Lactate Injection by Electric Currents for Bioremediation of Tetrachloroethylene in Clay.

Biological transformation of tetrachloroethylene (PCE) in silty clay samples by ionic injection of lactate under electric fields is evaluated. To prepare contaminated samples, a silty clay slurry was mixed with PCE, inoculated with KB-1(®) dechlorinators and was consolidated in a 40 cm long cell. A current density between 5.3 and 13.3 A m(-2) was applied across treated soil samples while circulating electrolytes containing 10 mg L(-1) lactate concentration between the anode and cathode compartments to maintain neutral pH and chemically reducing boundary conditions. The total adsorbed and aqueous PCE was degraded in the soil to trichloroethylene (TCE), cis-1,2-dichloroethene (cis-DCE), vinyl chloride (VC) and ethene in 120 d, which is about double the time expected for transformation. Lactate was delivered into the soil by a reactive transport rate of 3.7 cm(2) d(-1) V(-1). PCE degradation in the clay samples followed zero order transformation rates ranging from 1.5 to 5 mg L(-1) d(-1) without any significant formation of TCE. cis-DCE transformation followed first order transformation rates of 0.06 to 0.10 per day. A control experiment conducted with KB-1 and lactate, but without electricity did not show any significant lactate buildup or cis-DCE transformation because the soil was practically impermeable (hydraulic conductivity of 2×10(-7) cm s(-1)). It is concluded that ionic migration will deliver organic additives and induce biological activity and complete PCE transformation in clay, even though the transformation occurs under slower rates compared to ideal conditions.

Electrolytic transformation of ordinance related compounds (ORCs) in groundwater: laboratory mass balance studies.

Electrolytic reactive barriers (e(-) barriers) consist of closely spaced permeable electrodes installed across a groundwater contaminant plume in a permeable reactive barrier format. Application of sufficient potential to the electrodes results in sequential oxidation and reduction of the target contaminant. The objective of this study was to quantify the mass distribution of compounds produced during sequential electrolytic oxidation and reduction of ordinance related compounds (ORCs) in a laboratory analog to an e(-) barrier. In this study, a series of column tests were conducted using RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) and TNT (2,4,6-trinitrotoluene) as representative ORCs. The experimental setup consisted of a plexiglass column packed with quartz-feldspar sand to simulate aquifer conditions. A single set of porous electrodes consisting of expanded titanium-mixed metal oxide mesh was placed at the midpoint of the sand column as a one-dimensional analog to an e(-) barrier. Constant current of 20mA (variable voltage) was applied to the electrode set. Initial studies involved quantification of reaction products using unlabeled RDX and TNT. Approximately 70% of the influent concentration was transformed, in one pass, through sequential oxidation-reduction for both contaminants. Following the unlabeled studies, (14)C labeled RDX and TNT were introduced to determine the mass balance. An activity balance of up to 96% was achieved for both (14)C-RDX and (14)C-TNT. For both contaminants, approximately 21% of the influent activity was mineralized to (14)CO(2). The proportion of the initial activity in the dissolved fraction was different for the two test contaminants. Approximately 30% of the initial (14)C-RDX was recovered as unreacted in the dissolved phase. The balance of the (14)C-RDX was recovered as non-volatile, non-nitroso transformation products. None of the (14)C-RDX was sorbed to the column sand packing. For (14)C-TNT approximately 51% of the initial activity was recovered in the dissolved phase, the majority was unreacted TNT. The balance of the (14)C-TNT was either sorbed to the sand packing (approximately 24%) or dissolved/mineralized as unidentified ring cleavage products ( approximately 4%).

Applicability of alkaline hydrolysis for remediation of TNT-contaminated water.

This study was conducted to assess the applicability of alkaline hydrolysis as an alternative ex situ technology for remediating 2,4,6-trinitrotoluene (TNT)-contaminated water. TNT reactivity had a strong dependence on the reaction pH (11-12) and initial TNT (5-25 mg L(-1)) in batch systems, resulting in pseudo first-order transformation rate, k ranging between 1.9 x 10(-3) and 9.3 x 10(-5) min(-1). In continuous flow stirred-tank reactor (CFSTR) systems with initial TNT of 1 mg L(-1), the highest 74% of TNT reduction was achieved at the reaction pH of 11.9 and 2-day hydraulic retention time under steady-state condition. Oxalate was produced as the major hydrolysate in the CFSTRs, indicating a ring cleavage during alkaline hydrolysis. It was also believed that TNT alkaline hydrolysis occurred through the production of color-forming intermediates via dimerization. It is concluded that alkaline hydrolysis can be an alternative treatment technology for remediation of TNT-contaminated water.

Decolorization of alkaline TNT hydrolysis effluents using UV/H(2)O(2).

Effects of H(2)O(2) dosage (0, 10, 50, 100 and 300 mg/l), reaction pH (11.9, 6.5 and 2.5) and initial color intensity (85, 80 and 60 color unit) on decolorization of alkaline 2,4,6-trinitrotoluene (TNT) hydrolysis effluents were investigated at a fixed UV strength (40 W/m(2)). Results indicated that UV/H(2)O(2) oxidation could efficiently achieve decolorization and further mineralization. Pseudo first-order decolorization rate constants, k, ranged between 2.9 and 5.4 h(-1) with higher values for lower H(2)O(2) dosage (i.e., 10 mg/l H(2)O(2)) when the decolorization occurred at the reaction pH of 11.9, whereas a faster decolorization was achieved with increase in H(2)O(2) dosage at both pH 6.5 and 2.5, resulting in the values of k as fast as 15.4 and 26.6 h(-1) with 300 mg/l H(2)O(2) at pH 6.5 and 2.5, respectively. Difference in decolorization rates was attributed to the reaction pH rather than to the initial color intensity, resulting from the scavenging of hydroxyl radical by carbonate ion. About 40% of spontaneous mineralization was achieved with addition of 10 mg/l H(2)O(2) at pH 6.5. Efficient decolorization and extension of H(2)O(2) longevity were observed at pH 6.5 conditions. It is recommended that the colored effluents from alkaline TNT hydrolysis be neutralized prior to a decolorization step.

RDX biodegradation column study: comparison of electron donors for biologically induced reductive transformation in groundwater.

A series of column studies, using site-specific soil and groundwater, were conducted to determine the feasibility of biologically active zone enhancement (BAZE) process for reductive biotransformation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in groundwater. This treatability study examined the use of four amendments (acetate, ethanol, soluble starch, and acetate plus ammonium), which served as electron donors. Triplicate columns, with groundwater residence time of about 27.5 h, were used for each amendment treatment and the amendment control. In treatment columns amendment dosing was 500 mg/L C for carbon sources and 100 mg/L N for ammonium. Each of the amendment treatments reduced RDX inlet concentrations of 100 microg/L to less than 1 microg/L. The highest first-order RDX biodegradation rate ranged between 0.140 and 0.447 h(-1) for acetate amended columns as compared to 0.037 to 0.083 h(-1) in control columns (no amendment). The addition of soluble starch resulted in increased toxicity (based on Microtox analysis) that was partially removed by biological activity in the columns. Ethanol addition itself did not result in increased toxicity but biological activity in this system did induce Microtox toxicity. Acetate did not have any Microtox toxicity associated with it. The addition of ammonium as a nitrogen source did not significantly increase the removal rate of RDX. Based on these observations acetate was selected for the field demonstration.

Analysis of CL-20 in environmental matrices: water and soil.

Analytical techniques for the detection of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclo(5.5.0.05,9.03,11)dodecane (CL-20) in water and soil are developed by adapting methods traditionally used for the analysis of nitroaromatics. CL-20 (a new explosives compound) is thermally labile, exhibits high polarity, and has low solubility in water. These constraints make the use of specialized sample handling, preparation, extraction, and analysis necessary. The ability to determine the concentrations of this new explosive compound in environmental matrices is helpful in understanding the environmental fate and effects of CL-20; understanding the physical, chemical, and biological fate of CL-20; and can be used in developing remediation technologies and determining their efficiency. The toxicity and mobility of new explosives in soil and groundwater are also of interest, and analytical techniques for quantitating CL-20 and its degradation products in soil and natural waters make these investigations possible.

Electrolytic redox and electrochemical generated alkaline hydrolysis of hexahydro-1,3,5-trinitro-1,3,5 triazine (RDX) in sand columns.

Sand-packed horizontal flow columns (5 cm i.d. x 65 cm)l were used in laboratory experiments to simulate in situ electrolytic and alkaline hybrid treatment zone for aqueous phase decomposition of RDX. An upgradient cathode and downgradient anode, spaced 35 cm apart were used to create alkaline reducing conditions followed by oxic, acidic conditions to degrade RDX by combination of alkaline hydrolysis and direct electrolysis. A preliminary experiment (25 mg/L RDX influent) with seepage velocity of 30.5 cm/day and current density of 9.9 A/m2 was used to determine the treatment feasibility and the aqueous products of RDX decomposition. Three additional column experiments (0.5 mg/L RDX influent) under the same conditions as the preliminary column were used to observe the treatment process repeatability and the alkaline treatment zone development. The results demonstrated approximately 95% decomposition of RDX in the column with an applied current density of 9.9 A/m2. Aqueous end-products formate, nitrite, and nitrate were detected in the effluent. Approximately 75% of the RDX was destroyed near the cathode, presumably by electrolysis, with 23% decomposed downstream of the cathode by alkaline hydrolysis. The preliminary column pseudo first order alkaline hydrolysis rate coefficient of 10.7 x 10(-3) min(-1) was used to estimate a treatment zone length less than 100 cm for RDX treatment below the EPA drinking water lifetime health advisory of 0.002 mg/L.

Sorption of 2,4,6-trinitrotoluene to natural soils before and after hydrogen peroxide application.

Laboratory batch sorption experiments were conducted to investigate the impact of hydrogen peroxide (H2O2) pre-application on post-sorptive behavior of 2,4,6-trinitrotoluene (TNT) in different natural soils (average soil, high Fe soil, and high pH soil). After H2O2 application, the values of Freundlich coefficient Kf were increased by approximately 160% for the average and high pH soils and by approximately 120% for the high Fe soil, showing that the soils became more favorable for TNT sorption after H202 application. Nonlinearity in terms of the Freundlich exponent n was increased by approximately 40% for the average and high pH soils and by approximately 30% for the high Fe soil, showing greater sorption affinity of TNT for the oxidized soils at lower TNT concentrations and also implying greater TNT availability for transport at high concentrations. The increase in sorption extent for the H2O2-oxidized soils was presumably attributed to the oxygen-induced enhancement in the sorption capacity of the soils and the more dominant contribution of clay minerals to sorption. Therefore, enhanced sorption following H2O2 application may inhibit the subsequent formation of a TNT plume after either source zone remediation or plume remediation using H2O2 such as Fenton oxidation.