Determining the fate of lead (Pb) and phosphorus (P) in alkaline Pb-polluted soils amended with P and acidified using multiple synchrotron-based techniques.

The effect of acidification on lead (Pb) and phosphorus (P) speciation in alkaline Pb-polluted soils that are amended with P to stabilize Pb is still unclear. It was studied in three alkaline Pb-polluted soils containing specific amounts of Soil Organic Matter (SOM), using multiple synchrotron-based techniques, i.e. bulk X-ray Absorption Fine Structure (XAFS) spectroscopy at Pb LIII- and P K-edges, micro-X-ray Fluorescence (µ-XRF), and micro-X-ray Diffraction (µ-XRD). These techniques provided unambiguous evidences that the formation of pyromorphite, i.e. the desired Pb stabilized chemical form, was severely limited in the acidified soil samples amended with fish bones or phosphoric acid (H3PO4). Most Pb present in the H3PO4-amended soil samples did not convert to pyromorphite due to Pb and P leaching and PbSO4(s) formation. In contrast, most Pb present in the fish bone-amended soil samples was unaffected by acidification and did not convert to pyromorphite as it was inaccessible to soil solution or retained by SOM, similarly to P. Additionally, Pb-SOM association increased with increasing SOM content. Results had important implications on the applicability of the P-based method to stabilize Pb within the first centimeters below surface of Pb-polluted alkaline soils, which potentially represent the most hazardous part of these soils.

Lead Speciation and Association with Organic Matter in Various Particle-Size Fractions of Contaminated Soils.

Lead (Pb) stabilization in polluted soils treated by a Pb immobilization technique may be dependent on the speciation of Pb present in specific particle-size fractions of the soil. However, the scale-dependency of Pb speciation in contaminated soils is still not clearly understood. In this study, the natures and amounts of Pb chemical forms were determined in five Pb-polluted soil samples from Klity Village, Thailand, and their particle-size fractions. This was achieved using multiple analytical tools, including bulk extended X-ray absorption fine structure (EXAFS) spectroscopy at the Pb LIII edge. Results suggested that cerussite, Pb sorbed to goethite, and Pb-humate were present in specific amounts in all bulk samples and their particle-size fractions. The highest amounts of Pb-humate were found in the smallest particles of the soil samples. This Pb form was present in the fine particles of a soil sample, but remained undetected when analyzing the bulk sample. Since Pb-SOM association may impede the formation of pyromorphite in soils, the results implied that the extent of Pb immobilization in a polluted soil treated by P may be less than predicted if Pb speciation is only characterized at the macroscopic scale from the bulk soil sample prior remediation.

A field-scale study of cadmium phytoremediation in a contaminated agricultural soil at Mae Sot District, Tak Province, Thailand: (1) Determination of Cd-hyperaccumulating plants.

The cadmium (Cd) phytoremediation capabilities of Gynura pseudochina, Chromolaena odorata, Conyza sumatrensis, Crassocephalum crepidioides and Nicotiana tabacum were determined by conducting in-situ experiments in a highly Cd-contaminated agricultural field at Mae Sot District, Tak Province, Thailand. Most of these five plant species, which are commonly found in Thailand, previously demonstrated Cd-hyperaccumulating capacities under greenhouse conditions. This study represented an important initial step in determining if any of these plants could, under field-conditions, effectively remove Cd from the Mae Sot contaminated fields, which represent a health threat to thousands of local villagers. All plant species had at least a 95% survival rate on the final harvest day. Additionally, all plant species, except C. odorata, could hyperaccumulate the extractable Cd amounts present in the soil, based on their associated Bioaccumulation Factor (BAF), Translocation Factor (TF), and background Vegetation Factor (VF). Therefore, the four Cd-hyperaccumulating plant species identified in this study may successfully treat a majority of contaminated fields at Mae Sot, as it was previously reported that Cd amounts present in a number of these soils were mostly available.

Speciation and release kinetics of zinc in contaminated paddy soils.

Zinc is an important nutrient for plants, but it can be toxic at high concentrations. The solubility and speciation of Zn is controlled by many factors, especially soil pH and Eh, which can vary in lowland rice culture. This study determined Zn speciation and release kinetics in Cd-Zn cocontaminated alkaline and acidified paddy soils, under various flooding periods and draining conditions, by employing synchrotron-based techniques and a stirred-flow kinetic method. Results showed almost no change in Zn speciation and release kinetics in the two soils, although the soils were subjected to different flooding periods and draining conditions. The mineral phases in which Zn is immobilized in the soil samples were constrained by linear least squares fitting (LLSF) analyses of bulk X-ray absorption fine structure (XAFS) spectra. Only two main phases were identified by LLSF, i.e., Zn-layered double hydroxides (Zn/Mg-hydrotalcite-like, and ZnAl-LDH) and Zn-phyllosilicates (Zn-kerolite). Under all soil pHs, flooding, and draining conditions, less than 22% of Zn was desorbed from the soil after a two-hour desorption experiment. The information on Zn chemistry obtained in this study will be useful in finding the best strategy to control Cd and Zn bioavailability in the Cd-Zn cocontaminated paddy soils.

Speciation and release kinetics of cadmium in an alkaline paddy soil under various flooding periods and draining conditions.

This study determined Cd speciation and release kinetics in a Cd-Zn cocontaminated alkaline paddy soil, under various flooding periods and draining conditions, by employing synchrotron-based techniques, and a stirred-flow kinetic method. Results revealed that varying flooding periods and draining conditions affected Cd speciation and its release kinetics. Linear least-squares fitting (LLSF) of bulk X-ray absorption fine structure (XAFS) spectra of the air-dried, and the 1 day-flooded soil samples, showed that at least 50% of Cd was bound to humic acid. Cadmium carbonates were found as the major species at most flooding periods, while a small amount of cadmium sulfide was found after the soils were flooded for longer periods. Under all flooding and draining conditions, at least 14 mg/kg Cd was desorbed from the soil after a 2-hour desorption experiment. The results obtained by micro X-ray fluorescence (µ-XRF) spectroscopy showed that Cd was less associated with Zn than Ca, in most soil samples. Therefore, it is more likely that Cd and Ca will be present in the same mineral phases rather than Cd and Zn, although the source of these two latter elements may originate from the same surrounding Zn mines in the Mae Sot district.