Oxidative remobilization of biogenic uranium(IV) precipitates: effects of iron(II) and pH

The oxidative remobilization of uranium from biogenic U(IV) precipitates was investigated in bioreduced sediment suspensions in contact with atmospheric O2 with an emphasis on the influence of Fe(II) and pH on the rate and extent of U release from the solid to the aqueous phase. The sediment was collected from the U.S. Department of Energy Field Research Center (FRC) site at Oak Ridge, Tennessee. Biogenic U(IV) precipitates and bioreduced sediment were generated through anaerobic incubation with a dissimilatory metal reducing bacterium Shewanella putrefaciens strain CN32. The oxidative remobilization of freshly prepared and 1-yr aged biogenic U(IV) was conducted in 0.1 mol/L NaNO3 electrolyte with variable pH and Fe(II) concentrations. Biogenic U(IV)O2(s) was released into the aqueous phase with the highest rate and extent at pH 4 and 9, while the U remobilization was the lowest at circumneutral pH. Increasing Fe(II) significantly decreased U remobilization to the aqueous phase. From 70 to 100% of the U in the sediments used in all the tests was extractable at the experiment termination (41 d) with a bicarbonate solution (0.2 mol/L), indicating that biogenic U(IV) was oxidized regardless of Fe(II) concentration and pH. Sorption experiments and modeling calculations indicated that the inhibitive effect of Fe(II) on U(IV) oxidative remobilization was consistent with the Fe(III) oxide precipitation and U(VI) sorption to this secondary phase.     

Influence of quaternary ammonium on sorption of selected metal cations onto clinoptilolite zeolite

Clay minerals and zeolites have large cation exchange capacities, which enable them to be modified by cationic surfactant to enhance their sorption of organic and anionic contaminants. In this study, the influence of quaternary ammonium surfactants on sorption of five metal cations (Cs+, Sr+, La3+, Pb2+, and Zn2+) onto a clinoptilolite zeolite was investigated. Generally, the metal cation sorption capacity and affinity for the zeolite decreased, indicating that presorbed cationic surfactants blocked sorption sites for metal cations, as the surfactant loading on the zeolite increased. Cesium and Pb2+ sorption was affected to a small extent, indicating that selective sorption for Cs+ and specific sorption for Pb2+ play an important role in addition to cation exchange. Sorption of cationic surfactants on zeolite preloaded with different metal cations showed a strong correlation with the chain length of the surfactant tail group, while the roles of the charges and types of the metal cations were minimal. As the chain length increases, the critical micelle concentration decreases and the surfactant molecules become more hydrophobic, resulting in progressive bilayer coverage. Desorption of presorbed metal cations by cationic surfactants was strongly affected by the surfactant chain length and metal type. More metal cations, particularly Sr2+ and Zn2+, desorbed with an increase in surfactant chain length. The results, in combination with those from organic and oxyanion sorption on surfactant-modified zeolite, may be used for future surfactant modification to target sorption and desorption of a specific type of contaminant or a mixture of different types of contaminants.     

Surfactant-soil interactions during surfactant-amended remediation of contaminated soils by hydrophobic organic compounds: a review

Surfactants are amphiphilic molecules that reduce aqueous surface tension and increase the solubility of hydrophobic organic compounds (HOCs). Surfactant-amended remediation of HOC-contaminated soils and aquifers has received significant attention as an effective treatment strategy - similar in concept to using soaps and detergents as washing agents to remove grease from soiled fabrics. The proposed mechanisms involved in surfactant-amended remediation include: lowering of interfacial tension, surfactant solubilization of HOCs, and the phase transfer of HOC from soil-sorbed to pseudo-aqueous phase. However, as with any proposed chemical countermeasures, there is a concern regarding the fate of the added surfactant. This review summarizes the current state of knowledge regarding nonionic micelle-forming surfactant sorption onto soil, and serves as an introduction to research on that topic. Surfactant sorption onto soil appears to increase with increasing surfactant concentration until the onset of micellization. Sorbed-phase surfactant may account for the majority of added surfactant in surfactant-amended remediation applications, and this may result in increased HOC partitioning onto soil until HOC solubilization by micellar phase surfactant successfully competes with increased HOC sorption on surfactant-modified soil. This review provides discussion of equilibrium partitioning theory to account for the distribution of HOCs between soil, aqueous phase, sorbed surfactant, and micellar surfactant phases, as well as recently developed models for surfactant sorption onto soil. HOC partitioning is characterized by apparent soil-water distribution coefficients in the presence of surfactant.     

Soil and plant selenium at a reclaimed uranium mine

Selenium (Se) associated with reclaimed uranium (U) mine lands may result in increased food chain transfer and water contamination. To assess post-reclamation bioavailability of Se at a U mine site in southeastern Wyoming, we studied soil Se distribution, dissolution, speciation, and sorption characteristics and plant Se accumulation. Phosphate-extractable soil Se exceeded the critical limit of 0.5 mg/kg in all the samples, whereas total soil Se ranged from a low (0.6 mg/kg) to an extremely high (26 mg/kg) value. Selenite was the dominant species in phosphate and ammonium bicarbonate-diethylenetriamine pentaacetic acid (AB-DTPA) extracts, whereas selenate was the major Se species in hot water extracts. Extractable soil Se concentrations were in the order of KH2PO4 > AB-DTPA > hot water > saturated paste. The soils were undersaturated with respect to various Se solid phases, albeit with high levels of extractable Se surpassing the critical limit. Calcium and Mg minerals were the potential primary solids controlling Se dissolution, with dissolved organic carbon in the equilibrium solutions resulting in enhanced Se availability. Adsorption was a significant (r2 = 0.76-0.99 at P < 0.05) mechanism governing Se availability and was best described by the initial mass isotherm model, which predicted a maximum reserve Se pool corresponding to 87% of the phosphate-extractable Se concentrations. Grasses, forbs, and shrubs accumulated 11 to 1800 mg Se/kg dry weight. While elevated levels of bioavailable Se may be potentially toxic, the plants accumulating high Se may be used for phytoremediation, or the palatable forage species may be used as animal feed supplements in Se-deficient areas.     

Quantifying constraints imposed by calcium and iron on bacterial reduction of uranium(VI)

Uranium is a redox active contaminant of concern to both human health and ecological preservation. In anaerobic soils and sediments, the more mobile, oxidized form of uranium (UO(2)(2+) and associated species) may be reduced by dissimilatory metal-reducing bacteria. Despite rapid reduction in controlled, experimental systems, various factors within soils or sediments may limit biological reduction of U(VI), inclusive of competing electron acceptors and alterations in uranyl speciation. Here we elucidate the impact of U(VI) speciation on the extent and rate of reduction, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite, and hematite) varying in free energies of formation. Observed pseudo first-order rate coefficients for U(VI) reduction vary from 12 +/- 0.60 x 10(-3) h(-1) (0 mM Ca in the presence of goethite) to 2.0 +/- 0.10 x 10(-3) h(-1) (0.8 mM Ca in the presence of hematite). Nevertheless, dissolved Ca (at concentrations from 0.2 to 0.8 mM) decreases the extent of U(VI) reduction by approximately 25% after 528 h relative to rates without Ca present. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Ferrihydrite, in contrast, acts as a competitive electron acceptor and thus, like Ca, decreases uranium reduction. However, while ferrihydrite decreases U(VI) in solutions without Ca, with increasing Ca concentrations U(VI) reduction is enhanced in the presence of ferrihydrite (relative to its absence)-U(VI) reduction, in fact, becomes almost independent of Ca concentration. The quantitative framework described herein helps to predict the fate and transport of uranium within anaerobic environments.     

A comparative study for the sorption of Cd(II) by K-feldspar and sepiolite as soil components, and the recovery of Cd(II) using rhamnolipid biosurfactant

This study investigated the sorption characteristics and recovery of selected heavy metal Cd(II) from K-feldspar and sepiolite, representative soil components, using rhamnolipid biosurfactant. Although the proposed technique was classified as a soil bioremediation process, it can also be applied to treatment of waste waters containing Cd(II) ions with minor modifications. The effect of initial Cd(II) concentration on sorption capacity was characterized by determining the sorption isotherms. Of the four models examined, the Freundlich model showed the best fit for the sorption of Cd(II) on K-feldspar, whereas the Langmuir-model was used successfully to characterize the sorption of Cd(II) on sepiolite. Although a high Cd(II) uptake of 7.49 mmol/kg by K-feldspar was obtained, sepiolite was a superior Cd(II) accumulater, with a maximum Cd(II) uptake of 24.66 mmol Cd(II)/kg. The presence of Cd(II) in the sepiolite or K-feldspar prior to addition of the rhamnolipid generally resulted in less rhamnolipid sorption to sepiolite or K-feldspar. The maximum Cd(II) desorption efficiency by rhamnolipid from K-feldspar was substantially higher than that of sepiolite and determined to be 96% of the sorbed Cd(II), whereas only 10.1% of the sorbed Cd(II) from sepiolite was recovered by rhamnolipid solution.     

Sorption dynamics of organic and inorganic phosphorus compounds in soil

Phosphorus retention in soils is influenced by the form of P added. The potential impact of one P compound on the sorption of other P compounds in soils has not been widely reported. Sorption isotherms were utilized to quantify P retention by benchmark soils from Indiana, Missouri, and North Carolina when P was added as inorganic P (Pi) or organic P (beta-D-glucose-6-phosphate, G6P; adenosine 5'-triphosphate, ATP; and myoinositol hexaphosphate, IP6) and to determine whether soil P sorption by these organic P compounds and Pi was competitive. Isotherm supernatants were analyzed for pH and total P using standard protocols, while Pi and organic P compounds were assayed using ion chromatography. Under the controlled conditions of this study, the affinity of all soils for P sources followed the order IP6 > G6P > ATP > Pi. Each organic P source had a different potential to desorb Pi from soils, and the order of greatest to least Pi desorption was G6P > ATP > IP6. Glucose-6-phosphate and ATP competed more directly with Pi for sorption sites than IP6 at greater rates of P addition, but at the lesser rates of P addition, IP6 actually desorbed more Pi. Inositol hexaphosphate was strongly sorbed by all three soils and was relatively unaffected by the presence of other P sources. Decreased total P sorption due to desorption of Pi can be caused by relatively small additions of organic P, which may help explain vertical P movement in manured soils. Sorption isotherms performed using Pi alone did not accurately predict total P sorption in soils.     

Sorption of atmospheric ammonia by soil and perennial grass downwind from two large cattle feedlots

Livestock manure in feedlots releases ammonia (NH3), which can be sorbed by nearby soil and plants. Ammonia sorption by soil and its effects on soil and perennial grass N contents downwind from two large cattle feedlots in Alberta, Canada were investigated from June to October 2002. Atmospheric NH3 sorption was measured weekly by exposing air-dried soil at sampling points downwind along 1700-m transects. The amount of NH3 sorbed by soil was 2.60 to 3.16 kg N ha(-1) wk(-1) near the source, declining to about 0.25 kg N ha(-1) wk(-1) 1700 m downwind, reflecting diminishing atmospheric NH3 concentrations. Ammonia sorption at a control site away from NH3 sources was much lower: 0.085 kg N ha(-1) wk(-1). Based on these rates, about 19% of emitted NH3 is sorbed by soil within 1700 m downwind of feedlots. Field soil and grass samples from the transect lines were analyzed for total N (TN) and KCl-extractable N content (soil only). Nitrate N content in field soil followed a trend similar to that of atmospheric NH3 sorption. Soil TN contents, because of high background levels, showed no clear pattern. The TN content of grass, downwind of the newer feedlot, followed a pattern similar to that of NH3 sorption; downwind of the older feedlot, grass TN was correlated to soil TN. Our results suggest that atmospheric NH3 from livestock operations can contribute N to local soil and vegetation, and may need to be considered when determining fertilizer rates and assessing environmental impact.     

Concentration, pH, and surface charge effects on cadmium and lead sorption in three tropical soils

Reactions of heavy metals with soil are important in determining metal fates in the environment. Sorption characteristics of two heavy metals, Cd and Pb, in three tropical soils (Mollisol, Oxisol, and Ultisol) from Puerto Rico were assessed at varying metal concentrations (0 to 1.2 mM) and pH values (approximately 2 to 7). All soils sorbed more Pb than Cd. Sorption maxima were obtained for each metal for the Oxisol and Ultisol soils, but not the Mollisol. Sorption appeared to depend more on soil mineralogy than organic matter content. Sorption isotherms were linear within the sorption envelope with similar slopes for each soil-metal curve, when plotting metal sorption as a function of pH. Cadmium and Pb isotherms yielded average slopes of approximately 36+/-1 and 28+/-1 units (percent increase in metal sorption per 1-unit increase in pH), respectively. Metal sorption depended more on metal type than soil composition. Cadmium sorption displayed a greater pH dependence than Pb. Cadmium sorption was less than or equal to the amount of negative surface charge except at pH values greater than the point of zero net charge (PZNC). This suggests that Cd was probably sorbed via electrostatic surface reactions and/or possible inner-sphere complexation at pH > 3.7. However, the amount of Pb sorbed by the Oxisol was greater than the amount of negative surface charge, suggesting that Pb participates in inner-sphere surface reactions. Lead was sorbed more strongly than Cd in our soils and poses less of a threat to underlying ground water systems due to its lower mobility and availability.     

Sorptive and desorptive fractionation of dissolved organic matter by mineral soil matrices

Interactions of dissolved organic matter (DOM) with soil minerals, such as metal oxides and clays, involve various sorption mechanisms and may lead to sorptive fractionation of certain organic moieties. While sorption of DOM to soil minerals typically involves a degree of irreversibility, it is unclear which structural components of DOM correspond to the irreversibly bound fraction and which factors may be considered determinants. To assist in elucidating that, the current study aimed at investigating fractionation of DOM during sorption and desorption processes in soil. Batch DOM sorption and desorption experiments were conducted with organic matter poor, alkaline soils. Fourier-transform infrared (FTIR) and UV-Vis spectroscopy were used to analyze bulk DOM, sorbed DOM, and desorbed DOM fractions. Sorptive fractionation resulted mainly from the preferential uptake of aromatic, carboxylic, and phenolic moieties of DOM. Soil metal-oxide content positively affected DOM sorption and binding of some specific carboxylate and phenolate functional groups. Desorptive fractionation of DOM was expressed by the irreversible-binding nature of some carboxylic moieties, whereas other bound carboxylic moieties were readily desorbed. Inner-sphere, as opposed to outer-sphere, ligand-exchange complexation mechanisms may be responsible for these irreversible, as opposed to reversible, interactions, respectively. The interaction of aliphatic DOM constituents with soil, presumably through weak van der Waals forces, was minor and increased with increasing proportion of clay minerals in the soil. Revealing the nature of DOM-fractionation processes is of great importance to understanding carbon stabilization mechanisms in soils, as well as the overall fate of contaminants that might be associated with DOM.     

Apatite and phillipsite as sequestering agents for metals and radionuclides

Laboratory and greenhouse studies were conducted to quantify apatite and phillipsite (zeolite) sequestration of selected metal contaminants. The laboratory batch study measured the sorption of aqueous Co2+, Ba2+, Pb2+, Eu3+, and UO2(2+). Apatite sorbed more Co2+, Pb2+, Eu3+, and UO2(2+) from the spike solution than phillipsite, resulting in distribution coefficients (Kd values) of >200,000 L kg(-1). Phillipsite was more effective than apatite at sorbing aqueous Ba2+. Results from the laboratory study were used to design the greenhouse study that used a soil affected by a Zn-Pb smelter from Pribram, Czech Republic. Two application rates (25 and 50 g kg(-1)) of phillipsite and apatite and two plant species, maize (Zea mays L.) and oat (Avena sativa L.), were evaluated in this study. There was little (maize) to no (oat) plant growth in the unamended contaminated soil. Apatite and, to a slightly lesser extent, phillipsite additions significantly enhanced plant growth and reduced Cd, Pb, and Zn concentrations in all analyzed tissues (grain, leaves, and roots). The sequestering agents also affected some essential elements (Ca, Fe, and Mg). Phillipsite reduced Fe and apatite reduced P and Fe concentrations in oat tissues; however, the level of these elements in oat leaves and grains remained sufficient. Sequential extractions of the soil indicated that the Cd, Pb, and Zn were much more strongly sorbed onto the amended soil, making the contaminants less phytoavailable.     

Enhanced desorption of herbicides sorbed on soils by addition of Triton X-100

A study of the desorption of atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine) and linuron [1-methoxy-1-methyl-3-(3,4-dichlorophenyl)urea] adsorbed on soils with different organic matter (OM) and clay contents was conducted in water and in the presence of the non-ionic surfactant Triton X-100 at different concentrations. The aim was to gain insight into soil characteristics in surfactant-enhanced desorption of herbicides from soils. Adsorption and desorption isotherms in water, in all Triton X-100 solutions for atrazine, and in solutions of 0.75 times the critical micelle concentration (cmc) and 1.50cmc for linuron fit the Freundlich equation. All desorption isotherms showed hysteresis. Hysteresis coefficients decreased for linuron and increased or decreased for atrazine in Triton X-100 solutions. These variations were dependent on surfactant concentration and soil OM and clay contents. In the soil-water-surfactant system desorption of linuron from all soils was always greater than in the soil-water system but for atrazine this only occurred at concentrations higher than 50cmc. For the highest Triton X-100 concentration (100cmc), the desorption of the most hydrophobic herbicide (linuron) was increased more than 18-fold with respect to water in soil with an OM content of 10.3% while the atrazine desorption was increased 3-fold. The effect of Triton X-100 on the desorption of both herbicides was very low in soil with a high clay content. The results indicate the potential use of Triton X-100 to facilitate the desorption of these herbicides from soil to the water-surfactant system. They also contribute to better understanding of the interactions of different molecules and surfaces in the complex soil-herbicide-water surfactant system.     

Sorption and desorption of cadmium by different fractions of biosolids-amended soils

To evaluate the importance of both the inorganic and organic fractions in biosolids on Cd chemistry, a series of Cd sorption and desorption batch experiments (at pH 5.5) were conducted on different fractions of soils from a long-term field experimental site. The slope of the Cd sorption isotherm increased with rate of biosolids and was different for the different biosolids. Removal of organic carbon (OC) reduced the slope of the Cd sorption isotherm but did not account for the observed differences between biosolids-amended soils and a control soil, indicating that the increased adsorption associated with biosolids application was not limited to the increased OC from the addition of biosolids. Removal of both OC and Fe/Mn further reduced the slopes of Cd sorption isotherms and the sorption isotherm of the biosolids-amended soil was the same as that of the control, indicating both OC and Fe/Mn fractions added by the biosolids were important to the increased sorption observed for the biosolids-amended soil samples. Desorption experiments failed to remove from 60 to 90% of the sorbed Cd. This "apparent hysteresis" was higher for biosolids-amended soil than the control soil. Removal of both OC and Fe/Mn fractions was more effective in removing the observed differences between the biosolids-amended soil and the control than either alone. Results show that Cd added to biosolids-amended soil behaves differently than Cd added to soils without biosolids and support the hypothesis that the addition of Fe and Mn in the biosolids increased the retention of Cd in biosolids-amended soils.     

Effect of uranium(VI) speciation on simultaneous microbial reduction of uranium(VI) and iron(III)

Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates whether it will reside in the aqueous or solid phase and thus plays an integral role in the mobility of uranium within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO2(2+) and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO. However, various factors within soils and sediments, such as U(VI) speciation and the presence of competitive electron acceptors, may limit biological reduction of U(VI). Here we examine simultaneous dissimilatory reduction of Fe(III) and U(VI) in batch systems containing dissolved uranyl acetate and ferrihydrite-coated sand. Varying amounts of calcium were added to induce changes in aqueous U(VI) speciation. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% in absence of Ca or ferrihydrite, but only 24% (with ferrihydrite) and 14% (without ferrihydrite) were removed for systems with 0.8 mM Ca. Dissimilatory reduction of Fe(III) and U(VI) proceed through different enzyme pathways within one type of organism. We quantified the rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concecentration (0-0.8 mM). The mathematical construct, implemented with the reactive transport code MIN3P, reveals predominant factors controlling rates and extent of uranium reduction in complex geochemical systems.     

Contamination time effect on lead and cadmium fractionation in a tropical coastal clay

The capability of a tropical coastal clay to immobilize lead (Pb) and cadmium (Cd) was investigated in laboratory batch sorption tests conducted under acidic, neutral, and slightly alkaline conditions. The contact time was extended to 65 d. The distribution of Pb and Cd among various sorbed phases was examined using a sequential extraction technique. The sorbed phases were fractionated into the exchangeable, carbonate, reducible, organic, and residual fractions. There were only small changes in the total Pb and Cd sorption beyond a 1-d sorption period. The metal fractionation results show that the amount of Pb and Cd in various fractions changed with sorption time, and the changes were pH-dependent. These changes could be attributed to mineral dissolution and transformation or redistribution of the sorbed phases. Transformation of the sorbed phases resulted in increasing Pb and Cd retention in the more persistent fractions with time, at the expense of reductions in the loosely bound fractions. Nevertheless, Pb and Cd fractionation in the solid phase appeared to reach equilibrium within the 65-d sorption period. These Pb and Cd fractionation results reflect the effect of contamination time on the heavy metal lability and bioavailability in the subsurface environment.     

Sorption and fractionation of dissolved organic matter and associated phosphorus in agricultural soil

Mobility of dissolved organic matter (DOM) strongly affects the export of nitrogen (N) and phosphorus (P) from soils to surface waters. To study the sorption and mobility of dissolved organic C and P (DOC, DOP) in soil, the pH-dependent sorption of DOM to samples from Ap, EB, and Bt horizons from a Danish agricultural Humic Hapludult was investigated and a kinetic model applicable in field-scale models tested. Sorption experiments of 1 to 72 h duration were conducted at two pH levels (pH 5.0 and 7.0) and six initial DOC concentrations (0-4.7 mmol L(-1)). Most sorption/desorption occurred during the first few hours. Dissolved organic carbon and DOP sorption decreased strongly with increased pH and desorption dominated at pH 7, especially for DOC. Due to fractionation during DOM sorption/desorption at DOC concentrations up to 2 mmol L(-1), the solution fraction of DOM was enriched in P indicating preferred leaching of DOP. The kinetics of sorption was expressed as a function of how far the solution DOC or DOP concentrations deviate from "equilibrium." The model was able to simulate the kinetics of DOC and DOP sorption/desorption at all concentrations investigated and at both pH levels making it useful for incorporation in field-scale models for quantifying DOC and DOP dynamics.     

Sorption of iron-cyanide complexes on goethite in the presence of sulfate and desorption with phosphate and chloride

Soils are contaminated with potentially toxic iron-cyanide complexes by some industrial activities. The influence of sulfate on the sorption of the iron-cyanide complexes ferricyanide, [Fe(CN)6]3-, and ferrocyanide, [Fe(CN)6]4-, on goethite was investigated in batch experiments. The experiments were conducted as influenced by pH and varying sulfate/iron-cyanide complex concentration ratios. Furthermore, the desorption of iron-cyanide complexes sorbed on goethite was studied using phosphate and chloride solutions as influenced by pH and anion concentration. Over the whole pH range (pH 3.5 to 8), ferricyanide and sulfate showed similar affinities for the goethite surface. The extent of ferricyanide sorption strongly depended on sulfate concentrations and vice versa. In contrast, ferrocyanide sorption was only decreased (approximately 12%) by sulfate additions at pH 3.5. Ferricyanide was completely desorbed by 1 M chloride, ferrocyanide not at all. Unbuffered phosphate solutions (pH 8.3) desorbed both iron-cyanide complexes completely. Even in 70-fold excess, pH-adjusted phosphate solutions could not desorb ferrocyanide completely at pH 3.5. For ferricyanide we propose a sorption mechanism that is similar to the sulfate sorption mechanism, including outer-sphere and weak inner-sphere surface complexes on goethite. Ferrocyanide appears to form inner-sphere surface complexes. Additionally, we assume that ferrocyanide precipitates probably as a Berlin Blue-like phase at pH 3.5. Hence, ferrocyanide should be less mobile in the soil environment than ferricyanide or sulfate.     

Imazaquin adsorbed on pillared clay and crystal violet-montmorillonite complexes for reduced leaching in soil

Ground water pollution due to herbicide leaching has become a serious environmental problem. Imazaquin [2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)quinoline-3-carboxylic acid] is an herbicide used to control broadleaf weeds in legume crops. Imazaquin is negatively charged at the basic pH of calcareous soils and exhibits high leaching potential in soils. Our aim was to design formulation of imazaquin to reduce herbicide leaching. Imazaquin sorption on pillared clay (PC) and crystal violet (CV)-montmorillonite complexes was studied. The CV-montmorillonite complexes become positively charged with adsorption of CV above the cation exchange capacity (CEC) of montmorillonite, and thus can sorb imazaquin. The Langmuir equation provides a good fit to isotherms of imazaquin sorption on PC and CV-montmorillonite complexes, but for charged complexes an equation that combines electrostatics with specific binding was preferred. Maximal imazaquin sorption was 17.3 mmol kg-1 for PC and 22.2 mmol kg-1 for CV-montmorillonite complexes. The extents of imazaquin desorption into water were 21% for PC and 5% for CV-clay complexes. The presence of anions decreased imazaquin sorption on both sorbents in the sequence phosphate > acetate > sulfate. Reduction of imazaquin sorption by the anions and the extent of its desorption in electrolyte solutions were higher for PC than for CV-clay complexes. Leaching of imazaquin from CV-montmorillonite formulations through soil (Rhodoxeralf) columns was two times less than from PC formulations and four times less than that of technical imazaquin. The CV-montmorillonite complexes at a loading above the CEC appear to be suitable for preparation of organo-clay-imazaquin formulations that may reduce herbicide leaching significantly.     

Gas-phase sorption-desorption of propargyl bromide and 1,3-dichloropropene on plastic materials

The goal of this research was to provide information for choosing appropriate materials for studying gas-phase concentrations of propargyl bromide (3BP) and 1,3-dichloropropene (1,3-D) in laboratory experiments. Several materials were tested and found to sorb both gas-phase chemicals in the following order: stainless steel (SS) < Teflon polytetrafluoroethylene (PTFE-FEP) approximately flexible polyvinyl chloride (PVC) approximately acrylic < low-density polyethylene (PE) < vinyl approximately silicone < polyurethane foam (PUF). Sorption of SS was insignificant and PUF sorbed all the fumigant that was applied. For the other materials, linear sorption coefficients (Kd) for 3BP ranged from 3.0 cm3 g(-1) for PVC to 215 cm3 g(-1) for silicone. Freundlich sorption coefficients for 1,3-D ranged from 11.5 to 371 cm3 g(-1). First-order desorption rate constants in an open system ranged from 0.05 to 1.38 h(-1) for 3BP and from 0.07 to 1.73 h(-1) for 1,3-D. In a closed system, less than 2% of sorbed fumigant desorbed from vinyl while up to 99% desorbed from PVC within 24 h when equilibrated at the highest headspace concentration. Sorption of both fumigants was linearly related to the square root of time except for vinyl and silicone. This may indicate non-fickian diffusion of fumigant into the polymer matrix. Vinyl, silicone, PE, and PUF should be avoided for quantitative study of organic gases, except possibly as a trapping medium. Use of PTFE, PVC, and acrylic may require correction for sorption-desorption and diffusion.