No abstract

The use of arsenic (As) contaminated groundwater for irrigation of crops has resulted in elevated concentrations of arsenic in agricultural soils in Bangladesh, West Bengal (India), and elsewhere. Paddy rice (Oryza sativa L.) is the main agricultural crop grown in the arsenic-affected areas of Bangladesh. There is, therefore, concern regarding accumulation of arsenic in rice grown those soils. A greenhouse study was conducted to examine the effects of arsenic-contaminated irrigation water on the growth of rice and uptake and speciation of arsenic. Treatments of the greenhouse experiment consisted of two phosphate doses and seven different arsenate concentrations ranging from 0 to 8 mg of As L(-1) applied regularly throughout the 170-day post-transplantation growing period until plants were ready for harvesting. Increasing the concentration of arsenate in irrigation water significantly decreased plant height, grain yield, the number of filled grains, grain weight, and root biomass, while the arsenic concentrations in root, straw, and rice husk increased significantly. Concentrations of arsenic in rice grain did not exceed the food hygiene concentration limit (1.0 mg of As kg(-1) dry weight). The concentrations of arsenic in rice straw (up to 91.8 mg kg(-1) for the highest As treatment) were of the same order of magnitude as root arsenic concentrations (up to 107.5 mg kg(-1)), suggesting that arsenic can be readily translocated to the shoot. While not covered by food hygiene regulations, rice straw is used as cattle feed in many countries including Bangladesh. The high arsenic concentrations may have the potential for adverse health effects on the cattle and an increase of arsenic exposure in humans via the plant-animal-human pathway. Arsenic concentrations in rice plant parts except husk were not affected by application of phosphate. As the concentration of arsenic in the rice grain was low, arsenic speciation was performed only on rice straw to predict the risk associated with feeding contaminated straw to the cattle. Speciation of arsenic in tissues (using HPLC-ICP-MS) revealed that the predominant species present in straw was arsenate followed by arsenite and dimethylarsinic acid (DMAA). As DMAA is only present at low concentrations, it is unlikely this will greatly alter the toxicity of arsenic present in rice.

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Pyromorphite (Pb5(PO4)3Cl), the most stable lead mineral under a wide range of geochemical conditions [1], can form in urban and industrially contaminated soils [2] [3] [4] [5]. It has been suggested that the low solubility of this mineral could reduce the bioavailability of lead, and several studies have advocated pyromorphite formation as a remediation technique for lead-contaminated land [3] [5] [6], if necessary using addition of phosphate [6]. Many microorganisms can, however, make insoluble soil phosphate bioavailable [7] [8] [9] [10], and the solubilisation of insoluble metal phosphates by free-living and symbiotic fungi has been reported [11] [12] [13] [14] [15]. If pyromorphite can be solubilised by microbial phosphate-solubilising mechanisms, the question arises of what would happen to the released lead. We have now clearly demonstrated that pyromorphite can be solubilised by organic-acid-producing fungi, for example Aspergillus niger, and that plants grown with pyromorphite as sole phosphorus source take up both phosphorus and lead. We have also discovered the production of lead oxalate dihydrate by A. niger during pyromorphite transformation, which is the first recorded biogenic formation of this mineral. These mechanisms of lead solubilisation, or its immobilisation as a novel lead oxalate, have significant implications for metal mobility and transfer to other environmental compartments and organisms. The importance of considering microbial processes when developing remediation techniques for toxic metals in soils is therefore emphasised.

Arsenic speciation was determined in Lumbricus rubellus Hoffmeister from arsenic-contaminated mine spoil sites and an uncontaminated site using HPLC-MS, HPLC-ICP-MS and XAS. It was previously demonstrated that L. rubellus from mine soils were more arsenate resistant than from the uncontaminated site and we wished to investigate if arsenic speciation had a role in this resistance. Earthworms from contaminated sites had considerably higher arsenic body burdens (maximum 1,358 mg As kg-1) compared to the uncontaminated site (maximum 13 mg As kg-1). The only organo-arsenic species found in methanol/water extracts for all earthworm populations was arsenobetaine, quantified using both HPLC-MS and HPLC-ICP-MS. Arsenobetaine concentrations were high in L. rubellus from the uncontaminated site when concentrations were expressed as a percentage of the total arsenic burden (23% mean), but earthworms from the contaminated sites with relatively low arsenic burdens also had these high levels of arsenobetaine (17% mean). As arsenic body burden increased, the percentage of arsenobetaine present decreased in a dose dependent manner, although its absolute concentration rose with increasing arsenic burden. The origin of this arsenobetaine is discussed. XAS analysis of arsenic mine L. rubellus showed that arsenic was primarily present as As(III) co-ordinated with sulfur (30% approx.), with some As(v) with oxygen (5%). Spectra for As(III) complexed with glutathione gave a very good fit to the spectra obtained for the earthworms, suggesting a role for sulfur co-ordination in arsenic metabolism at higher earthworm arsenic burdens. It is also possible that the disintegration of As(III)-S complexes may have taken place due to (a) processing of the sample, (b) storage of the extract or (c) HPLC anion exchange. HPLC-ICP-MS analysis of methanol extracts showed the presence of arsenite and arsenate, suggesting that these sulfur complexes disintegrate on extraction. The role of arsenic speciation in the resistance of L. rubellus to arsenate is considered.

Calcium-rich pyromorphite [Pb5(P04)3Cl] has been positively identified as the major lead-bearing phase in mine-waste soils from the South Pennine Orefield, UK, by a combination of EXAFS spectroscopy, ATEM and XRD. Evidence for a pyromorphite-like structure was provided by electron diffraction of individual Ca-rich, lead chlorophosphate grains in the soil using ATEM. Approximate unit-cell parameters derived from electron diffraction were used to identify peaks on the powder XRD trace obtained from the soil sample, allowing the cell parameters to be refined. The unit-cell parameters derived for the Ca-rich pyromorphite [a = 0.9789 (7), c = 0.726( 1) nm] are smaller than those reported for pure end-member pyromorphite (a = 0.998, c = 0.733 nm; Baker, 1966) and are sufficiently different to prevent positive identification by conventional XRD analysis. Lead absorption spectra and interatomic distances obtained from EXAFS performed on bulk soils confirmed the predominance of pyromorphite-like structure. EXAFS is shown to be a useful tool in the identification of soil minerals. It gives information about the local environment of one specific element in solids, be they crystalline or amorphous, and is unaffected by the limited chemical substitution of Ca for Pb.The identification of impure Pb minerals in soil by techniques other than XRD suggests that previous studies, based on XRD, may have underestimated the amount of soil Pb present as discrete Pb compounds.

Garden soil and housedust samples, from households in a Derbyshire village closely associated with historic lead mining, have highly elevated lead levels. Handwipe samples from children also have relatively high lead concentrations suggesting that elevated levels of lead are transferred to the child by the soil-dust-hand-mouth pathway. However, this is not reflected in their blood lead concentrations which are within normal UK ranges and less than predicted by some lead exposure models. SEM analysis of soil grains has revealed that many are composed of pyromorphite [Pb5(PO4)3Cl], a stable soil-lead mineral. This mineral is formed from the weathering of galena [PbS] but it is not clear to what extent weathering has occurred in the soil. Pyromorphite has an extremely low solubility which may contribute to a low human bioavailability of lead in these soils, resulting in the lower than expected blood lead concentrations.

The ability of bonemeal additions (finely ground, poorly crystalline apatite, [Ca 10 (PO 4 ) 6 OH 2 ]) to immobilize pollutant metals in soils and reduce metal bioavailability through the formation of metal phosphates has been evaluated. Leaching column experiments were carried out on contaminated soils with pH varying between 2.7 and 7.1. Monitoring of leachates over a three month period indicated that bonemeal additions resulted in the immobilization of metals and an increase in the pH of the column leachate, the soil pore water and the soils themselves. Analytical scanning electron microscopy of the bonemeal treated soil at the end of the experiment revealed that Pb and Zn were associated with phosphorus. X-ray diffraction identified several newly formed phases in the bonemeal treated soil at the end of the experiments that had peaks of similar intensity and positions as reference Pb and Ca-Zn phosphates. Batch experiments and subsequent extraction of metals from controls and bonemeal amended soils using 0.01 M CaCl 2 and DTPA indicated that bonemeal additions reduced the availability of the metals in the soils.Bonemeal amendments appear to have potential as a remediation treatment for metal contaminated soils.