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.

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.

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Heavy metals produced and released during agricultural and industrial activities may pose a serious threat to the environment. This study investigated the effectiveness of phosphatic clay, a by-product of the phosphate mining industry, for immobilizing heavy metals (Pb(+2), Cd(+2), and Zn(+2)) from aqueous solutions. A batch equilibrium technique was adopted to evaluate metal sorption in the presence of 0.05 M KNO3 background electrolyte solution. The amounts of metals sorbed onto phosphatic clay decreased in the order Pb(+2) > Cd(+2) > Zn(+2). Desorption data suggest that a large fraction of metals sorbed onto phosphatic clay stayed intact under a wide variation in extracting solution pH (ranging from 3 to 10). Desorption rates were slowest for Pb followed by Cd and Zn. Only 8.1 to 23.1% of Pb, 8.4 to 45% of Cd, and 21.9 to 73.9% of Zn sorbed on phosphatic clay was mobilized by USEPA toxicity characteristic leaching procedure (TCLP) solutions at pH 2.93+/-0.05 and 4.93+/-0.05, respectively. Formation of fluoropyromorphite [Pb10(PO4)6(F2)], confirmed by scanning electron microscopy (SEM) and X-ray diffraction (XRD), after reaction of aqueous Pb with phosphatic clay suggested that precipitation remained the dominant mechanism for Pb removal from aqueous solution. In the case of aqueous Cd and Zn interaction with phosphatic clay, we are not able to confirm the formation of a new amorphous and/or crystalline phase on the basis of available information. Other possible sorption mechanisms for Cd and Zn may include sorption and coprecipitation. Thus, phosphatic clay may be an effective amendment for in situ immobilization of heavy metals in contaminated soils and sediments.