Satya P. Singh

Phosphate-induced metal immobilization in a contaminated site

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.

Field demonstration of in situ immobilization of soil Pb using P amendments

A long-term field-scale demonstration project on the feasibility of using P to immobilize Pb in a Pb-contaminated urban soil was conducted. Phosphate was applied at an average rate of 3040 mg P/kg soil based on a P/Pb molar ration of 4.0, with four treatments: T0, no P application; T1, H3PO4 only; T2, 1/2 H3PO4+1/2 CaH2PO4; and T3, 1/2 H3PO4+1/2 phosphate rock. Soil samples were collected and analyzed 220 days after the P applications. For all P treatments, toxicity characteristic leaching procedure (TCLP) extractable Pb levels in surface soils (0–10 cm) were reduced to below 5.0 mg Pb/l, with T2 also effective in reducing the TCLP Pb level in subsurface soils (10–30 cm, <4.63 mg/l). Sequential extraction analysis indicates that P was effective in transforming soil Pb from non-residual fractions to a residual fraction. Such a transformation was mainly through dissolution of Pb associated with carbonate fraction and precipitation of pyromorphite-like minerals, which were confirmed using X-ray diffraction (XRD). Among these three treatments, T3 was the most effective in reducing Pb mobility and minimizing P and Pb leaching in the soil. Our research clearly demonstrates that P amendments were effective in immobilizing Pb in contaminated soil.

The Chemical Nature of Mercury in Human Brain Following Poisoning or Environmental Exposure

Methylmercury is among the most potentially toxic species to which human populations are exposed, both at high levels through poisonings and at lower levels through consumption of fish and other seafood. However, the molecular mechanisms of methylmercury toxicity in humans remain poorly understood. We used synchrotron X-ray absorption spectroscopy (XAS) to study mercury chemical forms in human brain tissue. Individuals poisoned with high levels of methylmercury species showed elevated cortical selenium with significant proportions of nanoparticulate mercuric selenide plus some inorganic mercury and methylmercury bound to organic sulfur. Individuals with a lifetime of high fish consumption showed much lower levels of mercuric selenide and methylmercury cysteineate. Mercury exposure did not perturb organic selenium levels. These results elucidate a key detoxification pathway in the central nervous system and provide new insights into the appropriate methods for biological monitoring.

Leaching behaviour of Cd, Cu, Pb and Zn in surface soils derived from dredged sediments

Leaching of heavy metals from land-disposed dredged sediment spoils is a potential environmental hazard. The leaching behavior of Cd, Cu, Pb and Zn in surface soils sampled from abandoned dredged sediment disposal sites was assessed. Using simple mass-balance calculations, the significance of the leaching test results with respect to metal migration into underlying clean soil was appraised. The potential leachability, defined as the amounts released at constant pH 4, decreased in the order (% of total contents): Zn (58%) approximately equal to Cd (49%)>Cu (5%) approximately equal to Pb (2%). The kinetics of metal release were determined in a cascade shaking test using de-mineralized water acidified to pH 4 (HNO(3)). Metal concentrations in the leachates were low and metal migration was, assuming uniform convective flow, predicted to be of no environmental concern. It is emphasized that any long-term prediction of metal migration is uncertain.

Chemical Forms of Mercury And Selenium in Fish Following Digestion With Simulated Gastric Fluid

Fish is a major dietary source of potentially neurotoxic methylmercury compounds for humans. It is also a rich source of essential selenium. We have used in situ mercury L(III)-edge and selenium K-edge X-ray absorption spectroscopy to chemically characterize the methylmercury and selenium in both fresh fish and fish digested with simulated gastric fluid. For the mercury, we confirm our earlier finding [ Harris et al. ( 2003 ) Science 301 , 1203 ] that the methylmercury is coordinated by a single thiolate donor, which resembles cysteine, and for the selenium, we find a mixture of organic forms that resemble selenomethionine and an aliphatic selenenyl sulfide such as Cys-S-Se-Cys. We find that local chemical environments of mercury and selenium do not change upon digestion of the fish with simulated gastric fluid. We discuss the toxicological implications for humans consuming fish.

The Chemical Forms of Mercury in Aged and Fresh Dental Amalgam Surfaces

Mercury-containing dental amalgam is known to be a source of human exposure to mercury. We have explored the use of electron yield Hg L(III) X-ray absorption spectroscopy to characterize the chemical nature of dental amalgam surfaces. We find that the method is practical and that it shows extensive mercury depletion in the surface of the aged amalgam with significant differences between old and fresh amalgam surfaces. Whereas the fresh amalgam gives spectra that are typical of metallic mercury, the aged amalgam is predominantly beta-mercuric sulfide. The toxicological implications of these results are discussed.

Towards a custom chelator for mercury: evaluation of coordination environments by molecular modeling

A chelator is a molecule which binds a metal or metalloid ion by two or more functional groups to form a stable ring complex known as a chelate. Despite the widespread clinical use of so-called chelation therapy to remove mercury, none of the drugs currently in use have been shown to chelate mercury. Mercury can adopt three common coordination environments: linear diagonal, trigonal planar, and tetrahedral. We have previously discussed some of the structural criteria for optimal binding of mercury in linear-diagonal coordination with thiolate donors (George et al. in Chem. Res. Toxicol. 17:999–1006, 2004). Here we employed density functional theory and X-ray absorption spectroscopy to evaluate the ideal chain length for simple alkane dithiolate chelators of Hg2+. We have also extended our previous calculations of the optimum coordination geometries to the three-coordinate [Hg(SR)3]− case. Finally, we propose a new chelator “tripod” molecule, benzene-1,3,5-triamidopropanethiolate, or “Trithiopod,” which is expected to bind Hg2+ in three-coordinate geometry with very high affinity.Graphical Abstract

The chemical forms of mercury in human hair: a study using X-ray absorption spectroscopy

Human hair is frequently used as a bioindicator of mercury exposure. We have used X-ray absorption spectroscopy to examine the chemical forms of mercury in human hair samples taken from individuals with high fish consumption and concomitant exposure to methylmercury. The mercury is found to be predominantly methylmercury–cysteine or closely related species, comprising approximately 80% of the total mercury, with the remainder an inorganic thiolate-coordinated mercuric species. No appreciable role was found for selenium in coordinating mercury in hair.Graphical abstract

The chemical forms of mercury and selenium in whale skeletal muscle

Human exposure to potentially neurotoxic methylmercury species is a public-health concern for many populations worldwide. Both fish and whale are known to contain varying amounts of methylmercury species. However studies of populations that consume large quantities of fish or whale have provided no clear consensus as to the extent of the risk. The toxicological profile of an element depends strongly on its chemical form. We have used X-ray absorption spectroscopy to investigate the comparative chemical forms of mercury and selenium in fish and whale skeletal muscle. The predominant chemical form of mercury in whale is found to closely resemble that found in fish. In the samples of skeletal muscle studied, no involvement of selenium in coordination of mercury is indicated in either whale or fish, with no significant inorganic HgSe or HgS type phases being detected. The selenium speciation in fish and whale shows that similar chemical types are present in each, but in significantly different proportions. Our results suggest that for equal amounts of Hg in skeletal muscle, the direct detrimental effects arising from the mercury content from consuming skeletal muscle from whale and fish should be similar if the effects of interactions with other components in the meat are not considered.

Arsenic K-edge X-ray absorption spectroscopy of arsenic in seafood.

It is well known that seafood contains high levels of arsenic. For marine animals arsenic is predominantly present as arsenobetaine and related compounds which are not metabolized and are thought to present no toxic hazard to humans. With edible seaweeds, arsenic is present in different forms, of which arsenosugars are the best known. These species may be metabolized by mammals, and the high arsenic contents of these materials represent a significant environmental source for human exposure to arsenicals in some populations. In this work, we explore the utility of As K-edge X-ray absorption near-edge spectroscopy as an in situ probe of the chemical forms of arsenic in seaweeds. We find that three different chemical types of arsenic are present, consistent with arsenate, an arsenosugar or tetra-alkyl-arsonium species, and a trivalent arsenic species.