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Naturally selenium (Se)-rich soils often contain elevated cadmium (Cd) levels, complicating safe production of Se-enriched rice. This study employed diffusive gradients in thin-films (DGT) and DGT-induced fluxes in soils (DIFS) model to determine Se and Cd bioavailability in paddy soils. We investigated desorption kinetics and accumulation patterns in rice using paired rhizosphere and grain samples from 65 field sites in Guangxi, China, encompassing Se-enriched karst and non-karst soils. Despite greater total Se and Cd contents in karst soils, their elevated pH, along with greater soil organic matter and total Fe, Mn, and Ca contents, constrained Se and Cd bioavailability, resulting in similar accumulation levels in rice grains from both soil categories. DIFS-derived kinetic data revealed that Se was replenished 75.4 times faster than Cd, but Cd had an 83.2 times larger labile pool, leading to a stronger overall Cd resupply capacity. DGT-based labile Se:Cd molar ratios showed that rice Cd content declined sharply as the ratio increased from 0.7 to 4.0, stabilizing at its lowest level when exceeding 20. Moreover, DGT measurements demonstrated stronger correlations with grain Se and Cd concentrations compared to traditional methods. Our findings highlight the effectiveness of DGT and kinetic analyses in determining Se and Cd bioavailability in high-background paddy soils, offering insights for balancing Se fortification and Cd risk mitigation in rice production., 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 © 2024 Elsevier Ltd. All rights reserved.)

Recent results revealed that considerable Pb accumulation in plants is possible under specific soil conditions that make Pb phytoavailable. In this review, the sources and transformations of Pb in soils, the interaction of Pb with bacteria and specifically the microbiota in the soil, factors and mechanisms of Pb uptake, translocation and accumulation in plants and Pb toxicity in living organisms are comprehensively elaborated. Specific adsorption and post-adsorption transformations of Pb in soil are the main mechanisms affecting the mobility, bioavailability, and toxicity of Pb. The adsorption ability of Pb largely depends on the composition and properties of soils and environmental conditions. Microbial impact on Pb mobility in soil and bioavailability as well as bacterial resistance to Pb are considered. Specific mechanisms conferring Pb-resistance, including Pb-efflux, siderophores, and EPS, have been identified. Pathways of Pb entry into plants as well as mechanisms of in planta Pb transport are poorly understood. Available evidence suggests the involvement of Ca transporters, organic acids and the phytochelatin pathway in Pb transport, mobility and detoxification, respectively., 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 © 2022 Elsevier B.V. All rights reserved.)

Reducing lead (Pb) exposure via oral ingestion of contaminated soils is highly relevant for child health. Elevating dietary micronutrient iron (Fe) intake can reduce Pb oral bioavailability while being beneficial for child nutritional health. However, the practical performance of various Fe compounds was not assessed. Here, based on mouse bioassays, ten Fe compounds applied to diets (100-800 mg Fe kg -1 ) reduced Pb oral relative bioavailability (RBA) in two soils variedly depending on Fe forms. EDTA-FeNa was most efficient, which reduced Pb-RBA in a soil from 79.5 ± 14.7 % to 23.1 ± 2.72 % (71 % lower) at 100 mg Fe kg -1 in diet, more effective than other 9 compounds at equivalent or higher doses (3.6-68 % lower). When EDTA-FeNa, ferrous gluconate, ferric citrate, and ferrous bisglycinate were supplemented, Fe-Pb co-precipitation was not observed in the intestinal tract. EDTA-FeNa, ferrous gluconate, ferric citrate, and ferrous sulfate suppressed duodenal divalent metal transporter 1 (DMT1)mRNA relative expression similarly (27-68 % lower). In comparison, among ten compounds, EDTA-FeNa elevated Fe concentrations in mouse liver, kidney, and blood (1.50-2.69-fold higher) most efficiently, suggesting the most efficient Fe absorption that competed with Pb. In addition, EDTA was unique from other organic ligands, ingestion of which caused 12.0-fold higher Pb urinary excretion, decreasing Pb concentrations in mouse liver, kidney, and blood by 68-88 %. The two processes (Fe-Pb absorption competition and Pb urinary excretion with EDTA) interacted synergistically, leading to the lowest Pb absorption with EDTA-FeNa. The results provide evidence of a better inhibition of Pb absorption by EDTA-FeNa, highlighting that EDTA-FeNa may be the most appropriate supplement for intervention on human Pb exposure. Future researches are needed to assess the effectiveness of EDTA-FeNa for intervention on human Pb exposure., 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 © 2022 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Replant problem is widespread in agricultural production and causes serious economic losses, which has limited sustainable cultivation of Panax notoginseng (PN), a well-known medicinal plant in Asia. Here we conducted a field experiment to investigate the effectiveness and possible mechanisms of biochar to improve its survival under continuous cropping. Biochar from tobacco stems was applied at 4 rates of 9.0, 12, 15, and 18 t/ha to a soil where PN has been continuously cultivated for 10 years. After 18 months, soil properties, 5 allelochemicals, including p-hydroxybenzoic acid, vanillic acid, syringic acid, p-coumaric acid, and ferulic acid, key pathogen Fusarium oxysporum, microbial community, and PN survival rate were investigated. Our results show that 10 years' continuous PN cropping led to soil acidification, accumulation of NH 4 -N and F. oxysporum, and low PN survival rate. However, biochar increased its survival rate from 6.0% in the control to 69.5% under 15 t/ha treatment. Moreover, soil pH, available P and K, organic matter content, and microbial diversity were increased while NH + -N and allelochemicals vanillic acid and syringic acid contents were decreased under biochar treatment (P<0.05). Soil available K increased from 177 to 283 mg·kg 4 + -N and allelochemicals vanillic acid and syringic acid contents were decreased under biochar treatment (P<0.05). Soil available K increased from 177 to 283 mg·kg -1 under 15 t/ha treatment. Further, soil pH, available P and K, and microbial diversity (bacteria and fungi) were positively correlated with PN survival rate, however, NH 4 -N content was negatively correlated (P<0.05). Our study indicates that biochar effectively increased the survival rate of Panax notoginseng under continuous cropping by improving soil properties and microbial diversity.+ -N decreased from 6.73 to 4.79 mg·kg -1 under 15 t/ha treatment. Further, soil pH, available P and K, and microbial diversity (bacteria and fungi) were positively correlated with PN survival rate, however, NH 4 + -N content was negatively correlated (P<0.05). Our study indicates that biochar effectively increased the survival rate of Panax notoginseng under continuous cropping by improving soil properties and microbial diversity., 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 © 2022 Elsevier B.V. All rights reserved.)

Abnormally high concentrations of metals including nickel (Ni) in soils result from high geochemical background (HB) or anthropogenic contamination (AC). Metal bioaccessibility in AC-soils has been extensively explored, but studies in HB-soils are limited. This study examined the Ni bioaccessibility in basalt and black shale derived HB-soils, with AC-soils and soils without contamination (CT) being used for comparison. Although HB- and AC-soils had similar Ni levels (123 ± 43.0 vs 155 ± 84.7 mg kg -1 ), their Ni bioaccessibility based on the gastric phase of the Solubility Bioaccessibility Research Consortium (SBRC) in vitro assay was different. Nickel bioaccessibility in HB-soils was 6.42 ± 3.78%, 2-times lower than the CT-soils (12.0 ± 9.71%) and 6-times lower than that in AC-soils (42.6 ± 16.3%). Based on the sequential extraction, a much higher residual Ni fractionation in HB-soils than that in CT- and AC-soils was observed (81.9 ± 9.52% vs 68.6 ± 9.46% and 38.7 ± 16.0%). Further, correlation analysis indicate that the available Ni (exchangeable + carbonate-bound + Fe/Mn hydroxide-bound) was highly correlated with Ni bioaccessibility, which was also related to the organic carbon content in soils. The difference in co-localization between Ni and other elements (Fe, Mn and Ca) from high-resolution NanoSIMS analysis provided additional explanation for Ni bioaccessibility. In short, based on the large difference in Ni bioaccessibility in geochemical background and anthropogenic contaminated soils, it is important to base contamination sources for proper risk assessment of Ni-contaminated soils., (Copyright © 2022 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.)

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous organic contaminants, with soil being the most important sink. This study determined the concentrations, bioaccessibility and spatial distributions of 6 emerging PAHs in Orlando and Tampa urban soils. They included 3 carcinogenic (anthanthrene, 7H-benzo[c]fluorene, and dibenzo[a,l]pyrene: 3cPAHs) and 3 non-carcinogenic (dibenzo[a,e]pyrene, dibenzo[a,i]pyrene and dibenzo[a,h]pyrene) PAHs. Based on benzo[a]pyrene-equivalent, the 7 USEPA priority cPAHs (7cPAHs) and 3cPAHs in Orlando soils averaged 452 and 7387 μg kg -1 , and Tampa soils 802 and 4943 μg kg -1 , respectively, with ∑3cPAHs being 6-16 times greater than ∑7cPAHs. Based on ArcGIS maps, the concentrations of ∑3cPAHs in commercial sites, business district and heavy-traffic areas were higher. The concentrations of ∑3cPAHs have not been reported, but they had significant impacts on risk assessment of urban soils due to their high relative potency factor. However, their bioaccessibility based on n-butanol extraction in soils of both cities were low, averaging 3.4-7.4%. Therefore, to accurately assess the risk of soils contaminated with PAHs, emerging cPAHs together with USEPA 7cPAHs and their bioaccessibility need to be considered., (Copyright © 2019. Published by Elsevier B.V.)

Phosphorus (P) is a critical element affecting eutrophication in aquatic ecosystems. Its availability is closely related to calcium (Ca) in calcareous soils and sediments, but their relations are unclear. In this study, the spatial and temporal changes in P and Ca fractionation and distribution in a karst farmland-wetland ecosystem were investigated. The results showed that total P concentrations were 1.25-3.19 g kg -1 , with higher concentrations in paddy soil than in sediment. Total Ca concentrations were 3.93-10.2 g kg -1 , with higher Ca being accumulated in sediments than in soils. The P fractionations varied seasonally, with Ca-bound P being dominant. The moderately-stable Fe/Al-bound P showed temporal variation, while Ca was dominant in acid-soluble fraction, both probably playing an important role in controlling P availability. Correlation analysis showed seasonal relation between Ca and P distribution in soil/sediment. This study suggests that P migration from farmland to wetland may be a major source for P accumulation in sediments in a karst farmland-wetland system., (Published by Elsevier Ltd.)

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous organic contaminants, which are found in soils throughout the U.S. The objective of this study was to determine the background concentrations, distributions, and sources of 16 USEPA priority PAHs in two urban soils. A total of 114 soil samples were collected from two large cities in Florida: Orlando and Tampa. The results showed that soils were dominated by high molecular weight PAHs in both cities. The average ∑16-PAHs in Orlando and Tampa soils were 3227 and 4562 μg kg -1 , respectively. The averages of 7 carcinogenic PAHs based on the benzo[a]pyrene-equivalent (BaP-EQ) concentrations in the two cities were 452 and 802 μg kg -1 . BaP-EQ concentrations in 60-62% of samples were higher than the Florida Soil Cleanup Target Level (FSCTL) for residential soils at 100 μg kg -1 and 20-25% of samples were higher than FSCTL for industrial soils at 700 μg kg -1 . Based on molecular diagnostic ratios and PMF modeling, major sources of soil PAHs in both cities were similar, mainly from pyrogenic sources including vehicle emissions, and biomass and coal combustion. Based on ArcGIS mapping, PAH concentrations in soils near business districts and high traffic roads were higher. Thus, it is important to consider background PAH concentrations in urban soils when considering soil remediation., (Published by Elsevier Ltd.)

The ability of As-hyperaccumulator Pteris vittata to remove As from two contaminated soils (CCA from an As-treated wood facility and DVA from a cattle-dipping vat) over 5 years was investigated for the first time. The goal was to evaluate P. vittata's ability to continuously remove As during 10 harvests and identify how soil As was affected by P. vittata under P-sufficient (P-fertilizer) and P-limiting (phosphate rock) conditions. Sequential extraction was used to determine changes in metal distribution among different soil fractions. The high frond biomass production occurred on the 9th (62.1-63.9 and 35.6-63.5 g plant -1 ) and 10th harvest (58.6-60.7 and 51.9-57.1 g plant -1 ) for CCA and DVB soils, though frond As concentration decreased. Soil arsenic removal averaged 7-10% per harvest during the 1-6th harvests and was reduced to 0-3% during the 7-10th harvests for DVA and CCA soils. Arsenic from all fractions, excluding the residual fraction, was affected by plant uptake. The largest reduction occurred in the amorphous fraction of CCA-soil at 64-66% (61.2-61.5 to 20.8-21.8 mg kg -1 ) and in the crystalline fraction of DVA-soil at 50-86% (2.18-4.35 to 0.61-1.10 mg kg -1 ). Soil As concentrations were reduced by 37-47% from 26.7 to 129 to 15.6-16.8 and 68.9-70.1 mg kg -1 for the DVA and CCA soils, respectively. Our data indicated that P. vittata efficiently solubilized non-labile As under P-limiting conditions without impacting its As depletion., (Published by Elsevier Ltd.)

In this study, bioavailability of polychlorinated biphenyls (PCBs) in soil samples aged for various time intervals (7 days, 1 and 5 months) was assessed by in vivo tests using mice. The in vivo bioavailability of PCBs in soil ranged from 45% (PCB180 in soil aging for 5 month) to 119% (PCB52 in soil aging for 1 month), indicating that not all PCBs was available for absorption after ingestion of soil samples. The bioaccessibility was assessed using both physiologically-based extraction test (PBET) and Tenax improved PBET (TI-PBET). Acceptable in vivo-in vitro correlation (r 2  = 0.70 and slope = 1.30 ± 0.20) was observed for TI-PBET, not for PBET. Due to dominant role played by Tenax and bile, the TI-PBET was further simplified to Tenax and Tenax-bile extraction methods. However, poor in vivo-in vitro correlation (r 2  = 0.14 and 0.05) was observed for the two simplified methods, which may be attributed to the combined effect between sorption sink and components in PBET. Therefore, in order to simply TI-PBET or standardize in vitro methods, it is highly necessary to explore the mechanism about the interaction between in vitro method components and sorption sink, or to screen key factors for bioaccessibility results in the future studies., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Arsenic (As) in soils is often adsorbed on Fe-(hydro)oxides surface, rendering them more resistant to dissolution, which is undesirable for phytoremediation of As-contaminated soils. Arsenic hyperaccumulator Pteris vittata prefers to grow in calcareous soils where available Fe and As are low. To elucidate its mechanisms of acquiring Fe and As from insoluble sources in soils, we investigated dissolution of goethite with pre-adsorbed arsenate (AsV; As-goethite) in presence of four organic ligands, including two root exudates (oxalate and phytate, dominant in P. vittata) and two microbial siderophores (PG12-siderophore and desferrioxamine B). Their presence increased As solubilization from As-goethite from 0.03 to 0.27-5.33 mg L -1 compared to the control. The siderophore/phytate bi-ligand treatment released 7.42 mg L -1 soluble Fe, which was 1.2-fold that of the sum of siderophore and phytate, showing a synergy in promoting As-goethite dissolution. In the ligand-mineral-plant system, siderophore/phytate was most effective in releasing As and Fe from As-goethite. Moreover, the continuous plant uptake induced more As-goethite dissolution. The continued release of As and Fe significantly enhanced their plant uptake (from 0.01 to 0.43 mg plant -1 As and 2.7-14.8 mg plant -1 Fe) and plant growth (from 1.2 to 3.1 g plant -1 fw) in P. vittata. Since microbial siderophores and root exudates often coexist in soil rhizosphere, their synergy in enhancing dissolution of insoluble As-Fe minerals may play an important role in efficient phytoremediation of As-contaminated soils., (Copyright © 2017 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.)

Using in vitro bioaccessibility assays to predict Pb relative bioavailability (RBA) in contaminated soils has been demonstrated, however, limited research was performed on urban soils having lower Pb levels. In this study, 162 soils from urban parks in 27 capital cities in China were measured for Pb bioaccessibility using the SBRC assay, with Pb-RBA in 38 subsamples being measured using a mouse-kidney assay. Total Pb concentrations in soils were 9.3-1198 mg kg(-1), with 92% of the soils having Pb concentrations <100 mg kg(-1). Lead bioaccessibility in soils was 20-94%, increasing with Pb concentration up to 100 mg kg(-1) (r = 0.44), however, limited variability in Pb bioaccessibility (60-80%) was observed for soils with Pb > 100 mg kg(-1). On the basis of a stable isotope fingerprinting technique, coal combustion ash was identified as the major Pb source, contributing to the increased Pb bioaccessibility with increasing soil Pb concentration. Lead-RBA in soils was 17-87%, showing a strong linear correlation with Pb bioaccessibility (r(2) = 0.61), with cross validation of the correlation based on random subsampling and leave-one-out approaches yielding low prediction errors. On the basis of the large sample size of 38 soils, this study demonstrated that the Pb-RBA predictive capability of the SBRC assay can be extended from mining/smelting impacted soils to urban soils with lower Pb levels.

This study investigated the relationship between Pb relative bioavailability (RBA) and bioaccessibility, and their relationships with Pb in different pools in soils. Twelve Pb-contaminated soils representing different contamination sources from China were analyzed for Pb bioaccessibility using four in vitro methods (UBM, SBRC, IVG, and PBET), Pb-RBA using a mouse blood model, and Pb fractionation using sequential extraction. Lead bioaccessibility in the gastric phase (GP) and Pb-RBA was generally lower in mining soils (0.46-29% and 7.0-26%) than smelting (19-92% and 31-84%) and farming soils (13-99% and 51-61%), with more Pb in the residual fraction in mining soils. Lead bioaccessibility varied with assays, with SBRC (3.0-99%) producing significantly higher bioaccessible Pb than other assays (0.46-84%) in the gastric phase. However, Pb bioaccessibility in the intestinal phase (IP) of all assays sharply decreased to 0.01-20% possibly due to Pb sorption to solid phase at higher pH. Lead bioaccessibility by UBM-GP assay was best correlated with Pb-RBA (r(2) = 0.67), followed by IVG-GP (r(2) = 0.55). Among different Pb fractions, strong correlation was found between Pb bioaccessibility/Pb-RBA and the sum of exchangeable and carbonate fractions. Our study suggested that UBM-GP assay has potential to determine Pb bioaccessibility in contaminated soils in China., (Published by Elsevier B.V.)

Tree islands are habitat for wading birds and a characteristic landscape feature in the Everglades. A total of 93 surface soil and 3 soil core samples were collected from 7 degraded/ghost and 34 live tree islands. The mean Hg concentration in surface soils of ghost tree islands was low and similar to marsh soil. For live tree islands, Hg concentrations in the surface head region were considerably greater than those in mid and tail region, and marsh soils. Hg concentrations in bird guano (286 μg kg(-1)) were significantly higher than those in mammal droppings (105 μg kg(-1)) and plant leaves (53 μg kg(-1)). In addition, Hg concentrations and δ(15)N values displayed positive correlation in soils influenced by guano. During 1998-2010, estimated annual Hg deposition by guano was 148 μg m(-2) yr(-1) and ~8 times the atmospheric deposition., (Published by Elsevier Ltd.)

This study investigated the impacts of two best management practices (BMPs) recommended by US Environmental Protection Agency on Pb weathering and leachability in shooting range soils. The two BMPs included replacing soil berm with sand berm and periodically removing bullets or shot from a berm. A column experiment corresponding to the first BMP was conducted by mixing the bullets with sand/soil, or placing bullets on the surface of sand/soil. After a 16-18-week incubation under high or low rainfall simulations, total Pb concentrations in sand were lower than that in soil. Total leachable Pb in sand (8.48 and 5.52 μg kg(-1)) was also lower than that in soil (60.0 and 30.4 μg kg(-1)) when bullets were mixed with sand/soil; however, they were comparable when bullets were placed on the sand/soil surface. These results indicate that lower Pb concentration in the sand than in soil may be attributed to reduced weathering of bullets. Mechanical removal of Pb bullets in the field transferred Pb from large to finer particles, increasing total Pb in the soil (<2 mm) from 2,170 to 5,000 mg kg(-1). In contrast, mechanical removal of Pb shot effectively reduced the shot in the soil by 86-92 %. Thus, we concluded that, while replacing soil berm with sand berm can slow down Pb weathering, it may increase Pb leachability in the long term. Removal of Pb bullets and Pb shot can be effective, but caution needs to be exercised to minimize the adverse impacts, especially in pistol/rifle ranges because of increased total Pb content in the soil.

Arsenate interferes with enzymatic processes and inhibits inorganic phosphorus (Pi) uptake in many plants. This study examined the role of phytase and phosphatase in arsenate tolerance and phosphorus (P) acquisition in the arsenic hyperaccumulator Pteris vittata . Enzyme-mediated hydrolysis of phytate in P. vittata extracts was not inhibited by arsenate at 5 mM or by heating at 100 °C for 10 min. Root exudates of P. vittata exhibited the highest phytase activity (18 nmol Pi mg(-1) protein min(-1)) when available P was low, allowing its growth on media amended with phytate as the sole source of P. Phosphorus concentration in P. vittata gametophyte tissue grown on phytate was equivalent to plants grown with inorganic phosphate at 2208 mg kg(-1), and arsenic was increased from 1777 to 2630 mg kg(-1). After 2 h of mixing with three soils, P. vittata phytase retained more activity, decreasing from ∼ 26 to ∼ 25 nmol Pi mg(-1) protein min(-1), whereas those from Pteris ensiformis and wheat decreased from ∼ 18 to ∼ 1 nmol Pi mg(-1) protein min(-1). These results suggest P. vittata has a uniquely stable phytase enabling its P acquisition in P-limiting soil environments. Furthermore, the P. vittata phytase has potential use as a soil amendment, a transgenic tool, or as a feed additive supplement, reducing the need for nonrenewable, polluting P fertilizers.

It is important to examine mechanisms of Pb and Cd sorption in soils to understand their bioavailability. The ability of three tropical soils to retain Pb, Cd, and Ca was evaluated. The objectives of this study were to (1) determine the extent to which soil sorption sites are metal specific, (2) investigate the nature of reactions between metals and soil surfaces, and (3) identify how metals compete for sorption sites when they are introduced to soils sequentially or concurrently. Lead was shown to be much less exchangeable than Cd and inhibited Cd sorption. Cadmium had little effect on Pb sorption, though both Ca and Cd inhibited the adsorption of Pb at exchange sites. Lead appears to more readily undergo inner-sphere surface complexation with soil surface functional groups than either Cd or Ca. Thus, regardless of when Pb is introduced to a soil, it should be less labile than Cd.

This greenhouse experiment evaluated the influence of arsenic uptake by arsenic hyperaccumulator Pteris vittata L. and non-arsenic hyperaccumulator Nephrolepis exaltata L. on arsenic chemistry in bulk and rhizosphere soil. The plants were grown for 8 weeks in a rhizopot with a soil containing 105 mg kg(-1) arsenic. The soil arsenic was fractionated into five fractions with decreasing availability: non-specifically bound (N), specifically bound (S), amorphous hydrous-oxide bound (A), crystalline hydrous-oxide bound (C), and residual (R). P. vittata produced larger plant biomass (7.38 vs. 2.32 mg plant(-1)) and removed more arsenic (2.61 vs. 0.09 mg pot(-1) arsenic) than N. exaltata. Plant growth reduced water-soluble arsenic, and increased soil pH (P. vittata only) in the rhizosphere soil. P. vittata was more efficient than N. exaltata to access arsenic from all fractions (39-64% vs. 5-39% reduction). However, most of the arsenic taken up by both plants was from the A fraction (67-77%) in the rhizosphere soil, the most abundant (61.5%) instead of the most available (N fraction).

Leaching of arsenic (As) from chromated copper arsenate (CCA)-treated wood may elevate soil arsenic levels. Thus, an environmental concern arises regarding accumulation of As in vegetables grown in these soils. In this study, a greenhouse experiment was conducted to evaluate As accumulation by vegetables from the soils adjacent to the CCA-treated utility poles and fences and examine the effects of soil amendments on plant As accumulation. Carrot (Daucus carota L.) and lettuce (Lactuca sativa L.) were grown for ten weeks in the soil with or without compost and phosphate amendments. As expected, elevated As concentrations were observed in the pole soil (43 mg kg(-1)) and in the fence soil (27 mg kg(-1)), resulting in enhanced As accumulation of 44 mg kg(-1) in carrot and 32 mg kg(-1) in lettuce. Addition of phosphate to soils increased As accumulation by 4.56-9.3 times for carrot and 2.45-10.1 for lettuce due to increased soil water-soluble As via replacement of arsenate by phosphate in soil. However, biosolid compost application significantly reduced plant As uptake by 79-86%, relative to the untreated soils. This suppression is possibly because of As adsorbed by biosolid organic mater, which reduced As phytoavailability. Fractionation analysis showed that biosolid decreased As in soil water-soluble, exchangeable, and carbonate fraction by 45%, whereas phosphate increased it up to 2.61 times, compared to the untreated soils. Our results indicate that growing vegetables in soils near CCA-treated wood may pose a risk of As exposure for humans. Compost amendment can reduce such a risk by reducing As accumulation by vegetables and can be an important strategy for remediating CCA-contaminated soils. Caution should be taken for phosphate application since it enhances As accumulation.

Chinese brake fern (Pteris vittata L.), an arsenic (As) hyperaccumulator, has shown the potential to remediate As-contaminated soils. This study investigated the effects of soil amendments on the leachability of As from soils and As uptake by Chinese brake fern. The ferns were grown for 12 weeks in a chromated-copper-arsenate (CCA) contaminated soil or in As spiked contaminated (ASC) soil. Soils were treated with phosphate rock, municipal solid waste, or biosolid compost. Phosphate amendments significantly enhanced plant As uptake from the two tested soils with frond As concentrations increasing up to 265% relative to the control. After 12 weeks, plants grown in phosphate-amended soil removed >8% of soil As. Replacement of As by P from the soil binding sites was responsible for the enhanced mobility of As and subsequent increased plant uptake. Compost additions facilitated As uptake from the CCA soil, but decreased As uptake from the ASC soil. Elevated As uptake in the compost-treated CCA soil was related to the increase of soil water-soluble As and As(V) transformation into As(III). Reduced As uptake in the ASC soil may be attributed to As adsorption to the compost. Chinese brake fern took up As mainly from the iron-bound fraction in the CCA soil and from the water-soluble/exchangeable As in the ASC soil. Without ferns for As adsorption, compost and phosphate amendments increased As leaching from the CCA soil, but had decreased leaching with ferns when compared to the control. For the ASC soil, treatments reduced As leaching regardless of fern presence. This study suggest that growing Chinese brake fern in conjunction with phosphate amendments increases the effectiveness of remediating As-contaminated soils, by increasing As uptake and decreasing As leaching.

To assess the efficiency of P-induced metal immobilization in soils, a pilot-scale field experiment was conducted at a metal contaminated site located in central Florida. Phosphate was applied at a P/Pb molar ratio of 4.0 with three treatments: 100% of P from H3PO4, 50% of P from H3PO4+ 50% of P from Ca(H2PO4)2, and 50% of P from H3PO4+5% phosphate rock in the soil. Approximately 1 year after P application, soil and plant samples were collected to determine mobility and bioavailability of selected metals (Pb, Zn, and Cu) using sequential extraction procedure and mineralogical characterization using X-ray diffraction (XRD) and scanning electron microscope-energy dispersive X-ray (SEM-EDX) analysis. Phosphorus distribution and soil pH effects were also evaluated. Phosphate was more effective in transforming soil Pb (to 53%) from the non-residual to the residual phase than soil Zn (to 15%) and soil Cu (to 13%). This was because Pb was immobilized by P via formation of an insoluble pyromorphite-like mineral in the surface and subsurface of the soil, whereas no phosphate mineral Zn or Cu was identified. While P amendment enhanced metal uptake in the roots of St. Augustine grass (Stenotaphrum secundatum), it significantly reduced metal translocation from root to shoot, especially Pb via formation of a pyromorphite-like mineral on the membrane surface of the root. A mixture of H3PO4 and phosphate rock was effective in metal immobilization, with less soil pH reduction and less soluble P. Although H3PO4 was effective in immobilizing Pb, its use should be limited to minimize soil pH reduction and potential eutrophication risk.

Soil amendments can be used to cost-effectively reduce the bioavailability and mobility of toxic metals in contaminated soils. In this study a field demonstration was conducted at a Pb-contaminated site to evaluate the effectiveness of P-induced Pb immobilization. Phosphate was applied at a 4.0 molar ratio of P to Pb with three treatments: T1, 100% of P from H3PO4; T2, 50% P from H3PO4 + 50% P from Ca(H2PO4)2; and T3, 50% P from H3PO4 + 5% phosphate rock. Phosphate amendments effectively transformed soil Pb from the nonresidual (sum of exchangeable, carbonate, Fe/Mn, and organic) to the residual fraction, with residual Pb increase by 19-48% for T1, 22-50% for T2, and 11-55% for T3, respectively. Lead immobilization was attributed to the P-induced formation of chloropyromorphite [Pb10(PO4)6Cl2], which was identified in the surface soil, subsurface soil, and plant rhizosphere soil. Occurrence of chloropyromorphite was evident 220 days after P addition for T1 and T2 treatments and 330 days for T3. Visual MINTEQ model and activity-ratio diagram indicated that lead phosphate minerals controlled Pb2+ activities in the P-treated soils. Phosphate treatments significantly reduced Pb translocation from the roots to the shoots in the St. Augustine grass (Stenotaphrum secundatum), possibly via the formation of chloropyromorphite on the cell walls of roots. This field observation suggested that P amendments are efficient in reducing Pb mobility via in situ formation of insoluble chloropyromorphite minerals at a field setting. Lead immobilization shows a long-term stability. A mixture of H3PO4 and phosphate rock yields the best overall results for in situ Pb immobilization, with less soil pH change and less P leaching. Application of combined H3PO4 with phosphate rock may provide an effective alternative to the current phosphate remediation technologies for contaminated soils.

Colloid transport in subsurface has received considerable attention recently because mobile colloids can facilitate the transport of heavy metals in soils to contaminate groundwater. Many studies on colloid mobility in the subsurface consider soils as well-defined porous media. Though similar in many aspects, soils are different from well-defined porous media. The authors emphasize the impacts of soil properties on soil-colloid deposition, release, and association with heavy metals to provide an overview of colloidal dynamics in natural soils. The electrical double layer and Derjaguin-Landau-Verwey-Overbeek (DVLO) theories are summarized in Section II as theoretical bases for further discussions of colloid dynamics in soils, and their interactions with heavy metals. After discussions of theory developments and experimental results on the characteristics of soil colloids in Section III and soil porous media in Section IV, the authors compares the deposition of colloidal particles in well-defined porous media with that in natural soils in Section V. In Section VI, processes that affect colloid release in soils are summarized and theories of ion transfer processes in soils during colloid release are reviewed and discussed. Finally, the authors give a brief overview of the adsorption and precipitation of heavy metals to soil colloidal particles and their influences on colloid surface charge development in Section VII. The authors conclude with remarks on the importance of colloid deposition and release in soils and their association with heavy metals. [ABSTRACT FROM AUTHOR]

This greenhouse study examined the root characteristics (biomass, length, area, and diameter) and root uptake efficiency of Pteris vittata, an arsenic (As) hyperaccumulator and Nephrolepis exaltata, not an As hyperaccumulator, in relation to plant uptake of As and nutrients in an As-contaminated and a control soil. After 8 weeks of growth, on a per plant basis, P. vittata accumulated 7.3-8.8 g of biomass and removed 2.51 mg of As from the As-contaminated soil compared to 2.4-2.7 g of biomass and 0.09 mg of As for N. exaltata. This was partially because P. vittata developed a more extensive root system, 2.4-3.8 times greater (biomass, length, and area), and possessed a greater proportion of fine roots than N. exaltata. In addition, the As root-uptake efficiency (defined as As concentrations in plant tissue per unit root) for fronds of P. vittata was 15-23 times greater than that of N. exaltata in both soils. Whereas N. exaltata removed phosphorus (P) more efficiently from the soils, P. vittata removed As more efficiently. The larger root biomass coupled with more efficient root-uptake systems for As may have contributed to As hyperaccumulation by P. vittata. [ABSTRACT FROM AUTHOR]

The use of lead bullets and shot at shooting ranges is under increasing scrutiny as a potentially significant source of Pb pollution. This study assessed Pb contamination in the soils of two shooting ranges (TRR and MPR) in Florida. Soil samples were collected from the two ranges and analyzed for total Pb to determine Pb contamination. Selected spent bullets and berm soil samples were mineralogically characterized to identify Pb transformation. Total Pb in the range soils was significantly elevated with the highest (up to 4.84% by weight) in the berm soils. Most soils failed the synthetic precipitation leaching procedure (SPLP) test. Also, at the MPR shooting range, a substantial amount of Pb migrated down in the subsurface soil, possibly due to the enhanced solubilization of organic Pb complexes at alkaline pH, whereas high cation exchange capacity of the profile soil may be responsible for Pb retention in the subsoil. The weathering products on the surface of the spent bullets were predominantly hydrocerussite [Pb3(CO3)2(OH)2] and cerussite (PbCO3). Hydrocerussite was mainly found in the MPR range soils, whereas Pb was transformed into hydroxypyromorphite [Pb5(PO4)3OH] in the TRR range soils because of the presence of more P. Sequential extraction and lead activity ratio modeling showed that the soil Pb solubility was controlled by Pb carbonate minerals in the MPR shooting range, and by less soluble Pb phosphate minerals in the TRR shooting range. This research suggests that it is important to develop and implement efficient management practices to minimize adverse impacts of Pb at shooting ranges. Phosphate-induced Pb immobilization may be an effective alternative for reducing Pb mobility in the shooting range soils. [Copyright &y& Elsevier]

Few studies have assessed As bioaccessibility in housedust using different in vitro assays and compared to those in contaminated soils. We determined As bioaccessibility in 24 housedust samples (4.48–38.2 mg kg −1 ) using SBRC, IVG, DIN, and PBET assays and they averaged 73, 68, 53, and 48% in the gastric phase and 26, 46, 55 and 43% in the intestinal phase of the 4 assays. The corresponding As bioaccessibility in 34 As-contaminated soils (22–6899 mg kg −1 ) were 34, 25, 22, and 22% in the gastric phase and 18, 19, 21, and 20% in the intestinal phase, which was 1.5–2.7 fold lower than those in housedust possibly due to differences in contamination sources and properties. Based on the gastric phase of SBRC assay, As bioaccessibility was 44–96% in housedust and 2.3–80% in soils. Variation in As bioaccessibility among assays was similar for housedust and soils, with SBRC assay providing the highest bioaccessibility in gastric phase. In intestinal phase, dissolved As was probably adsorbed onto precipitated iron oxides, causing a sharp decrease in As bioaccessibility by SBRC assay. Unlike SBRC assay, gastric constituents (pepsin, mucin, phosphate, and citrate) in other 3 assays inhibited As adsorption and/or enhanced As dissolution, leading to greater As bioaccessibility. The greater As bioaccessibility in housedust than soil suggests the potential of greater health risk from As exposure to housedust than soil. [ABSTRACT FROM AUTHOR]

Abstract: The two dimensional, small-scale, distribution of labile trace metals was investigated in a sandy loam soil historically treated with sewage sludge. After deployment of two DGT (diffusive gradients in thin-films) probes, their 1.8×15cm windows were sliced into 5×5mm and 5×8mm rectangles to provide three vertical profiles with 5mm resolution. Both sets of profiles showed sharp maxima of Mn, Cd, Co, Cu, Ni and Zn, which varied systematically, both vertically and horizontally. The observed mobilisation of metals was highly localised, as each measurement corresponded to a volume of soil as little as 25–40μL. Regression analysis indicated mobilisation of Cd, Co, Cu, Ni and Zn were strongly linked to mobilisation of Mn, while there was a strong linkage between Pb and Fe mobilisation. Localised reductive dissolution of Mn oxides or a localised lowering of pH were considered as possible mechanisms. [Copyright &y& Elsevier]