.6 for TF. Conversely, the other investigated metals did not show significant bioaccumulation (EFr < 1), and they showed TF > 1 only at a few sites., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Extensive contamination of grassland with cadmium (Cd), lead (Pb) and zinc (Zn) is a typical problem close to Pb/Zn smelter sites. The entry of Cd or Pb into the food chain is very likely, as are toxicity effects of Zn in plants. Previous promising results from pot and field experiments showed the high potential of using amendments for immobilisation to reduce metal input into the food chain via crops grown on smelter-contaminated soils at Arnoldstein (Austria) (Friesl et al., 2006). The aim of this study was to find a practical solution for large-scale contaminations in hilly regions that avoids erosion. Field application of amendments without destroying the vegetation cover (grassland) involved two approaches: (a) slurrying (Slu) the amendments into cut gaps in the vegetation cover and (b) injecting (Inj) the amendments through the vegetation cover. Here, we investigate the immobilising and long-term efficiency of treatments [gravel sludge (2.5%) + red mud (0.5%) (GS + RM)]. Risk assessment was based on soil, plant and water samples taken over a period of 10 years. Ammonium-nitrate-extractable Cd was reduced up to 50%, Pb up to 90%, and Zn over 90%. Plant uptake into the grass mixture and narrow leaf plantain was significantly reduced for Cd, Pb, and Zn. Harvesting early in vegetation period can further reduce uptake and meet the threshold for fodder crops. The reduction of these elements in the seepage water in 24 samplings within these 10 years reached 40%, 45% and 50%, respectively. Immobilisation increased microbial biomass and decreased human bioaccessibility for Pb. Our investigation of the long-term efficiency of GS + RM in all treatments shows that the Slu and Inj amendment application techniques have promising potential as a realistic and practical method for extensively contaminated hilly land. Slurrying performed best. We conclude that grassland remediation methods involving tillage are counterproductive from the viewpoint of bioaccessibility and soil protection and therefore should be avoided., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

A systematic investigation into cadmium (Cd) and lead (Pb) concentrations and their oral bioaccessibility in market vegetables in the Pearl River Delta region were carried out to assess their potential health risks to local residents. The average concentrations of Cd and Pb in six species of fresh vegetables varied within 0.09-37.7 and 2.3-43.4 μg kg -1 , respectively. Cadmium and Pb bioaccessibility were 35-66 % and 20-51 % in the raw vegetables, respectively, and found to be significantly higher than the cooked vegetables with 34-64 % for Cd and 11-48 % for Pb. The results indicated that Cd bioaccessibility was higher in the gastric phase and Pb bioaccessibility was higher in the small intestinal phase (except for fruit vegetables). Cooking slightly reduced the total concentrations and bioaccessibility of Cd and Pb in all vegetables. The bioaccessible estimated daily intakes of Cd and Pb from vegetables were far below the tolerable limits.

In this study, a high efficiency and low cost biochar-supported nano-hydroxyapatite (nHAP@BC) material was used in the remediation of lead (Pb)-contaminated soil. The remediation effect of nHAP@BC on Pb-contaminated soil was evaluated through batch experiments. The stability, bioaccessibility of Pb in the soil and the change in soil characteristics are discussed. Furthermore, the effects of the amendments on the growth of cabbage mustard seedlings and the accumulation of Pb were studied. The results showed that the immobilization rates of Pb in the soil were 71.9% and 56.8%, respectively, after a 28 day remediation using 8% nHAP and nHAP@BC materials, and the unit immobilization amount of nHAP@BC was 5.6 times that of nHAP, indicating that nHAP@BC can greatly reduce the cost of remediation of Pb in soil. After the nHAP@BC remediation, the residual fraction Pb increased by 61.4%, which greatly reduced the bioaccessibility of Pb in the soil. Moreover, nHAP@BC could effectively reduce the accumulation of Pb in plants by 31.4%. Overall, nHAP@BC can effectively remediate Pb-contaminated soil and accelerate the recovery of soil fertility., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Biochar derived from various materials has been investigated with regard to its ability to decrease the bioavailability of heavy metals in contaminated soils, and thus reduce their potential to enter the food chain. However, little attention has been given to the adsorption capacity of untreated crop straws, which are commonly used as a biochar feedstock, especially in soils. Hence, this study was conducted to investigate the effect of crop straws on heavy metal immobilization and subsequent heavy metal uptake by maize and ryegrass in a soil artificially polluted by Cd and Pb. Bamboo biochar, rice straw, and wheat straw were mixed into soil four weeks before the experiment, enabling them to reach equilibrium at 2% (w/w), 1% (w/w), and 1% (w/w), respectively. The results showed that soil pH for both species was significantly increased by all treatments, except when wheat straw was used for ryegrass cultivation. Soil organic carbon was only improved in the rice straw treatment and the soil alkali-hydrolyzable N content was significantly decreased with all of the amendments, which may have contributed to the lack of an effect on plant biomass. Soil available Cd was significantly lower in the rice straw treatment than in the control soil, while Pb levels clearly decreased in wheat straw treatment. The Cd concentration in shoots of maize was reduced by 50.9%, 69.5%, and 66.9% with biochar, rice straw, and wheat straw, respectively. In addition, shoot Cd accumulation was decreased by 47.3%, 67.1%, and 66.4%, respectively. Shoot Pb concentration and accumulation were only reduced with the rice straw treatment for both species. However, metal uptake in plant roots was more complex, with increased metal concentrations also detected. Overall, the direct application of crop straw could be considered a feasible way to immobilize selected metals in soil, once the long-term effects are confirmed., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Secondary metabolites play important roles in plant interactions with the environment. The co-occurrence of heavy metal contamination of soils and rising atmospheric CO2 has important effects on plant. It is important to explore the ways in which production of plant secondary metabolites is affected by heavy metals under elevated atmospheric CO2. We examined the effects of elevated CO2 on secondary metabolite contents in Robinia pseudoacacia seedlings grown in Cd- and lead (Pb)-contaminated soils. The increase in secondary metabolites was greater under Cd + Pb exposure than under exposure to individual metals regardless of elevated CO2 with the exception of condensed tannins in leaves and total alkaloids in stems. Except for phenolic compounds and condensed tannins, elevated CO2 was associated with increased secondary metabolite contents in leaves and stems of plants exposed to Cd, Pb, and Cd + Pb compared to plants exposed to ambient CO2 + metals. Changes in saponins in leaves and alkaloids in stems were greater than changes in the other secondary metabolites. Significant interactive effects of CO2, Cd, and Pb on secondary metabolites were observed. Saponins in leaves and alkaloids in stems were more sensitive than other secondary metabolites to elevated CO2 + Cd + Pb. Elevated CO2 could modulate plant protection and defense mechanisms in R. pseudoacacia seedlings exposed to heavy metals by altering the production of secondary metabolites. The increased Cd and Pb uptake under elevated CO2 suggested that R. pseudoacacia may be used in the phytoremediation of heavy metal-contaminated soils under global environmental scenarios., (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.)

The leaf litters of tree species, Acacia pycnantha (Ap) and Eucalyptus camaldulensis (Ec), predominantly growing at an abandoned copper (Cu) mine and mine soils including controls, were assessed for determining the metal toxicity and bioavailability using earthworm species Eisenia fetida, in a microcosm. Significant reduction in body weight as well as mortality were observed when the worms were introduced into mine soil or its combination with mine Ap litter. Virtually, there were no juveniles when the worms were fed on substratum that contained mine soil or mine leaf litter. The extent of bioaccumulation was dependent on water-soluble fraction of a metal in soil. The accumulation of cadmium, lead and copper in worm tissue was significantly more in treatments that received mine soil with or without mine leaf litter. However, the tissue concentration of zinc did not differ much in earthworms irrespective of its exposure to control or contaminated samples. Mine leaf litter from Ec, a known Cu hyperaccumulator, was more hospitable to earthworm survival and juvenile than that of Ap litter. Validation of the data on bioaccumulation of metals indicated that the mine leaf litter significantly contributed to metal bioavailability. However, it was primarily the metal concentration in mine soil that was responsible for earthworm toxicity and bioavailability. Our data also indicate that detrivores like earthworm is greatly responsible for heavy metal transfer from mines into the ecosystem., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Lead (Pb) in soil is an important exposure source for children. Thus, determining bioavailability of Pb in soil is critical in evaluating risk and selecting appropriate strategies to minimize exposure. A mouse model was developed to estimate relative bioavailability of Pb in NIST SRM 2710a (Montana 1 Soil). Based on Pb levels in tissues, the mean relative bioavailability of this metal in this soil was 0.5. Estimates of relative bioavailabilities derived from mouse compared favorably with those obtained in juvenile swine. The mouse model is thus an efficient and inexpensive method to obtain estimates of relative bioavailability of soil Pb.

A study of the concentrations of zinc and lead in an engineered soil capping system overlying sulphide mine tailings was undertaken. Tailings geochemistry, soil cover and vegetation were monitored over a 4-year period, and a cattle grazing demonstration exercise was conducted over a 1-year period. Whilst the tailings had a relatively high pyrite content and demonstrated oxidation, a circum neutral pH was observed for the duration of the study period due to the high dolomitic content. No evidence of metal mobility into the soil cover and vegetation was observed over the monitoring period. Relatively high Zn herbage content is attributed to the glacial till component of the soil cover. Similarly, no evidence of metal transfer to grazing cattle was observed through blood and tissue analysis with Zn content not significantly different from control animals. Pb tissue content was below limit of detection.