Biochars, when applied to contaminated solutions or soils, may sequester potentially toxic elements while releasing necessary plant nutrients. This purpose of this study focused on quantifying both phenomenon following wheat straw (Triticum aestivum L.) biochar application (0, 5, and 15% by wt) to a Cd containing solution and a Cd-contaminated paddy soil using 240-day laboratory batch experiments. Following both experiments, solid phases were analyzed for elemental associations using a combination of wet chemical sequential extractions and synchrotron-based X-ray absorption spectroscopy (XAS). When wheat straw biochar was applied at 15% to Cd containing solutions, Cd and Zn concentrations decreased to below detection in some instances, Ca and Mg concentrations increased by up to 290%, and solution pH increased as compared to the 5% biochar application rate. Similar responses were observed when biochar was added to the Cd-contaminated paddy soil, suggesting that this particular biochar has the ability to sequester potentially toxic elements while releasing necessary plant nutrients to the soil solution. When significant, positive correlations existed between nutrient release over time, while negative correlations were present between biochar application rate, potentially toxic element sorption and pH. The latter suggests that potentially toxic elements were sorbed by a combination of organic functional groups or mineral precipitation based on whether pH was above or below ~ 7. In support of this contention, the wet chemical sequential extraction procedure in conjunction with previously observed Cd or current Zn XAS showed that biochar application promoted the formation of layered double hydroxides, sorption to (oxy)hydroxides, and organically bound to biochar as Zn species. As a multi-functional material, biochar appears to play an important role in sequestering Cd while releasing essential plant nutrients. These findings suggest that biochar may be a ‘win–win’ for improving environmental quality in potentially toxic element contaminated agroecosystems.

In this study, a novel method for lead (Pb) immobilization was developed in contaminated soils using iron (III) (Fe3+) in conjunction with 0.05 M H2SO4. During method optimization, a range of microwave treatment times, solid to solution ratios, and Fe2(SO4)3/H2SO4 concentrations were assessed using a mining/smelting impacted soil (BHK2, Pb: 3031 mg/kg), followed by treatment of additional Pb contaminated soils (PP, Pb: 1506 mg/kg, G10, Pb: 2454 mg/kg and SoFC-1, Pb: 6340 mg/kg) using the optimized method. Pb bioaccessibility was assessed using USEPA Method 1340, with Pb speciation determined by X-ray Absorption (XAS) spectroscopy. Treatment efficacy was also validated using an in vivo mouse assay, where Pb accumulation in femur, kidney and liver was assessed to confirm in vitro bioaccessibility outcomes. Results showed that Pb bioaccessibility could be reduced by 77.4-97.0% following treatment of soil with Fe2(SO4)3 (0.4-1.0 M), H2SO4 (0.05 M) at 150 degrees C for 60 min in a closed microwave system. Results of bioavailability assessment demonstrated treatment effect ratio of 0.06-0.07 in femur, 0.06-0.27 in kidney and 0.06-0.11 in liver (bioavailability reduction between 73% and 93%). Formation of plumbojarosite in treated soils was confirmed by XAS analysis.

Exposure to lead (Pb) during early life has persistent adverse health effects. During childhood, ingestion of bioavailable Pb in contaminated soils can be a major route of Pb absorption. Remediation to alter physiochemical properties of soil-borne Pb can reduce Pb bioavailability. Our laboratory-based approach for soil Pb remediation uses addition of iron (Fe) sulfate and application of heat to promote formation of plumbojarosite (PLJ), a sparingly soluble Pb-Fe hydroxysulfate mineral. We treated two soils with anthropogenic Pb contamination and samples of clean topsoil spiked with various Pb compounds (i.e., carbonate, chloride, phosphate [P], or sulfate) to convert native Pb species to PLJ and used a mouse assay to assess relative bioavailability (RBA) of Pb in untreated (U) and remediated soils. Bone and blood Pb levels were significantly lower (P < 0.001, Student's t test) in mice that consumed diets amended with remediated soils than with U soils. Estimated RBA for Pb in both remediated natural soils and Pb-mineral spiked soils were reduced by >90% relative to Pb RBA for U soils, which is substantially more effective than other soil amendments, including P. X-ray absorption spectroscopy showed that >90% of all Pb species in remediated soils were converted to PLJ, and ingested PLJ was not chemically transformed during gastrointestinal tract transit. Post treatment neutralization of soil pH did not affect PLJ stability, indicating the feasibility in field conditions. These results suggest that formation of PLJ in contaminated soils can reduce the RBA of Pb and minimize this medium's role as a source of Pb exposure for young children.

Effects of dietary P level on the oral bioavailability of Pb present in soil were examined in a mouse model. Adult female C57BL/6 mice had free access to AIN-93G purified rodent diet amended with Pb as a soluble salt, Pb acetate, or in a soil matrix (NIST SRM 2710a). In these studies, the basal diet contained P at a nutritionally sufficient level (0.3% w/w) and the modified diets contained P at a lower (0.15%) or a higher (1.2%) level. For either dietary Pb source (Pb acetate or NIST SRM 2710a), low dietary P level markedly increased accumulation of Pb in bone, blood, and kidney. Tissue Pb levels in mice fed a high P in diet were not different from mice fed the basal P diet. Dietary P and Pb interacted to affect body weight change and feed efficiency in mice. The relative contribution of different Pb species in diet and feces was also affected by dietary P level. Differences in Pb species between diet and feces indicated that transformation of Pb species can occur during gastrointestinal tract transit. These interactions between Pb and P that alter Pb speciation may be important determinants of the bioavailability of Pb ingested in soil.

Lead (Pb) exposure from household dust is a major childhood health concern because of its adverse impact on cognitive development. This study investigated the absorption kinetics of Pb from indoor dust following a single dose instillation into C57BL/6 mice. Blood Pb concentration (PbB) was assessed over 24 h, and the dynamics of particles in the lung and gastro-intestinal (GI) tract were visualized using X-ray fluorescence (XRF) microscopy. The influence of mineralogy on Pb absorption and particle retention was investigated using X-ray absorption near-edge structure spectroscopy. A rapid rise in PbB was observed between 0.25 and 4 h after instillation, peaking at 8 h and slowly declining during a period of 24 h. Following clearance from the lungs, Pb particles were detected in the stomach and small intestine at 4 and 8 h, respectively. Analysis of Pb mineralogy in the residual particles in tissues at 8 h showed that mineral-sorbed Pb and Pb-phosphates dominated the lung, while organic-bound Pb and galena were the main phases in the small intestines. This is the first study to visualize Pb dynamics in the lung and GI tract using XRF microscopy and link the inhalation and ingestion pathways for metal exposure assessment from dust.

Cadmium contamination in waters and soils can lead to food chain accumulation and ultimately deterioration in human health; means for reducing bioavailable Cd are desperately required, and biochars may play a role. Long-term (240 d) lab incubation experiments were utilized to explain wheat straw-derived biochar effects on Cd sorption and decreasing Cd bioavailability in soils and solutions (0, 5, and 15% biochar as wt:wt or wt:vol, respectively), and to identify Cd forms present using both the European Community Bureau of Reference (BCR) chemical sequential extraction procedure and synchrotron-based X-ray absorption spectroscopy (XAS). Biochar Cd removal was up to ~90% from Cd-containing solutions and contaminated soil as compared to the control. Based on the wet chemical sequential extraction procedure in conjunction with XAS, biochar application promoted the formation of (oxy)hydroxide, carbonate, and organically bound Cd phases. As a material, biochar may be promoted as a tool for reducing and removing bioavailable Cd from contaminated waters and soils. Thus, biochar may play a role in reducing Cd bioaccumulation, trophic transfer, and improving environmental quality and human health.

With similar chemistry, Mn and Fe interact in their many essential roles in plants but the magnitude and mechanisms involved of these interactions are poorly understood. Leaves of soybean (a Mn-sensitive species) developed a mild chlorosis and small dark spots and distorted trifoliate leaves with 30 μM Mn and 0.6 μM Fe in nutrient solution (pH 5.6; 3 mM ionic strength). At 0.6 μM Fe, lower alternate leaves of sunflower (a Mn-tolerant species) were chlorotic at 30 μM Mn and had a pale chlorosis and necrosis at 400 μM Mn. A concentration of 30 and 300 μM Fe in solution alleviated these typical symptoms of Mn toxicity and decreased the concentration of Mn from >3000 to ca. 800 mg kg-1 dry mass (DM) in all leaf tissues. As expected, increased Fe supply increased Fe in leaves from <100 up to 1350 mg Fe kg-1 DM. In situ synchrotron-based X-ray fluorescence microscopy showed that increased Fe supply caused an overall decrease in Mn in the leaf tissue but had little effect on the pattern of its distribution. Similarly, X-ray absorption spectroscopy identified only slight effects of Fe supply on Mn speciation in leaf tissues. Thus, the results of this study indicate that increased Fe supply ameliorated Mn toxicity in soybean and sunflower largely through decreased Mn uptake and translocation to leaf tissues rather than through changes in Mn distribution or speciation within the leaves.

Effects of different treatments on the bioavailability of lead (Pb) in soil from a smelter emission contaminated site in Joplin, Missouri, were evaluated in a mouse model. Similar estimates of relative bioavailability for Pb in untreated or treated soil were obtained in mice and in the well-established juvenile swine model. In the mouse model, treatments that used phosphate (phosphoric acid or triple superphosphate) combined with iron oxide or biosolids compost significantly reduced soil Pb bioavailability. Notably, effects of these remediation procedures were persistent, given that up to 16 years had elapsed between soil treatment and sample collection. Remediation of soils was associated with changes in Pb species present in soil. Differences in Pb species in ingested soil and in feces from treated mice indicated that changes in Pb speciation occurred during transit through the gastrointestinal tract. Use of the mouse model facilitates evaluation of remediation procedures and allows monitoring of the performance of procedures under laboratory and field conditions.

Bioavailability research of soil metals has advanced considerably from default values to validated in vitro bioaccessibility (IVBA) assays for site-specific risk assessment. Previously, USEPA determined that the soil-size fraction representative of dermal adherence and consequent soil ingestion was <250 μm. This size fraction was widely used in testing efforts for both in vivo and in vitro experiments. However, recent studies indicate the <150-μm size fraction better represents the particle size that adheres to skin for potential ingestion. At issue is the relevance of validated in vivo and in vitro methods developed with <250 μm moving to the <150-μm fraction. The objectives of this study were to investigate <250-μm versus <150-μm particle size and particle size groups for evaluating lead (Pb) and arsenic (As) IVBA and speciation. Soils with different properties were homogenized, oven dried, and sieved: <250 to > 150, <150 to >75, <75 to >38, and <38 μm. Sieved versus ground subsamples of <250-μm and <150-μm bulk soils were also used for IVBA and synchrotron-based Pb and As speciation. Although we observed an increase in total and IVBA-extractable Pb and As with decreased soil particle size, changes in %IVBA of Pb and As (dependent on the ratio extractable:total) remained consistent in all of the tested soils. No significant changes in Pb and As speciation were observed across the soil fractions. The results suggest that using the more relevant <150-μm fraction will not undermine currently validated IVBA protocols in future bioavailability studies.