PbO2 has been identified as an important scale in some distribution systems that historically use lead service lines and free chlorine for maintaining a disinfectant residual. The stability of this highly insoluble scale with respect to its reductive dissolution may play an important role in lead release into drinking water. In this study, we investigated the release of lead from a commercially available PbO2 in the presence of natural organic matter (NOM) using a hydrophobic acid extracted from the Iowa River. Experiments were conducted using synthetic solutions with different NOM concentrations, solution pH, and NOM samples with different levels of prechlorination. It was found that release of lead from PbO2 occurred both in solutions with and without NOM, and the extent of lead release increased with increasing NOM concentration and decreasing pH value. Furthermore, the released lead was Pb(II) and not particulate PbO2 conclusively showing that reductive dissolution occurred. Prechlorination of NOM reduced the rate of lead release. Our results indicate that PbO2 can be reduced both by water and NOM. Characterization of final solid phases by scanning electron microscopy and X-ray photoelectron spectroscopy are also presented.
The inhibition of calcite precipitation by natural organic material (NOM) in solutions seeded with calcite was investigated using a pH-stat system. Experiments were carried out using three NOMs with different physical/chemical properties. For each of the materials, inhibition was found to be more effective at lower carbonate/calcium ratios and lower pH values. The reduction in the precipitation rate could be explained by a Langmuir adsorption model using a conditional equilibrium constant. By identification of the type of site on the NOM molecules that is involved in the adsorption reaction, the "conditional" equilibrium constants obtained at different solution compositions converged to a single "nonconditional" value. The thermodynamic data determined at 25 degrees C and 1 atm suggest that the interaction between NOM molecules and the calcite surface is chemisorptive in nature and that adsorption is an endothermic reaction driven by the entropy change. The greatest degree of inhibition was observed for the NOM with the highest molecular weight and aromatic carbon content. For a given type of NOM, the degree of inhibition of calcite precipitation was dictated bythe balance between the enthalpy change and the entropy change of the adsorption reaction.
Lead oxide (PbO2) can be an important form of lead mineral scale occurring in some water distribution systems. It is believed to be formed by the oxidation of lead-containing plumbing materials by free chlorine. Its reactivity in water, however, has not been well studied. Iodide is also found in source drinking waters, albeit at low concentrations. Consideration of thermodynamics suggests that iodide can be oxidized by PbO2. In this investigation, iodide ion was used as a probe compound to study the reduction of PbO2 and the formation of iodoform, which has been predicted to be a carcinogen, in the presence of natural organic matter (NOM). The reduction of PbO2 by iodide can be expressed as PbO2 + 31(-) + 4H+ --> Pb(2+) + I3(-) + 2H2O, and the reaction kinetics has been determined in this study. In the presence of NOM, I3- reacts with NOM to form iodoform and its concentration is proportional to the NOM concentration. Our results indicate that PbO2 is a very powerful oxidant and can possibly serve as an oxidant reservoir for the formation of iodinated disinfection byproduct through a novel reaction pathway.
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