Kinetic and thermodynamic study of chlorophenol sorption in an allophanic soil.

The sorption of 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol by a allophanic soil was studied in a series of batch experiments. Chlorophenol sorption behavior was evaluated as a function of reaction time (0-96h) and input concentration at a fixed ionic strength (0.1mol L(-1) KCl) at 25, 35, and 45 degrees C. Sorption results for the various reaction temperatures were used in calculating thermodynamic parameters. Chlorophenol sorption increased with temperature, suggesting an endothermic process. The Elovich equation was used to describe the kinetic data. Data from the isotherm experiments were described by the Triple-Layer Model in which monodentate outer- and inner-sphere complexes were formed between deprotonated organic molecules and active sites on the variable-charge soil. The calculated thermodynamic parameters suggest that chlorophenol sorption is a spontaneous (DeltaG<0), endothermic (DeltaH>0) and entropy-driven reaction (DeltaS>0).

Transcriptomic analysis of Rhizobium leguminosarum biovar viciae in symbiosis with host plants Pisum sativum and Vicia cracca.

Rhizobium leguminosarum bv. viciae forms nitrogen-fixing nodules on several legumes, including pea (Pisum sativum) and vetch (Vicia cracca), and has been widely used as a model to study nodule biochemistry. To understand the complex biochemical and developmental changes undergone by R. leguminosarum bv. viciae during bacteroid development, microarray experiments were first performed with cultured bacteria grown on a variety of carbon substrates (glucose, pyruvate, succinate, inositol, acetate, and acetoacetate) and then compared to bacteroids. Bacteroid metabolism is essentially that of dicarboxylate-grown cells (i.e., induction of dicarboxylate transport, gluconeogenesis and alanine synthesis, and repression of sugar utilization). The decarboxylating arm of the tricarboxylic acid cycle is highly induced, as is gamma-aminobutyrate metabolism, particularly in bacteroids from early (7-day) nodules. To investigate bacteroid development, gene expression in bacteroids was analyzed at 7, 15, and 21 days postinoculation of peas. This revealed that bacterial rRNA isolated from pea, but not vetch, is extensively processed in mature bacteroids. In early development (7 days), there were large changes in the expression of regulators, exported and cell surface molecules, multidrug exporters, and heat and cold shock proteins. fix genes were induced early but continued to increase in mature bacteroids, while nif genes were induced strongly in older bacteroids. Mutation of 37 genes that were strongly upregulated in mature bacteroids revealed that none were essential for nitrogen fixation. However, screening of 3,072 mini-Tn5 mutants on peas revealed previously uncharacterized genes essential for nitrogen fixation. These encoded a potential magnesium transporter, an AAA domain protein, and proteins involved in cytochrome synthesis.

Adsorption behavior of 2,4-dichlorophenol and pentachlorophenol in an allophanic soil.

The adsorption of 2,4-dichlorophenol (2,4-DCP) and pentachlorophenol (PCP) by a variable-charge soil from southern Chile was studied in a series of batch equilibration experiments. 2,4-DCP and PCP adsorption behavior was evaluated as a function of pH (pH values of 4.5, 6.0 and 7.5) in a 0.1M KCl (25 degrees C) background solution for soil material collected at three different depths (0-20 cm, 20-40 cm, and 40-60 cm). 2,4-DCP and PCP adsorption decreased with increasing soil pH, suggesting that the undissociated species were adsorbed more readily and that electrostatic repulsion may inhibit partitioning as pH increases. The PCP adsorption was greater than observed for 2,4-DCP and decreased with soil depth. Multiple regression analysis between K(d) and various soil properties indicated that the soil organic carbon content is a strong indicator of chlorophenol adsorption, and in addition to organic carbon, the soil pH is an important property controlling adsorption behavior.

Fate of arsenic compounds in poultry litter upon land application.

The use of the organic As compound, roxarsone, as an antibiotic additive to poultry feed continues to raise concern over potential negative environmental impacts. Total As concentration in poultry litter can reach >40 mg kg(-1) and both roxarsone and its mineralization product As(V) have been identified in poultry litters (PL). To investigate the fate of these As species upon land application of PL we conducted two studies. In the first, an Orangeburg soil (Ultisol from the Atlantic Coastal Plain) was spiked with either 20 mg kg(-1) As(V) or roxarsone and incubated at 10% moisture content for 4 months. Exchangeable As was determined periodically by extraction with 0.1M PO(4). Both As(V) and roxarsone displayed similar desorption; initially, approximately 70% of added As was ligand exchangeable and this decreased to 35% after 4 months incubation, presumably due to either slow sorption reactions or a change in solid phase speciation of As to less exchangeable forms. In the second study, various manipulations of two PL samples were applied to the Orangeburg soil at realistic field application rates. The treatments were wet to 10% moisture content and water soluble As, Cu and organic carbon (DOC) was measured over 30 days. Arsenic and Cu solubility were highest from the dried litter samples. Ashing of the PLs decreased soluble As and Cu, presumably because of the loss of organic matter from the ashed litter and subsequent decrease in DOC. Application of leachates from either PL resulted in higher concentrations of soluble As and Cu than when the soil was amended with equivalent concentrations of soluble As and Cu dissolved in DI H(2)O. We hypothesize that the increased levels of DOC from the PL treatments enhance As and Cu solubility through competitive sorption and complexation, respectively. In fact, As and Cu solubility was correlated to DOC levels in the amended soil extracts. Even though land application of PL introduced relatively low concentrations of As and Cu to soil it appeared that other soluble constituents of PL significantly enhanced As and Cu solubility.

Describing chlorophenol sorption on variable-charge soil using the triple-layer model.

The sorption of 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol by a variable-charge soil from southern Chile was studied in a series of batch experiments. The chlorophenol sorption behavior was evaluated as a function of pH (pH range 4-8) at two different ionic strengths, 0.01 and 0.1 M KCl (25 degrees C). Chlorophenol sorption depended on pH and a downward shift in the soil PZC was observed with increasing chlorophenol concentration. Chlorophenol sorption decreased with increasing pH, suggesting that the undissociated species is sorbed more readily and that electrostatic repulsion may inhibit partitioning as pH increases. Data from the sorption experiments were fitted by the triple-layer model, in which monodentate outer- and inner-sphere complexes were formed between deprotonated organic molecules and active sites on the variable-charge soil.

Trace element speciation in poultry litter.

Trace elements are added to poultry feed for disease prevention and enhanced feed efficiency. High concentrations are found in poultry litter (PL), which raises concerns regarding trace element loading of soils. Trace metal cation solubility from PL may be enhanced by complexation with dissolved organic carbon (DOC). Mineralization of organo-As compounds may result in more toxic species such as As(III) and As(V). Speciation of these elements in PL leachates should assist in predicting their fate in soil. Elemental concentrations of 40 PL samples from the southeastern USA were determined. Water-soluble extractions (WSE) were fractionated into hydrophobic, anionic, and cationic species with solid-phase extraction columns. Arsenic speciation of seven As species, including the main As poultry feed additives, roxarsone (ROX; 3-nitro-4-hydroxyphenylarsonic acid) and p-arsanilic acid (p-ASA; 4-aminophenylarsonic acid), was performed by ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS). Total As concentrations in the litter varied from 1 to 39 mg kg(-1), averaging 16 mg kg(-1). Mean total Cu, Ni, and Zn concentrations were 479, 11, and 373 mg kg(-1), respectively. Copper and Ni were relatively soluble (49 and 41% respectively) while only 6% of Zn was soluble. Arsenic was highly soluble with an average of 71% WSE. Roxarsone was the major As species in 50% of PL samples. However, the presence of As(V) as the major species in 50% of the PL samples indicates that mineralization of ROX had occurred. The high solubility of As from litter and its apparent ready mineralization to inorganic forms coupled with the large quantity of litter that is annually land-applied in the USA suggests a potential detrimental effect on soil and water quality in the long term.

Immobilization of cesium-137 and uranium in contaminated sediments using soil amendments.

Batch and dynamic leaching methods were used to evaluate the effectiveness of hydroxyapatite (HA), illite, and zeolite, alone and in combination, as soil additives for reducing the migration of cesium-137 (137Cs+) and uranium (U) from contaminated sediments. Amendment treatments ranging from 0 to 50 g kg(-1) were added to the sediment and equilibrated in 0.001 M CaCl2. After equilibration, the treatment supernatants were analyzed for 137Cs+, U, PO4, and other metals. The residual sediments were then extracted overnight using one of the following: 1.0 M NH4Cl, 0.5 M CaCl2, or the Toxicity Characteristic Leaching Procedure (TCLP) extractant. Cesium was strongly sorbed to the contaminated sediments, presumably due to interlayer fixation within native illitic clays. In fact, 137Cs+ was below detection limits in the initial equilibration solutions, the CaCl2 extract, and the TCLP solution, regardless of amendment. Extractants selective for interlayer cations (1.0 M NH4Cl) were necessary to extract measurable levels of 137Cs+. Addition of illitic clays further reduced Cs+ extractability, even when subjected to the aggressive extractants. Zeolite, however, was ineffective in reducing Cs+ mobility when subjected to the aggressive extractants. Hydroxyapatite was less effective than illite at reducing NH4+-extractable Cs+. Hydroxyapatite, and mixtures of HA with illite or zeolite, were highly effective in reducing U extractability in both batch and leaching tests. Uranium immobilization by HA was rapid with similar final U concentrations observed for equilibration times ranging from 1 h to 30 d. The current results demonstrate the effectiveness of soil amendments in reducing the mobility of U and Cs+, which makes in-place immobilization an effective remediation alternative.

Immobilization of nickel and other metals in contaminated sediments by hydroxyapatite addition.

Batch experiments were conducted to evaluate the ability of hydroxyapatte (HA) to reduce the solubility of metals, including the primary contaminants of concern, Ni and U, from contaminated sediments located on the Department of Energy's Savannah River Site, near Aiken, SC. Hydroxyapatitie was added to the sediments at application rates of 0, 5, 15.8, and 50 g kg-1. After equilibrating in either 0.02 M KCl or 0.01 M CaCl2, the samples were centrifuged and the supernatants filtered prior to metal, dissolved organic C, and PO4 analyses. The treated soils were then air-dried and changes in solid-phase metal distribution were evaluated using sequential extractions and electron-based microanalysis techniques. Hydroxyapatite was effective at reducing the solubility of U and, to a lesser degree, Ni. Hydroxyapatite was also effective in reducing the solubility of Al, Ba, Cd, Co, Mn, and Pb. Sequential extractions indicate that HA transfers such metals from more chemically labile forms, such as the water-soluble and exchangeable fractions, by altering solid-phase speciation in favor of secondary phosphate precipitates. Hydroxyapatite effectiveness was somewhat reduced in the presence of soluble organics that likely increased contaminant metal solubility through complexation. Arsenic and Cr solubility increased with HA addition, suggesting that the increase in pH and competition from PO4 reduced sorption of oxyanion contaminants. Energy dispersive x-ray (EDXA) analysis conducted in the transmission electron microscope (TEM) confirmed that HA amendment sequesters U, Ni, Pb, and possibly other contaminant metals in association with secondary Al-phosphates.

Characterization of complex mineral assemblages: implications for contaminant transport and environmental remediation.

Surface reactive phases of soils and aquifers, comprised of phyllosilicate and metal oxohydroxide minerals along with humic substances, play a critical role in the regulation of contaminant fate and transport. Much of our knowledge concerning contaminant-mineral interactions at the molecular level, however, is derived from extensive experimentation on model mineral systems. Although these investigations have provided a foundation for understanding reactive surface functional groups on individual mineral phases, the information cannot be readily extrapolated to complex mineral assemblages in natural systems. Recent studies have elucidated the role of less abundant mineral and organic substrates as important surface chemical modifiers and have demonstrated complex coupling of reactivity between permanent-charge phyllosilicates and variable-charge Fe-oxohydroxide phases. Surface chemical modifiers were observed to control colloid generation and transport processes in surface and subsurface environments as well as the transport of solutes and ionic tracers. The surface charging mechanisms operative in the complex mineral assemblages cannot be predicted based on bulk mineralogy or by considering surface reactivity of less abundant mineral phases based on results from model systems. The fragile nature of mineral assemblages isolated from natural systems requires novel techniques and experimental approaches for investigating their surface chemistry and reactivity free of artifacts. A complete understanding of the surface chemistry of complex mineral assemblages is prerequisite to accurately assessing environmental and human health risks of contaminants or in designing environmentally sound, cost-effective chemical and biological remediation strategies.

Immobilization of Uranium in Contaminated Sediments by Hydroxyapatite Addition.

Batch equilibrations were performed to investigate the ability of hydroxyapatite (Ca5(PO4)3OH) to chemically immobilize U in two contaminated sediment samples having different organic carbon contents (123 and 49 g kg(-1), respectively). Apatite additions lowered aqueous U to near proposed drinking water standards in batch equilibrations of two distinct sediment strata having total U concentrations of 1703 and 2100 mg kg(-1), respectively. Apatite addition of 50 g kg(-1) reduced the solubility of U to values less than would be expected if autunite (Ca(UO2)2(PO4)2·10H2O) was the controlling solid phase. A comparison of the two sediment types suggests that aqueous phase U may be controlled by both the DOC content through complexation and the equilibrium pH for a given apatite application rate. Sequential chemical extractions demonstrated that apatite amendment transfers U from more chemically labile fractions, including water-soluble, exchangeable, and acid-soluble (pH ≈ 2.55) fractions, to the Mn-occluded fraction (pH ≈ 1.26). This suggests that apatite amendment redirects solid-phase speciation with secondary U phosphates being solubilized due to the lower pH of the Mn-occluded extractant, despite the lack of significant quantities of Mn oxides within these sediments. Energy dispersive X-ray (EDX) analysis conducted in a transmission electron microscope (TEM) confirmed that apatite amendment sequesters some U in secondary Al/Fe phosphate phases.