Pilot-scale treatment of RDX-contaminated soil with zerovalent iron

Soils in Technical Area 16 at Los Alamos National Laboratory (LANL) are severely contaminated from past explosives testing and research. Our objective was to conduct laboratory and pilot-scale experiments to determine if zerovalent iron (Fe(0)) could effectively transform RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) in two LANL soils that differed in physicochemical properties (Soils A and B). Laboratory tests indicated that Soil A was highly alkaline and needed to be acidified [with H2SO4, Al2(SO4)3, or CH3COOH] before Fe(0) could transform RDX. Pilot-scale experiments were performed by mixing Fe(0) and contaminated soil (70 kg), and acidifying amendments with a high-speed mixer that was a one-sixth replica of a field-scale unit. Soils were kept unsaturated (soil water content = 0.30-0.34 kg kg(-1)) and sampled with time (0-120 d). While adding CH3COOH improved the effectiveness of Fe(0) to remove RDX in Soil A (98% destruction), CH3COOH had a negative effect in Soil B. We believe that this difference is a result of high concentrations of organic matter and Ba. Adding CH3COOH to Soil B lowered pH and facilitated Ba release from BaSO4 or BaCO3, which decreased Fe(0) performance by promoting flocculation of humic material on the iron. Despite problems encountered with CH3COOH, pilot-scale treatment of Soil B (12 100 mg RDX kg(-1)) with Fe(0) or Fe(0) + Al2(SO4)3 showed high RDX destruction (96-98%). This indicates that RDX-contaminated soil can be remediated at the field scale with Fe(0) and soil-specific problems (i.e., alkalinity, high organic matter or Ba) can be overcome by adjustments to the Fe(0) treatment.     

Contribution of hydrolysis in the abiotic attenuation of RDX and HMX in coastal waters

Sinking of military ships, dumping of munitions during the two World Wars, and military training have resulted in the undersea deposition of numerous unexploded ordnances (UXOs). Leaching of energetic compounds such as hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) from these UXOs may cause adverse ecological effects so that the long-term fate of these chemicals in the sea should be known. The present study assesses the contribution of alkaline hydrolysis into the natural attenuation of RDX and HMX in coastal waters. Alkaline hydrolysis rates were shown to be unaffected by the presence of sodium chloride, the most common component in marine waters. Kinetic parameters (E(a), ln A, k(2)) quantified for the alkaline hydrolysis of RDX and HMX in deionized water (30-50 degrees C, pH 10-12) agreed relatively well with abiotic degradation rates determined in sterilized natural coastal waters (50 and 60 degrees C, variable salinity) even if the latter were generally slightly faster than the former. Furthermore, similar products (HCHO, NO(2)(-), O(2)NNHCH(2)NHCHO) were obtained on alkaline hydrolysis in deionized water and abiotic degradation in coastal waters. These two findings suggested that degradation of nitramines in sterilized natural coastal waters, away from light, was mainly governed by alkaline hydrolysis. Kinetic calculations using the present parameters showed that alkaline hydrolysis of RDX and HMX in marine waters at 10 degrees C would respectively take 112 +/- 10 and 2408 +/- 217 yr to be completed (99.0%). We concluded that under natural conditions hydrolysis should not contribute significantly to the natural attenuation of HMX in coastal waters whereas it could play an active role in the natural attenuation of RDX.     

Dissolution and transport of TNT, RDX, and composition B in saturated soil columns

Low-order detonations and blow-in-place procedures on military training ranges can result in residual solid explosive formulations to serve as distributed point sources for ground water contamination. This study was conducted to determine if distribution coefficients from batch studies and transport parameters of pure compounds in solution adequately describe explosive transport where compounds are present as solid particles in formulations. Saturated column transport experiments were conducted with 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and the explosive formulation, Composition B (Comp B) (59.5 +/- 2.0% RDX, 39.5 +/- 2.3% TNT, and 1% wax) in solid and dissolved forms. The two soils used were Plymouth loamy sand (mesic, coated Typic Quartzipsamments) from Camp Edwards, MA and Adler silt loam (coarse-silty, mixed, superactive, thermic Fluvaquentic Eutrudepts) from Vicksburg, MS. Interrupted flow experiments were used to determine if explosives were at equilibrium distribution between soil and solution phases. The HYDRUS-1D code was used to determine fate and transport parameters. Results indicated that sorption of high explosives was rate limited. The behavior of dissolved Comp B was similar to the behavior of pure TNT and RDX. Behavior of solid Comp B was controlled by dissolution that depended on physical properties of the Comp B sample. Adsorption coefficients determined by HYDRUS-1D were different from those determined in batch tests for the same soils. Use of parameters specific to formulations will improve fate and transport predictions.     

Remediating RDX-contaminated ground water with permanganate: laboratory investigations for the Pantex perched aquifer

Ground water beneath the U.S. Department of Energy Pantex Plant is contaminated with the high explosive RDX (hexahydro-1,3,5-trinitro-1,3,5 triazine). The USDOE Innovative Treatment and Remediation Demonstration (ITRD) program identified in situ oxidation by permanganate as a technology fit for further investigation. We evaluated the efficacy of KMnO(4) to transform and mineralize RDX by determining degradation kinetics and carbon mass balances using (14)C-RDX. Aqueous RDX solutions (2-5 mg L(-1)) and RDX-contaminated slurries (50% solids, w/v) were treated with KMnO(4) at 1000, 2000, 4000, and 20000 mg L(-1). Treating an aqueous RDX solution of 2.8 mg L(-1) with 20000 mg KMnO(4) L(-1) decreased RDX to 0.1 mg L(-1) within 11 d while cumulative mineralization proceeded for 14 d until 87% of the labeled carbon was trapped as (14)CO(2). Similar cumulative mineralization was obtained when Pantex aquifer material was included in the solution matrix. Other experiments using 4000 mg KMnO(4) L(-1) showed that initial RDX concentrations (1.3-10.4 mg L(-1)) or initial pH (4-11) had little effect on reaction rates. Attempts to identify RDX degradates and reaction products showed that N(2)O was a product of permanganate oxidation and constituted 20 to 30% of the N balance. Time-course measurements of a (14)C-RDX solution treated with KMnO(4) revealed few (14)C-labeled degradates but through liquid chromatography-mass spectrometry (LC-MS) analysis, we present evidence that 4-nitro-2,4-diaza-butanol is formed. Aquifer microcosm studies confirmed that the transformation products not mineralized by KMnO(4) were much more biodegradable than parent RDX. These results indicate permanganate can effectively transform and mineralize RDX in the presence of aquifer material and support its use as an in situ chemical oxidation treatment for the Pantex perched aquifer.     

RDX loss in a surface soil under saturated and well drained conditions

On military training ranges, low-order, incomplete detonations deposit RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) into surface soils. In this study, we evaluated RDX biodegradation in surface soils obtained from a military training range in Alaska. Two factors were compared: (i) soil water potential during the incubations; and (ii) the use of acetonitrile (ACN) as an RDX carrier to spike samples. Organic solvents have been used in laboratory studies to dissolve slightly water-soluble contaminants before addition to soil. We added ACN to obtain final soil ACN concentrations of 0 mg kg(-1) (0%), 1000 mg kg(-1) (0.1%) and 10 000 mg kg(-1) (1%). We then compared RDX attenuation in the soil under saturated and unsaturated conditions. RDX fell below the limit of detection within 3 wk of study initiation under the saturated condition. A maximum degradation rate of 0.15 mg RDX L(-1) d(-1) was measured. Under the unsaturated condition, 42% of the original RDX was still present at study termination (5 wk). The addition of acetonitrile at 0.1 or 1.0% had no affect on RDX loss in the saturated soil. In the unsaturated soil, however, ACN at 1.0% inhibited RDX loss by as much as 25%. These findings indicate that soil water potential and carrier solvent concentrations can impact the rate and extent to which RDX is attenuated in a surface soil.     

Coupled abiotic-biotic mineralization of 2,4,6-trinitrotoluene (TNT) in soil slurry

The explosive 2,4,6-trinitrotoluene (TNT) is a contaminant of soils and ground waters worldwide. To help alleviate such environmental contamination, we investigated a coupled abiotic-biotic treatment scheme for remediating TNT-contaminated soil in slurry solutions. Two types of soil were used (sandy and silt loam) to simulate different soils that might be found at actual sites. These soils were subsequently contaminated with 5000 mg kg(-1) TNT. Mineralization of TNT was initially optimized for minimum reactant use (Fe(3+) and H(2)O(2)) and maximum soil slurry percentage (percent solids) using modified Fenton reactions conducted in the absence of light followed by the addition of an uncharacterized aerobic biomass. Greater than 97% TNT degradation was observed under optimum reaction conditions for both soils. Using two optimum reactant concentrations for each soil, coupled abiotic-biotic reactions showed an increase in TNT mineralization, from 41 to 73% and 34 to 64% in the sandy soil (10 and 20% slurry, respectively, 1470 mM H(2)O(2)), and increases from 12 to 23% and 13 to 28% in the silt loam soil (5% slurry, 294 and 1470 mM H(2)O(2), respectively). These results show promise in the use of combined abiotic-biotic treatment processes for soils contaminated with high concentrations of TNT.     

Biotic and abiotic degradation of CL-20 and RDX in soils

The caged cyclic nitramine 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) is a new explosive that has the potential to replace existing military explosives, but little is known about its environmental toxicity, transport, and fate. We quantified and compared the aerobic environmental fate of CL-20 to the widely used cyclic nitramine explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in surface and subsurface soil microcosms. Soil-free controls and biologically attenuated soil controls were used to separate abiotic processes from biologically mediated processes. Both abiotic and biological processes significantly degraded CL-20 in all soils examined. Apparent abiotic, first-order degradation rates (k) for CL-20 were not significantly different between soil-free controls (0.018 < k < 0.030 d(-1)) and biologically attenuated soil controls (0.003 < k < 0.277 d(-1)). The addition of glucose to biologically active soil microcosms significantly increased CL-20 degradation rates (0.068 < k < 1.22 d(-1)). Extents of mineralization of (14)C-CL-20 to (14)CO(2) in biologically active soil microcosms were 41.1 to 55.7%, indicating that the CL-20 cage was broken, since all carbons are part of the heterocyclic cage. Under aerobic conditions, abiotic degradation rates of RDX were generally slower (0 < k < 0.032 d(-1)) than abiotic CL-20 degradation rates. In biologically active soil microcosms amended with glucose aerobic RDX degradation rates varied between 0.010 and 0.474 d(-1). Biodegradation was a key factor in determining the environmental fate of RDX, while a combination of biotic and abiotic processes was important with CL-20. Our data suggest that CL-20 should be less recalcitrant than RDX in aerobic soils.     

Metolachlor dechlorination by zerovalent iron during unsaturated transport

Permeable zerovalent iron (Fe0) barriers have become an established technology for remediating contaminated ground water. This same technology may be applicable for treating pesticides amenable to dehalogenation as they move downward in the vadose zone. By conducting miscible displacement experiments in the laboratory with metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide; a chloroacetanilide herbicide] under unsaturated flow, we provide proof-of-concept for such an approach. Transport experiments were conducted in repacked, unsaturated soil columns attached to vacuum chambers and run under constant matrix potential (-30 kPa) and Darcy flux (approximately 2 cm d(-1)). Treatments included soil columns equipped with and without a permeable reactive barrier (PRB) consisting of a Fe0-sand (50:50) mixture supplemented with Al2(SO4)3. A continuous pulse of 14C-labeled metolachlor (1.45 mM) and tritiated water (3H2O) was applied to top of the columns for 10 d. Results indicated complete (100%) metolachlor destruction, with the dehalogenated product observed as the primary degradate in the leachate. Similar results were obtained with a 25:75 Fe0-sand barrier but metolachlor destruction was not as efficient when unannealed iron was used or Al2(SO4)3 was omitted from the barrier. A second set of transport experiments used metolachlor-contaminated soil in lieu of a 14C-metolachlor pulse. Under these conditions, the iron barrier decreased metolachlor concentration in the leachate by approximately 50%. These results provide initial evidence that permeable iron barriers can effectively reduce metolachlor leaching under unsaturated flow.     

Enhancing metolachlor destruction rates with aluminum and iron salts during zerovalent iron treatment

Pesticide-contaminated soil may require remediation to mitigate ground and surface water contamination. We determined the effectiveness of zerovalent iron (Fe(0)) to dechlorinate metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methyl ethyl) acetamide] in the presence of aluminum and iron salts. By treating aqueous solutions of metolachlor with Fe(0), we found destruction kinetics were greatly enhanced when Al, Fe(II), or Fe(II) salts were added, with the following order of destruction kinetics observed: Al2(SO4)3 > AlCl3 > Fe2(SO4)3 > FeCl3. A common observation was the formation of green rusts, mixed Fe(II)-Fe(III) hydroxides with interlayer anions that impart a greenish-blue color. Central to the mechanism responsible for enhanced metolachlor loss may be the role these salts play in facilitating Fe(II) release. By tracking Al and Fe(II) in a Fe(0) + Al2(SO4)3 treatment of metolachlor, we observed that Al was readily sorbed by the corroding iron with a corresponding release of Fe(II). The manufacturing process used to produce the Fe(0) also profoundly affected destruction rates. Metolachlor destruction rates with salt-amended Fe(0) were greater with annealed iron (indirectly heated under a reducing atmosphere) than unannealed iron. Moreover, the optimum pH for metolachlor dechlorination in water and soil differed between iron sources (pH 3 for unannealed, pH 5 for annealed). Our results indicate that metolachlor destruction by Fe(0) treatment may be enhanced by adding Fe or Al salts and creating pH and redox conditions favoring the formation of green rusts.     

Simulation of phytoremediation of a TNT-contaminated soil using the CTSPAC model

Knowledge of water movement in the plant-xylem system and contaminant bioavailability in the soil environment is crucial to evaluate the success of phytoremediation practices. This study investigated the removal of 2,4,6-trinitrotoluene (TNT) from a contaminated sandy soil by a single poplar (Populus fastigiata) tree through the examinations of temporal variations of xylem water potential, root water uptake, and soil TNT bioavailability. A mathematical model, CTSPAC (Coupled Transport of water, heat, and solutes in the Soil-Plant-Atmosphere Continuum), was modified for the purpose of this study. The model was calibrated using laboratory measurements before its application. Our simulations show that the xylem water potential was high in the roots and low in the leaves with a potential head difference of 3.55 cm H2O, which created a driving force for water flow and chemical transport upward from the roots through the stem to the leaves. The daily average root water uptake rate was 25 cm3 h(-1) when an equilibrium condition was reached after 24 h. Our simulations further reveal that no TNT was found in the stem and leaves and only about 1% of total TNT mass was observed in the roots due to the rapid biodegradation and transformation of TNT into its daughter products. About 13% of the soil TNT was removed by the poplar tree, resulting mainly from root uptake since TNT is a recalcitrant compound. In general, the soil TNT bioavailability decreased with time due to the depletion of soil solution TNT by the poplar tree. A constant bioavailability (i.e., 3.1 x 10(-6)) was obtained in 14 d in which the soil TNT concentration was about 10 mg L(-1). Our study suggests that CTSPAC is a useful model to simulate phytoremediation of TNT-contaminated sites.     

Environmental impacts of training activities at an air weapons range

Within Canada, it has been recognized in the last decade that military training activities may have impacts on the environmental quality of training ranges. However, impacts of activities specific to Air Force Bases have not yet been intensely documented. A hydrogeological study was accomplished at the Cold Lake Air Weapons Range, Alberta, to evaluate the environmental impacts of using bombs, rockets, strafing, and open burning/open detonation (OB/OD) on the quality of soil, ground water, surface water, and lake sediments. Samples were analyzed for metals, anions, ammonium perchlorate (NH(4)ClO(4)), and energetic materials (EM). It was found that training activities did not result in measured values being exceeded on the basis of guidance values for surface water and lake sediments. Contamination by metals was mostly limited to soils, and some metals may be related to the use of bombs (Cd, Cu, Pb), strafe (Cu), and rockets (As, Ba, Cd, Cr, Cu, Fe, Ni, Pb, U, V, Zn). TNT (2,4,6-trinitrotoluene) was the main EM found in soils, while RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) was more common in ground water. Both are related to live bombing, while nitroglycerine (NG) is related to rocket use and was detected in soils only. Aluminum, nitrate, and ammonium perchlorate detected in ground water may be related to live bombing or rockets. OB/OD operations resulted in the presence of various EM in soils, and of perchlorate and nitrate in ground water. Contamination by metals and explosives in soils was localized around the targets and varied significantly in time; however, in ground water it was more constant and may persist for a period of several years after a target has been removed.     

Solid-state nitrogen-15 nuclear magnetic resonance analysis of biologically reduced 2,4,6-trinitrotoluene in a soil slurry remediation

Soil contaminated with 2,4,6-trinitrotoluene (TNT) and spiked with [14C]- and [15N3]-TNT was subjected to an anaerobic-aerobic soil slurry treatment and subsequently analyzed by radiocounting and solid-state 15N nuclear magnetic resonance (NMR) spectroscopy. This treatment led to a complete disappearance of extractable radioactivity originating from TNT and almost all of the radioactivity was recovered in the insoluble soil fraction. As revealed by solid-state 15N NMR, a major fraction of partially reduced metabolites of TNT was immobilized into the soil during the early stage of the anaerobic treatment, although some of the compounds (i.e., aminodinitrotoluenes and azoxy compounds) were extractable by methanol. Considerable 15N intensity was assigned to condensation products of TNT metabolites. A smaller signal indicated the formation of azoxy N. This signal and the signal for nitro groups were not observed at the end of the anaerobic phase, revealing further reduction and/or transformation of their corresponding compounds. An increase of the relative proportion of the condensation products occurred with increasing anaerobic incubation. Aerobic incubation resulted in a further decrease of aromatic amines, presumably due to oxidative transformations or their involvement in further condensation reactions. The results of the study demonstrate that the anaerobic-aerobic soil slurry treatment represents an efficient strategy for immobilizing reduced TNT in soils.     

Coupled abiotic-biotic mineralization of 2,4,6-trinitrotoluene (TNT)

Munitions wastes such as TNT are widespread contaminants in soils and ground waters. We investigated a coupled abiotic-biotic treatment scheme for remediation of aqueous solutions of TNT. Mineralization of aqueous TNT (0.22 mM) was initially optimized with minimum reactant use (Fe3+ and H2O2) in light-assisted and dark, modified Fenton reactions at acidic and neutral pH. Complete TNT degradation occurred under all reaction conditions within 24 h. Using the optimum reactant concentrations, coupled abiotic-biotic reactions showed an increase in TNT mineralization, from 47 to 80%, after biomass addition to the acidic, dark Fenton-like reaction. Comparable increases of TNT mineralization were observed under neutral pH with similar reaction conditions. In light-assisted Fenton-like reactions at neutral pH, no increase in cumulative TNT mineralization (66%) was seen in coupled abiotic-biotic reactions. Abiotic photo-Fenton-like reactions alone, at acidic pH, produced complete TNT mineralization and required no biotic assistance. While light-enhanced Fenton reactions alone can provide high levels of TNT mineralization, the dark abiotic-biotic reaction scheme has perhaps a wider use due to a similar extent of TNT mineralization in the absence of light, leading to possible applications in soil slurry and in situ processes in the subsurface.     

Enzymatic transformation and binding of labeled 2,4,6-trinitrotoluene to humic substances during an anaerobic/aerobic incubation

Organic pollutants are degraded in soil and simultaneously nonextractable residues are formed. However, proof is lacking that this fixation has a detoxifying effect. We investigated the transformation and binding of 2,4,6-trinitrotoluene (TNT) with catechol or soil humic acid as cosubstrates. Carbon-14-labeled TNT and its reaction products were quantified by radiocounting; extractable compounds were identified by high performance liquid chromatography (HPLC). Bound and extractable residues of 15N-labeled TNT and metabolites were studied by 15N nuclear magnetic resonance spectroscopy (15N NMR). Since TNT is not easily transformed under oxidizing conditions an anaerobic/aerobic treatment was used. Anaerobic microorganisms from cow manure were used to reduce TNT during the anaerobic phase and subsequently, a laccase from Trametes villosa was used in the aerobic phase to oxidatively couple the metabolites to humic matter. Seventy-four percent of TNT was immobilized with catechol as cosubstrate, but only 25% with humic acid. With catechol the main extractable component was TNT, while with humic acid it was mostly the metabolite 4-aminodinitrotoluene. For both co-substrates, the spectra of immobilized metabolites obtained by solid-state 15N-cross polarization magic angle spinning (CPMAS) NMR spectroscopy showed signals in the chemical shift region for protonated aromatic amino compounds. However, in the presence of catechol, an additional signal from nonextractable nitro groups was found, which could represent sequestered TNT. The partially reduced metabolites of TNT that formed nonextractable residues in humic acid are not likely to be remobilized easily and are thus regarded as detoxified.     

Field-scale remediation of a metolachlor-contaminated spill site using zerovalent iron

Pesticide spills are common occurrences at agricultural cooperatives and farmsteads. When inadvertent spills occur, chemicals normally beneficial can become point sources of ground and surface water contamination. We report results from a field trial where approximately 765 m3 of soil from a metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] spill site was treated with zerovalent iron (Fe0). Preliminary laboratory experiments confirmed metolachlor dechlorination by Fe0 in aqueous solution and that this process could be accelerated by adding appropriate proportions of Al2(SO4)3 or acetic acid (CH3COOH). The field project was initiated by moving the stockpiled, contaminated soil into windrows using common earth-moving equipment. The soil was then mixed with water (0.35-0.40 kg H2O kg(-1)) and various combinations of 5% Fe0 (w/w),2% Al2(SO4)3 (w/w), and 0.5% acetic acid (v/w). Windrows were covered with clear plastic and incubated without additional mixing for 90 d. Approximately every 14 d, the plastic sheeting was removed for soil sampling and the surface of the windrows rewetted. Metolachlor concentrations were significantly reduced and varied among treatments. The addition of Fe0 alone decreased metolachlor concentration from 1789 to 504 mg kg(-1) within 90 d, whereas adding Fe0 with Al2(SO4)3 and CH3COOH decreased the concentration from 1402 to 13 mg kg(-1). These results provide evidence that zerovalent iron can be used for on-site, field-scale treatment of pesticide-contaminated soil.     

Bioremediation of soils contaminated with explosives

The large-scale industrial production and processing of munitions such as 2,4,6-trinitrotoluene (TNT) over the past 100 years led to the disposal of wastes containing explosives and nitrated organic by-products into the environment. In the US, the Army alone has estimated that over 1.2 million tons of soil have been contaminated with explosives, and the impact of explosives contamination in other countries is of similar magnitude. In recent years, growing concern about the health and ecological threats posed by man-made chemicals have led to studies of the toxicology of explosives, which have identified toxic and mutagenic effects of the common military explosives and their transformation products (Bruns-Nagel et al., 1999a; Fuchs et al., 2001; Homma-Takeda et al., 2002; Honeycutt et al., 1996; Rosenblatt et al., 1991; Spanggord et al., 1982; Tan et al., 1992 and Won et al., 1976). Because the cleanup of areas contaminated by explosives is now mandated because of public health concerns, considerable effort has been invested in finding economical remediation technologies. Biological treatment processes are often considered, since these are usually the least expensive means of destroying organic pollution. This review examines the most important groups of chemicals that must be treated at sites contaminated by explosives processing, the chemical and biological transformations they undergo, and commercial processes developed to exploit these transformations for treatment of contaminated soil. We critically examine about 150 papers on the topic, including approximately 60 published within the past 5 years.     

Combined effect of natural organic matter and surfactants on the apparent solubility of polycyclic aromatic hydrocarbons

Both natural organic matter (NOM) and surfactants are known to enhance the apparent aqueous solubility of hydrophobic organic contaminants (HOCs) in aqueous systems. In this study, the combined effect of NOM and surfactants on enhancing the solubility of HOCs was investigated, since both may occur and affect the fate and transport of HOCs in natural aqueous environments. Experimental results indicated that the apparent solubility of naphthalene, phenanthrene, and pyrene in NOM and anionic surfactant solution was lower than their solubility in NOM solution alone. However, the apparent solubility of an HOC in NOM and nonionic surfactant solution is almost the same as the sum of the HOC's solubility in NOM solution plus its solubility in nonionic surfactant solution. The observation that apparent aqueous solubility of HOCs in NOM and anionic surfactant solution is decreased is probably due to the fact that the cations that are released when the anionic surfactant dissociates may form ion pairs with acidic or phenolic groups associated with the NOM. This serves to increase the size of hydration of these groups, thereby decreasing the effective size of the nonpolar moieties associated with the NOM, and thus decreasing hydrophobic partitioning of the HOCs into the NOM. The results presented here will help us to understand the effect of NOM and surfactants on the fate and transport of HOCs in aquatic systems.     

改性沸石对水体中硝酸盐的吸附机理及其残渣的资源化利用

利用HDTMA改性沸石制成吸附剂,研究对水体中硝酸盐的吸附能力和机理及吸附剂残渣的资源化应用前景。结果表明:HDTMA改性沸石可增强其对硝酸盐的吸附能力。通过红外光谱和差热分析它的吸附机理,表明:改性沸石HZ4吸附有十六烷基三甲基溴化铵(HDTMA)分子;吸附剂残渣NHZ4吸附有十六烷基三甲基溴化铵(HDTMA)分子和硝酸盐。盆栽实验结果表明:吸附剂残渣NHZ4能提高玉米生物量,最大增幅为30.4%。     

Impact of sample preparation on mineralogical analysis of zero-valent iron reactive barrier materials

Permeable reactive barriers (PRBs) of zero-valent iron (Fe(0)) are increasingly being used to remediate contaminated ground water. Corrosion of Fe(0) filings and the formation of precipitates can occur when the PRB material comes in contact with ground water and may reduce the lifespan and effectiveness of the barrier. At present, there are no routine procedures for preparing and analyzing the mineral precipitates from Fe(0) PRB material. These procedures are needed because mineralogical composition of corrosion products used to interpret the barrier processes can change with iron oxidation and sample preparation. The objectives of this study were (i) to investigate a method of preparing Fe(0) reactive barrier material for mineralogical analysis by X-ray diffraction (XRD), and (ii) to identify Fe mineral phases and rates of transformations induced by different mineralogical preparation techniques. Materials from an in situ Fe(0) PRB were collected by undisturbed coring and processed for XRD analysis after different times since sampling for three size fractions and by various drying treatments. We found that whole-sample preparation for analysis was necessary because mineral precipitates occurred within the PRB material in different size fractions of the samples. Green rusts quickly disappeared from acetone-dried samples and were not present in air-dried and oven-dried samples. Maghemite/magnetite content increased over time and in oven-dried samples, especially after heating to 105 degrees C. We conclude that care must be taken during sample preparation of Fe(0) PRB material, especially for detection of green rusts, to ensure accurate identification of minerals present within the barrier system.     

Retention of gases by hexadecyltrimethylammonium-montmorillonite clays

Intercalated montmorillonite clays with different amounts of organic hexadecyltrimethylammonium (HDTMA) cations were studied to analyse their CO, CH(4), and SO(2) gas retentions. Equilibrium adsorption was measured by using a standard volumetric apparatus at 25 degrees C and 0.1 MPa. The solids were characterised by X-ray diffraction. The levels of adsorption of SO(2) by organo-montmorillonites (0.3595-1.6403 mmol/g) were higher than those of CO (up to 0.0202 mmol/g) and CH(4) (up to 0.0273 mmol/g) gases. HDTMA montmorillonites may be effective adsorbents for removing SO(2) and for its potential separation in the presence of CO and/or CH(4) molecules, which can be present in contaminated air.