Bioaccessibility of lead sequestered to corundum and ferrihydrite in a simulated gastrointestinal system.

Lead (Pb) sorption onto oxide surfaces in soils may strongly influence the risk posed from incidental ingestion of Pb-contaminated soil. Lead was sorbed to model oxide minerals of corundum (alpha-Al(2)O(3)) and ferrihydrite (Fe(5)HO(8).4H(2)O). The Pb-sorbed minerals were placed in a simulated gastrointestinal tract (in vitro) to simulate ingestion of Pb-contaminated soil. The changes in Pb speciation were determined using extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge spectroscopy (XANES). Both corundum (sorption maximum of 2.13 g kg(-1)) and ferrihydrite (sorption maximum of 38.6 g kg(-1)) have been shown to sorb Pb, with ferrihydrite having a very high affinity for Pb. The gastric bioaccessible Pb for corundum was >85% for corundum when the concentration of Pb was >200 mg kg(-1). Bioaccessible Pb was not detectable at 4. However, much of the sorbed Pb will become bioaccessible under gastric conditions (pH 1.5-2.5) if this soil is ingested. Caution should be used before using these materials to remediate a soil where soil ingestion is an important exposure pathway.

Chemical and physical properties of dry flue gas desulfurization products.

Beneficial and environmentally safe recycling of flue gas desulfurization (FGD) products requires detailed knowledge of their chemical and physical properties. We analyzed 59 dry FGD samples collected from 13 locations representing four major FGD scrubbing technologies. The chemistry of all samples was dominated by Ca, S, Al, Fe, and Si and strong preferential partitioning into the acid insoluble residue (i.e., coal ash residue) was observed for Al, Ba, Be, Cr, Fe, Li, K, Pb, Si, and V. Sulfur, Ca, and Mg occurred primarily in water- or acid-soluble forms associated with the sorbents or scrubber reaction products. Deionized water leachates (American Society for Testing and Materials [ASTM] method) and dilute acetic acid leachates (toxicity characteristic leaching procedure [TCLP] method) had mean pH values of >11.2 and high mean concentrations of S primarily as SO(2-)4 and Ca. Concentrations of Ag, As, Ba, Cd, Cr, Hg, Pb, and Se (except for ASTM Se in two samples) were below drinking water standards in both ASTM and TCLP leachates. Total toxicity equivalents (TEQ) of dioxins, for two FGD products used for mine reclamation, were 0.48 and 0.53 ng kg(-1). This was similar to the background level of the mine spoil (0.57 ng kg(-1)). The FGD materials were mostly uniform in particle size. Specific surface area (m2 g(-1)) was related to particle size and varied from 1.3 for bed ash to 9.5 for spray dryer material. Many of the chemical and physical properties of these FGD samples were associated with the quality of the coal rather than the combustion and SO2 scrubbing processes used.

Fate of polydimethylsilicone in biosolids-amended field plots.

This research examined the fate of polydimethylsilicones (PDMS) in agricultural test plots amended with municipal biosolids. This 4 yr field study involved addition of 0, 15, and 100 Mg ha(-1) of municipal biosolids, which contained ambient concentrations of PDMS (1272 mg kg(-1) biosolids), to corn and soybean test plots. Soil samples collected at intermittent time intervals were analyzed for soil water, soil organic C, extractable PDMS and PDMS hydrolysis products. Above normal precipitation during the field study maintained soil water levels in excess of 100 g kg(-1) for most of the testing period of 1994-1998. Under these conditions half-lives for PDMS (based on field dissipation data) ranged from 876 to 1443 d. When biosolids amended soil samples were brought into the laboratory and subjected to more rapid drying, >80% of the PDMS was transformed to lower molecular weight hydrolysis products within 20 d. No difference in relative PDMS transformation rates were evident for soils that received PDMS in the form of a biosolids amendment or directly dosed to the soil (in the absence of biosolids) indicating little if any effect of direct PDMS-biosolids interactions on PDMS transformation rates. These results support that the overriding factor controlling the fate of PDMS in field soils is the soil moisture content.

Removal of mercury from sediment by ultrasound combined with biomass (transgenic Chlamydomonas reinhardtii).

As one of the most pervasive environmental problems, Hg pollution in sediment is particularly difficult to remediate because it cannot be decomposed. The application of ultrasound combined with biomass (transgenic Chlamydomonas reinhardtii (C. reinhardtii), a green alga) for the removal of Hg from model and contaminated sediments (Al(2)O(3), α-HgS, and PACS-2 marine sediment) was investigated in this study. Ultrasound was found to enhance Hg release from Al(2)O(3), α-HgS, and PACS-2 marine sediment into the aqueous phase compared to mechanical shaking. A transgenic C. reinhardtii (2AMT-2) expressing a plasmamembrane-anchored metallothionein polymer effectively recovered Hg(II) released into the aqueous phase by sonication over a broad pH range from 2.0 to 9.0. The results showed that this combined technique of ultrasound and alga biomass (2AMT-2) engineered for enhanced metal recovery was effective to remove Hg from solids and sediments, especially from Al(2)O(3) and α-HgS with no natural organic matter. The results of this study are discussed with respect to the development of in situ remediation techniques for Hg-contaminated sediments.

Linking solid phase speciation of Pb sequestered to birnessite to oral Pb bioaccessibility: implications for soil remediation.

Lead (Pb) sorption onto oxide surfaces in soils may strongly influence the risk posed from incidental ingestion of lead-contaminated soils. In this study, Pb was sorbed to a model soil mineral, birnessite, and was placed in a simulated gastrointestinal tract (in vitro) to simulate the possible effects of ingestion of a soil contaminated with Pb. The changes in Pb speciation were determined using extended X-ray absorption fine structure and X-ray absorption near edge spectroscopy. Birnessite has a very high affinity for Pb with a sorption maximum of 0.59 mol Pb kg(-1) (approximately 12% Pb sorbed by mass) in which there was no detectable bioaccessible Pb (< 0.002%). Surface speciation of the birnessite Pb was determined to be a triple corner sharing complex in the birnessite interlayer. Lead sorbed to Mn oxide in contaminated media will have a very low (approximately equal to 0) Pb bioaccessibility and present little risk associated with incidental ingestion of soil. These results suggest that birnessite, and other Mn oxides would be powerful remediation tools for Pb-contaminated media because of their high affinity for Pb.

Sonochemical dissolution of cinnabar (alpha-HgS).

To investigate the sonochemical dissolution of cinnabar, sulfur oxidation products (S(ox)) and dissolved Hg(II) released into the aqueous solution were determined. Detected S(ox), in the presence of ultrasound suggests that dissolution of cinnabar occurred. Terephthalic acid (TA) used to scavenge *OH in bulk solution formed from sonication showed that oxidative dissolution occurred in both the bulk solution and the interfacial areas of cavitation bubbles. Dissolved S(-II) was not detected, and SO4(2-) was the main S(ox) indicating that the formation of S(-II) from cinnabar by physical and thermal effects of sonication was the rate-limiting step. Hg(Il) released was much lower than S species measured. Hg(II) adsorption isotherms indicated that dissolved Hg(II) adsorbed back onto the remaining cinnabar particles lowering Hg(II) release. Ultrasound significantly reduced cinnabar particle size and increased surface area, leading to higher Hg(ll) adsorption. In addition, the cinnabar surface isoelectric point (IEP) increased after sonication, indicating adsorption of Hg(II) and/ or mineral phase transformation from cinnabar to metacinnabar. The presence of humic acid (HA) and ultrasound enhanced cinnabar dissolution and greatly increased the dissolved Hg(ll) concentration due to the synergistic effects of ultrasound and HA.

Sonolytic desorption of mercury from aluminum oxide: effects of pH, chloride, and organic matter.

The effects of pH, Cl-, and humic acid (HA) on sonolytic desorption of Hg(II) from aluminum oxide were examined. Results showed that Hg(II) desorption was achieved by lowering the pH from 7.0 to 4.0. Ultrasound enhanced Hg(II) release at short times compared to both hydrodynamic mixing and that expected on the basis of the pH-dependent Hg(II) adsorption curve. However, prolonged sonication led to decreases in Hg(II) desorption due to occlusion by aluminum hydroxide precipitation induced by ultrasound. The presence of Cl- greatly improved Hg(II) desorption at pH 4.0 due to the formation of stable nonadsorbing HgCl2(0) complexes at low pH, reducing free Hg(II) ion in solution. However, Cl- did not affect Hg(ll) desorption at pH 8.0, where Hg(OH)2(0) is the dominant Hg species rather than HgCl2(0). Hg(ll) desorption from HA-laden Al2O3 was dominated by HA. The greater the desorption of HA, the greater the desorption of Hg(II). Ultrasound enhanced the initial Hg(II) release by facilitating HA desorption. However, decreases in Hg(II) desorption were observed over longer sonication times due to the sonochemically induced reassociation of desorbed HA back onto Al2O3. Information obtained in this study provides insight into understanding sonolytic release of Hg from Hg-contaminated particles and sediments.

Bioaccessibility of arsenic(V) bound to ferrihydrite using a simulated gastrointestinal system.

The risk posed from incidental ingestion to humans of arsenic-contaminated soil may depend on sorption of arsenate (As(V)) to oxide surfaces in soil. Arsenate sorbed to ferrihydrite, a model soil mineral, was used to simulate possible effects on ingestion of soil contaminated with As-(V) sorbed to Fe oxide surfaces. Arsenate sorbed to ferrihydrite was placed in a simulated gastrointestinal tract (in vitro) to ascertain the bioaccessibility of As(V) and changes in As(V) surface speciation caused by the gastrointestinal system. The speciation of As was determined using extended X-ray absorption fine structure (EXAFS) analysis and X-ray absorption near-edge spectroscopy (XANES). The As(V) adsorption maximum was found to be 93 mmol kg(-1). The bioaccessible As(V) ranged from 0 to 5%, and surface speciation was determined to be binuclear bidentate with no changes in speciation observed post in vitro. Arsenate concentration in the intestine was not constant and varied from 0.001 to 0.53 mM for the 177 mmol kg(-1) As(V) treated sample. These results suggest that the bioaccessibility of As(V) is related to the As(V) concentration, the As(V) adsorption maximum, and that multiple measurements of dissolved As(V) in the intestinal phase may be needed to calculate the bioaccessibility of As(V) adsorbed to ferrihydrite.

Cr(VI) reduction and immobilization by magnetite under alkaline pH conditions: the role of passivation.

This study investigated Cr(VI) reduction and immobilization by magnetite under alkaline pH conditions similar to those present at the Hanford site. Compared to acidic and neutral pH, chromium(VI) reduction by magnetite at high pH conditions is limited (<20% of potential reduction capacity), and the extent of reduction does not vary significantly with increasing NaOH concentration. This is due to the formation of maghemite, goethite, and/or Fe1-xCrxOOH, which may form a passivation layer on the magnetite surface, stopping further chromate reduction. Maghemite is formed in lower NaOH concentrations. The extent of goethite formation increases with NaOH concentration. Goethite may be formed through two mechanisms: (i) dissolution of magnetite leads to the precipitation of goethite and/or (ii) dissolution of newly formed maghemite intermediate, followed by precipitation of goethite. Extended X-ray absorption fine structure spectroscopy shows that Cr has a similar structural environment at alkaline pH as at acidic and circumneutral conditions.

Sonolytic desorption of mercury from aluminum oxide.

As discrete particles and/or as coatings on other mineral surfaces in natural systems, aluminum (hydr)oxides are efficient sinks for Hg(II). Ultrasound at 20 kHz was applied to enhance the desorption of Hg(II) from aluminum oxide particles (5.0 micromol of Hg g(-1)). Results showed that at short times ultrasound enhanced Hg(II) release at pH 4.0 compared to both that from hydrodynamic mixing and that expected on the basis of the Hg(II) sorption isotherm. The higher the input power of sonication, the higher the desorption of Hg(II). However, with longer times, much less desorption occurred by ultrasound than by hydrodynamic mixing, with mass balance measurements demonstrating that the desorbed Hg(II) was resorbed back to the particles. The particles were characterized to explore the mechanism for resorption of Hg(II) by prolonged sonication. No surface area change was observed even though ultrasound dramatically reduced the particle size and changed the surface morphology. Although a decrease in the point of zero charge (PZC) due to sonication was observed, it was excluded as the primary mechanism for Hg(II) resorption. Hg(II) occlusion by aluminum hydroxide precipitation was supported by X-ray photoelectron spectroscopy results and the formation of solutions supersaturated with AI. Experiments on presonicated particles verified the occlusion theory by ruling out the effects of the surface area and PZC.

Sorptive Characteristics of Acridine-Surfactant-Phyllosilicate Systems.

The effects of the presence of a cationic surfactant on the sorption of two typical nitrogen heterocyclic compounds (NHCs) on swelling and nonswelling phyllosilicates were investigated. The addition of a cationic surfactant to a NHC-phyllosilicate system can either solubilize the sorbed NHC molecules or immobilize the suspended NHC molecules, depending upon the concentration and sequence of the surfactant added. The presence of surfactant molecules on the clay mineral surfaces promoted sorption of more neutral NHC molecules due to hydrophobic effect, and this resulted in a considerable increase in sorption at high pH conditions. Both surfactant and NHC molecules were sorbed not only on the external surfaces of the phyllosilicates but also on the interlayer spaces of swelling-type clay minerals, and the resulting change in basal spacings indicates the competition between the two groups of molecules in the interlayer space. Copyright 2000 Academic Press.

Inhibited Cr(VI) reduction by aqueous Fe(II) under hyperalkaline conditions.

This study investigated Cr(VI) reduction by dissolved Fe(II) in hyperalkaline pH conditions as found in fluid wastes associated with the U.S. nuclear weapons program. The results show that Cr(VI) reduction by Fe(II) at alkaline pH solutions proceeds very quickly. The amount of Cr(VI) removed from solution and the amount reduced increases with Fe(II):Cr(VI) ratio. However, the Cr(VI) reduction under alkaline pH condition is nonstoichiometric, probably due to Fe(II) precipitation and mixed iron(III)-chromium-(III) (oxy)hydroxides blocking Fe(II) surface sites, as well as removing Fe(II) from solution through O2 oxidation. After Cr(VI) was reduced to Cr(III), it precipitated out as mixed Fe(x)Cr1-xO3(solids) and various Fe(III) precipitates with an overall Cr:Fe ratio of 1:3; all Cr remaining in the solution phase was unreduced Cr(VI). EXAFS data showed that Cr-O and Cr-Cr distances in the precipitates equal to 1.98 and 3.01 A, respectively, consistent with the spinel-type structure as chromite.

Abiotic degradation of pentachloronitrobenzene by Fe(III): reactions on goethite and iron oxide nanoparticles.

Pentachloronitrobenzene is a fungicide that is degraded in anoxic soils and sediments through unknown processes that are often thought to be biologically mediated. The present research describes the kinetics for the abiotic reduction of this compound in aqueous Fe(II)/goethite systems at near-neutral pH values. The results provide evidence for a rate-affecting surface-association process rather than a direct (i.e., kinetically second-order) reaction with an adsorbed Fe(II) species. It is therefore likely that the iron oxide surface participates directly in the reaction. Furthermore, reduction is observed in the apparent presence of trace amounts of suspended iron oxide nanoparticles, formed in situ by the oxidation of Fe(II). Given that Fe(III) colloids and other nanoscale phases may occur in natural sediments, such abiotic reactions could significantly influence the environmental fate of nitroaromatic compounds.

Ralstonia basilensis M91-3, a denitrifying soil bacterium capable of using s-triazines as nitrogen sources.

The purpose of this study was to characterize the phylogenetic and phenotypic traits of M91-3, a soil bacterium capable of mineralizing atrazine (2-chloro-4-N-isopropyl-6-N-ethyl-s-triazine). The isolate was identified as Ralstonia basilensis based on 99.5% homology of the 16S rRNA sequence and various chemotaxonomic data. The isolate used atrazine as the sole source of energy, carbon, and nitrogen. It could also use several other s-triazines as nitrogen sources. Ralstonia basilensis M91-3 was capable of denitrification, which was confirmed by gas chromatographic analysis of nitrous oxide under acetylene blockage conditions.