Quantification of potassium permanganate consumption and PCE oxidation in subsurface materials

A series of laboratory scale batch slurry experiments were conducted in order to establish a data set for oxidant demand by sandy and clayey subsurface materials as well as to identify the reaction kinetic rates of permanganate (MnO(4)(-)) consumption and PCE oxidation as a function of the MnO(4)(-) concentration. The laboratory experiments were carried out with 31 sandy and clayey subsurface sediments from 12 Danish sites. The results show that the consumption of MnO(4)(-) by reaction with the sediment, termed the natural oxidant demand (NOD), is the primary reaction with regards to quantification of MnO(4)(-) consumption. Dissolved PCE in concentrations up to 100 mg/l in the sediments investigated is not a significant factor in the total MnO(4)(-) consumption. Consumption of MnO(4)(-) increases with an increasing initial MnO(4)(-) concentration. The sediment type is also important as NOD is (generally) higher in clayey than in sandy sediments for a given MnO(4)(-) concentration. For the different sediment types the typical NOD values are 0.5-2 g MnO(4)(-)/kg dry weight (dw) for glacial meltwater sand, 1-8 g MnO(4)(-)/kg dw for sandy till and 5-20 g MnO(4)(-)/kg dw for clayey till. The long term consumption of MnO(4)(-) and oxidation of PCE can not be described with a single rate constant, as the total MnO(4)(-) reduction is comprised of several different reactions with individual rates. During the initial hours of reaction, first order kinetics can be applied, where the short term first order rate constants for consumption of MnO(4)(-) and oxidation of PCE are 0.05-0.5 h(-1) and 0.5-4.5 h(-1), respectively. The sediment does not act as an instantaneous sink for MnO(4)(-). The consumption of MnO(4)(-) by reaction with the reactive species in the sediment is the result of several parallel reactions, during which the reaction between the contaminant and MnO(4)(-) also takes place. Hence, application of low MnO(4)(-) concentrations can cause partly oxidation of PCE, as the oxidant demand of the sediment does not need to be met fully before PCE is oxidised.     

Reaction-enhanced mass transfer and transport from non-aqueous phase liquid source zones

The objective of the following research is to theoretically quantify the enhancement of interphase mass transfer of dissolved non-aqueous phase liquid (NAPL) compounds from the non-aqueous phase to the aqueous phase and the enhancement of dispersive mass transport from a NAPL zone due to destruction of dissolved NAPL compounds. For relatively slow reaction rates, such as for permanganate and perchloroethene (PCE), local-scale mass transfer enhancement is expected to be small. Dispersive mass transport with reaction from a horizontal NAPL zone can be quantified using equations derived for a mathematically equivalent falling film reactor system. In contrast to local-scale interphase mass transfer, dispersive mass transport from NAPL zones may be significantly increased by reaction. Enhancement factors due to destruction of the NAPL compound(s) are mainly dependent on NAPL solubility and oxidant concentration and to a lesser extent on reaction rate, stoichiometry, and transverse dispersion coefficients. Higher NAPL solubility and/or lower oxidant concentration reduces the maximum expected enhancement factor. Reaction enhancement factors for mass transport from NAPL zones are expected to be in the range of 5-50 for permanganate and chlorinated solvents. Theoretical results suggest that assuming instantaneous reaction rates may be appropriate for dispersive mass transport from NAPL zones.     

Kinetics of acid-catalyzed aldol condensation reactions of aliphatic aldehydes

Field observations of atmospheric aerosols have established that organic compounds compose a large fraction of the atmospheric aerosol mass. However, the physical/chemical pathway by which organic compounds are incorporated into atmospheric aerosols remains unclear. The potential role of acid-catalyzed reactions of organic compounds on acidic aerosols has been explored as a possible chemical pathway for the incorporation of organic material into aerosols. In the present study, ultraviolet–visible (UV–vis) spectroscopy was used to monitor the kinetics of formation of the products of the acid-catalyzed aldol condensation reaction of a range of aliphatic aldehydes (C₂–C₈). The experiments were carried out at various sulfuric acid concentrations and a range of temperatures in order to estimate the rate constants of such reactions on sulfuric acid aerosols under tropospheric conditions. The rate constants were generally found to decrease as the chain length of the aliphatic aldehyde increased (except for acetaldehyde, which had an unusually small rate constant), increase as a function of sulfuric acid concentration as predicted by excess acidity theory, and showed normal Arrhenius behavior as a function of temperature. While the kinetic data are generally consistent with previous laboratory reports of aldehyde reactivity in various sulfuric acid media, the aldol condensation reactions involving aliphatic aldehydes do not appear fast enough to be responsible for significant transfer of organic material into atmospheric aerosols.     

Cosolvent effect on the catalytic reductive dechlorination of PCE

Reductive dechlorination of chlorinated organic contaminants is an effective approach to treat this widespread group of environmentally hazardous substances. Metalloporphyrins can be used to catalyze reduction reactions by shuttling electrons from a reducing agent (electron donor) to chlorinated organic contaminants, thus rendering them to non-chlorinated acetylene, ethylene or ethane as major products. Iron, nickel and vanadium oxide tetraphenyl porphyrins (TPPs) were used as models of non-soluble metalloporphyrins that are common in subsurface environments, and hence may inflect on the ability to use natural ones. The effect of cosolvents on metalloporphyrins is demonstrated to switch the reduction of tetrachlorethylene (PCE) from no reaction to complete PCE transformation within 24 h and the production of final non-chlorinated compounds. Variations in product distributions for the different metalloporphyrins indicate that changes in the core metal can influence reaction rates and effective pathways. Furthermore, different cosolvents can generate varied product distributions, again suggesting that different pathways and/or rates are operative in the reduction reactions. Comparison of different cosolvent effects on PCE reduction using vitamin B12--a soluble natural metalloporphyrinogen--as the catalyst shows less pronounced differences between reactions in various cosolvent solutions versus only aqueous solution.     

Effects of black carbon and montmorillonite clay on multiphasic hexachlorobenzene desorption from sediments

The desorption kinetics of hexachlorobenzene (HCB) in four freshly spiked artificial sediments were determined using a polymeric adsorbent Tenax-mediated desorption. The sediments included a standard sediment (SS) prepared as per Organisation for Economic Cooperation and Development 218 guidelines and three derived artificial sediments prepared by supplementing the SS sediment with various levels of black carbon (lamp black soot) and/or montmorillonite clay. The desorption kinetics exhibited biphasic behavior, i.e., a fast desorbing fraction followed by a slow desorbing fraction. The addition of either lamp black soot or montmorillonite clay resulted in the reduction of the fast desorbing fraction (Ffast) of HCB in three derived sediments compared with SS sediment. Both black carbon and montmorillonite clay treatment effects on the fast desorbing fraction were statistically significant for the four artificial sediments. The black carbon treatment (i.e., addition of 0.5% wt/wt lamp black soot) effect was an average reduction of Ffast by approximately 11%, whereas the montmorillonite treatment (i.e., addition of 15% wt/wt montmorillonite clay) effect was an average reduction of Ffast by approximately 17%. The presence of soot black carbon particles reduced the desorption rate of HCB in sediments since black carbon exhibits very high sorption capacity and extremely slow diffusion rate compared with those of the natural organic matter in sediment.     

Three-dimensional density-dependent flow and multicomponent reactive transport modeling of chlorinated solvent oxidation by potassium permanganate

A popular method for the treatment of aquifers contaminated with chlorinated solvents is chemical oxidation based on the injection of potassium permanganate (KMnO₄). Both the high density (1025 gL^− 1) and reactivity of the treatment solution influence the fate of permanganate (MnO₄) in the subsurface and affect the degree of contaminant treatment. The MIN3P multicomponent reactive transport code was enhanced to simulate permanganate-based remediation, to evaluate the pathways of MnO₄ utilization, and to assess the role of density contrasts for the delivery of the treatment solution. The modified code (MIN3P-D) provides a direct coupling between density-dependent fluid flow, solute transport, contaminant treatment, and geochemical reactions. The model is used to simulate a field trial of TCE oxidation in a sandy aquifer that is underlain by an aquitard. Three-dimensional simulations are conducted for a coupled reactive system comprised of ten aqueous components, two mineral phases, TCE (dissolved, adsorbed, and NAPL), reactive organic matter, and including ion exchange reactions. Model parameters are constrained by literature data and a detailed data set from the field site under investigation. The general spatial and transient evolution in observed concentrations of the oxidant, dissolved TCE, and reaction products are adequately reproduced by the simulations. The model elucidates the important role of density-induced flow and transport on the distribution of the treatment solution into NAPL containing regions located at the aquifer–aquitard interface. Model results further suggest that reactions that do not directly affect the stability of MnO₄ have a negligible effect on solution density and MnO₄ delivery.     

Effects of sorption on transverse mixing in transient flows

Transverse mixing has been identified as a potentially limiting factor for natural attenuation of plumes originating from continuously emitting sources. Under steady-state flow conditions, dispersion is the only process leading to lateral mixing. This process is very slow and cannot explain the lateral spread of plumes observed in the field. When the flow direction fluctuates with time, transverse dispersion is slightly enhanced, but not very pronounced. Under these flow conditions, however, sorption can contribute to mixing into the mean transverse direction. If the reacting compounds differ in their strength of sorption, chromatographic mixing and separation alternate in time-periodic flows. For instantaneous sorption, the plumes may overlap within a stripe of fixed width. In contrast to sorption in local equilibrium, kinetic sorption contributes to mixing also for compounds with identical sorption strength. I derive an analytical expression for the equivalent transverse dispersion coefficient of a kinetically sorbing compound in a spatially uniform flow field undergoing sinusoidal fluctuations in time. This expression may be used for reactive transport calculations in an equivalent domain with constant flow. The effects are the strongest for compounds with a dimensionless partitioning coefficient of about unity, slow sorption kinetics, and slowly fluctuating velocities. For realistic parameters, kinetic sorption contributes to transverse mixing in the same range as heterogeneity.     

Degradation of volatile organic compounds with thermally activated persulfate oxidation

This study investigated the extent and treatability of the degradation of 59 volatile organic compounds (VOCs) listed in the EPA SW-846 Method 8260B with thermally activated persulfate oxidation. Data on the degradation of the 59 VOCs (in mixture) reacted with sodium persulfate in concentrations of 1 g l(-1) and 5 g l(-1) and at temperatures of 20 degrees C, 30 degrees C, and 40 degrees C were obtained. The results indicate that persulfate oxidation mechanisms are effective in degrading many VOCs including chlorinated ethenes (CEs), BTEXs and trichloroethanes that are frequently detected in the subsurface at contaminated sites. Most of the targeted VOCs were rapidly degraded under the experimental conditions while some showed persistence to the persulfate oxidation. Compounds with "CC" bonds or with benzene rings bonded to reactive functional groups were readily degraded. Saturated hydrocarbons and halogenated alkanes were much more stable and difficult to degrade. For those highly persulfate-degradable VOCs, degradation was well fitted with a pseudo first-order decay model. Activation energies of reactions of CEs and BTEXs with persulfate were determined. The degradation rates increased with increasing reaction temperature and oxidant concentration. Nevertheless, to achieve complete degradation of persulfate-degradable compounds, the systems required sufficient amounts of persulfate to sustain the degradation reaction.     

Intermediate-scale 2D experimental investigation of in situ chemical oxidation using potassium permanganate for remediation of complex DNAPL source zones

In situ chemical oxidation is a technology that has been applied to speed up remediation of a contaminant source zone by inducing increased mass transfer from DNAPL sources into the aqueous phase for subsequent destruction. The DNAPL source zone can consist of one or more individual sources that may be present as an interconnected pool of high saturation, as a region of disconnected ganglia at residual saturation, or as combinations of these two morphologies. Potassium permanganate (KMnO(4)) is a commonly employed oxidant that has been shown to rapidly destroy DNAPL compounds like PCE and TCE following second-order kinetics in an aqueous system. During the oxidation of a target DNAPL compound, or naturally occurring reduced species in the subsurface, manganese oxide (MnO(2)) solids are produced. Research has shown that these manganese oxide solids may result in permeability reductions in the porous media thus reducing the ability for oxidant to be transported to individual DNAPL sources. It can also occur at the DNAPL-water interface, decreasing contact of the oxidant with the DNAPL. Additionally, MnO(2) formation at the DNAPL-water interface, and/or flow-bypassing as a result of permeability reductions around the source, may alter the mass transfer from the DNAPL into the aqueous phase, potentially diminishing the magnitude of any DNAPL mass depletion rate increase induced by oxidation. An experiment was performed in a two-dimensional (2D) sand-filled tank that included several discrete DNAPL source zones. Spatial and temporal monitoring of aqueous PCE, chloride, and permanganate concentrations was used to relate changes in mass depletion of, and mass flux, from DNAPL residual and pool source zones to chemical oxidation performance and MnO(2) formation. During the experiment, permeability changes were monitored throughout the 2D tank and these were related to MnO(2) deposition as measured through post-oxidation soil coring. Under the conditions of this experiment, MnO(2) formation was found to reduce permeability in and around DNAPL source zones resulting in changes to the overall flow pattern, with the effects depending on source zone configuration. A pool with little or no residual around it, in a relatively homogeneous flow field, appeared to benefit from resulting MnO(2) pore-blocking that substantially reduced mass transfer from the pool even though there was relatively little PCE mass removed from the pool. In contrast, a pool with residual around it (in a more typical heterogeneous flow field) appeared to undergo increased mass transfer as MnO(2) reduced permeability, altering the water flow and increasing the mixing at the DNAPL-water interface. Further, the magnitude of increased PCE mass depletion during oxidation appeared to depend on the PCE source configuration (pool versus ganglia) and decreased as MnO(2) was formed and deposited at the DNAPL-water interface. Overall, the oxidation of PCE mass appeared to be rate-limited by the mass transfer from the DNAPL to aqueous phase.     

A standardized method for assessment of oxidative transformations of brominated phenols in water

The term persistence has been used to confusion since it is used as a conceptual parameter without a uniform definition. Work is therefore being done in order to unite ideas and describe persistence based on the chemical reactivity and chemico-physical properties of compounds via investigation of the main degradation pathways in the environment; photolysis, hydrolysis-substitution-elimination (hse), oxidation, reduction and radical reactions. The present work is focused on developing a method to determine oxidative degradation rates of chemicals and thereby measurement of their susceptibility to undergo oxidation reactions. The method based on potassium permanganate works well for water soluble compounds and is easy, robust, inexpensive and reproducible. By using the method and varying the analysed substances, the degradation rates for brominated phenols, two chlorinated phenols and high volume production compounds such as tetrabromobisphenol A (TBBPA), tetrachlorobisphenol A (TCBPA) and bisphenol A (BPA) have been determined at pH 7.6+/-0.2. The reaction rates of the two halogenated BPA's are particularly fast, giving half-lives in seconds. The other test compounds have slower reaction rates but easily measured under the reaction conditions applied. The reactions are temperature dependent. There is evidence that pK(a) and the substitution pattern of the halogens affects the rate of the reactions. The method is robust and applicable for reaction rate constant measurements of present and potential future environmental contaminants.     

高锰酸钾降解地下水中PCE的研究

以氯代有机污染物中常见的PCE为目标污染物,以自制高锰酸钾溶液为氧化剂,采用批实验方法,探讨了高锰酸钾降解PCE的反应动力学、影响因素以及反应机理。反应结果表明,高锰酸钾降解PCE的反应符合一级动力学方程,反应活化能E为57.119 kJ/mol,在30℃条件下,反应速率常数为0.0076 min^-1,半衰期为91.20 min。在pH在3～10,离子强度在0～0.1030 mol/L之间变化时,反应速率不受明显影响。     

Fe2+活化过硫酸钠降解1,2-二氯苯

以Na2S2O8为氧化剂,柠檬酸螯合Fe2+为活化剂,对水中1,2-二氯苯进行处理。首先研究了Na2S2O8浓度、FeSO4浓度、柠檬酸浓度及初始pH值等因素对1,2-二氯苯降解的影响;然后通过正交实验,发现在Na2S2O8浓度14.28 mmol/L、FeSO4浓度7.14 mmol/L、柠檬酸浓度3.57 mmol/L、初始pH值3.0的条件,1,2-二氯苯降解率达到最大(99.28%)。进一步研究表明,柠檬酸螯合FeSO4活化Na2S2O8降解1,2-二氯苯的过程可分为2个阶段,其中第1阶段为快速反应,第2阶段反应速度较慢并且符合一级反应动力学规律。     

Photodegradation of pentachlorophenol by sunlight in aquatic surface microlayers

Photodegradation of pentachlorophenol (PCP) in aquatic surface microlayer (SM) was examined under natural sunlight. SM samples were collected using a glass plate, along with corresponding subsurface waters. PCP was added to samples of the SM and subsurface water. When all samples were exposed to the same natural sunlight conditions, the first order photodegradation rates of PCP in the SM water samples were different from those of PCP in corresponding subsurface water samples. The difference was correlated with the enrichment of dissolved organic carbon (DOC) in SM compared to the corresponding subsurface waters. Enhanced photodegradation in SM may be due to increased abundance of photoreactants related to the UV-absorbing properties of dissolved organic materials in the SM as the result of photo-induced reactions. Effects of environmental factors, pH and salinity, on photodegradation process of PCP in SM were also evaluated.     

Modeling in situ ozonation for the remediation of nonvolatile PAH-contaminated unsaturated soils

Mathematical models were developed to investigate the characteristics of gaseous ozone transport under various soil conditions and the feasibility of in situ ozone venting for the remediation of unsaturated soils contaminated with phenanthrene. On the basis of assumptions for the mass transfer and reactions of ozone, three approaches were considered: equilibrium, kinetic, and lump models. Water-saturation-dependent reactions of gaseous ozone with soil organic matter (SOM) and phenanthrene were employed. The models were solved numerically by using the finite-difference method, and the model parameters were determined by using the experimental data of Hsu [The use of gaseous ozone to remediate the organic contaminants in the unsaturated soils, PhD Thesis, Michigan State Univ., East Lansing, MI, 1995]. The transport of gas-phase ozone is significantly retarded by ozone consumption due to reactions with SOM and phenanthrene, in addition to dissolution. An operation time of 156 h was required to completely remove phenanthrene in a 5-m natural soil column. In actual situations, however, the operation time is likely to be longer than the ideal time because of unknown factors including heterogeneity of the porous medium and the distribution of SOM and contaminant. The ozone transport front length was found to be very limited (< 1 m). The sensitivity analysis indicated that SOM is the single most important factor affecting in situ ozonation for the remediation of unsaturated soil contaminated with phenanthrene. Models were found to be insensitive to the reaction mechanisms of phenathrene with either gas-phase ozone or dissolved ozone. More study is required to quantify the effect of OH* formation on the removal of contaminant and on ozone transport in the subsurface.     

Sorption kinetics and its effects on retention and leaching.

Sorption of pesticides to substrates used in biopurification systems is important as it controls the system's efficiency. Ideally, pesticide sorption should occur fast so that leaching of the pesticide in the biopurification system is minimized. Although modeling of pesticide transport commonly assumes equilibrium, this may not always be true in practice. Sorption kinetics have to be taken into account. This study investigated the batch sorption kinetics of linuron, isoproturon, metalaxyl, isoxaben and lenacil on substrates commonly used in a biopurification system, i.e. cow manure, straw, willow chopping, sandy loam soil, coconut chips, garden waste compost and peat mix. The first-order sorption kinetics model was fitted to the observed pesticide concentrations versus time resulting in an estimated kinetic rate constant alpha. Sorption appeared to be fast for the pesticides linuron and isoxaben, pesticides which were classified as immobile, while less mobile pesticides displayed an overall slower sorption. However, the substrate does not seem to be the main parameter influencing the sorption kinetics. Coconut chips, which is a substrate with a high organic matter content showed slow sorption for most of the pesticides. The effect of different estimated alpha values on the breakthrough of pesticides through a biopurification system was evaluated using the HYDRUS 1D model. Significant differences in leaching behavior were observed as a result of the obtained differences in sorption kinetics.     

Efficient removal of triphenylmethane dyes from aqueous medium by in situ electrogenerated Fenton's reagent at carbon-felt cathode

Fenton's reagent (Fe2+ +H2O2) has been electrogenerated in situ in an undivided electrolytic cell from the effective reduction of Fe3+ and O2 at carbon-felt cathode for the treatment of aqueous solutions of four triphenylmethane dyes (TPMs), namely malachite green (MG), crystal violet (CV), methyl green (MeG) and fast green FCF (FCF), at pH 3.0 and room temperature. MG has been used as a model among them to study the influence of some experimental parameters on the decay kinetics, COD removal and current efficiency. The results in such electro-Fenton system are explained in terms of the many parasitic reactions involving .OH. Higher efficiency values are obtained with rising organic content and decreasing applied current. The first stage of the mineralization process, involving aromatic by-products, leads to fast decoloration as well as quick initial COD removal that fit well to a pseudo-first-order kinetics. At prolonged electrolysis time, the mineralization rate and efficiency decrease due to the formation of hardly oxidizable compounds and the enhancement of wasting reactions. Solutions of all four TPMs are quickly degraded following a pseudo-first-order decay kinetics. The absolute rate constant (kTPM) for their reaction with .OH increases in the order MeG相似文献   

Oxidative transformation of polybrominated diphenyl ether congeners (PBDEs) and of hydroxylated PBDEs (OH-PBDEs)

BACKGROUND, AIM, AND SCOPE: The historical and widespread use of polybrominated diphenyl ethers (PBDEs) as flame retardants in consumer products worldwide has caused PBDEs to now be regarded as pervasive environmental contaminants. Most recently, hydroxylated PBDEs (OH-PBDEs) and methoxylated PBDEs (MeO-PBDEs) have emerged as environmentally relevant due to reports of their natural production and metabolism. An important parameter for assessing the environmental impact of a chemical substance is persistence. By formulating the concept that persistence is the result of the substance's physicochemical properties and chemical reactivity, Green and Bergman have proposed a new methodology to determine the inherent persistence of a chemical. If persistence could be predicted by straightforward methods, substances with this quality could be screened out before large-scale production/manufacturing begins. To provide data to implement this concept, we have developed new methodologies to study chemical transformations through photolysis; hydrolysis, substitution, and elimination; and via oxidation. This study has focused on adapting an oxidative reaction method to be applicable to non-water soluble organic pollutants. MATERIALS AND METHODS: PBDEs and one MeO-PBDE were dissolved in tetrahydrofuran/methanol and then diluted in alkaline water. The OH-PBDEs were dissolved in alkaline water prior to reaction. The oxidation degradation reaction was performed at 50 degrees C using potassium permanganate as described elsewhere. The pH was maintained at 7.6 with disodium hydrogen phosphate and barium hydrogen phosphate, the latter also serving as a trapping agent for manganate ions. The oxidation reactions were monitored by high-performance liquid chromatography and reaction rates were calculated. RESULTS: The OH-PBDEs have very fast oxidative transformation rates compared to the PBDEs. The reaction rates seem to be primarily dependent on substitution pattern of the pi-electron-donating bromine substituents and of bromine content. There are indications that further reactions of OH-PBDEs, e.g., methylation to the MeO-PBDEs, decrease the oxidation rates, and thereby generate more persistent substances. DISCUSSION: The resistance of PBDEs to oxidation, a major degradation pathway in air, should be further investigated, since these compounds do undergo long range transport. With slight modifications, the original method has been adapted to include a larger variety of chemical substances, and preliminary data are now available on the oxidative transformation rates for PBDEs and of OH-PBDEs. CONCLUSIONS: The original oxidation degradation method can now include non-water soluble compounds. This modification, using low concentrations of test chemicals, allows us to measure oxidative transformation rates, for some of the lower brominated DEs, data that can be used to assess their persistence in future model calculations. Oxidative transformation rates for PBDEs are slow compared to those for the OH-PBDEs. This suggests that OH-PBDEs, when released into the environment, undergo faster oxidative metabolism and excretion than the PBDEs. RECOMMENDATIONS AND PERSPECTIVES: To evaluate the modified method, more degradation reactions with non-water soluble compounds should be investigated. Recent studies show that OH-PBDEs are present in rats and in humans and, because of their activity as endocrine disruptors, determining their subsequent environmental fate is of importance. The resistance of PBDEs to oxidative degradation should be acknowledged as of possible future concern. Several other compound classes (such as polychlorinated biphenyls (PCBs), hydroxylated polychlorinated biphenyls (OH-PCBs), and pharmaceuticals) need to be subjected to this screening method to increase the database of transformation rates that can be used with this model.     

Laboratory-scale in situ chemical oxidation of a perchloroethylene pool using permanganate

In situ chemical oxidation (ISCO) is an emerging technology for the destruction of some chlorinated solvents present in subsurface environments. A laboratory investigation using a physical model was designed to assess the effectiveness of using permanganate as an oxidant to reduce the mass of a perchloroethylene (PCE) pool. The physical model was filled with silica sand overlying a silica flour base, simulating a two-dimensional saturated sand zone overlying a capillary barrier. PCE was introduced into the model so that it rested on top of the silica flour base, forming a dense nonaqueous phase liquid pool. The experimental methodology involved flushing the model with a permanganate solution for 146 days. During this period, measurements of chloride were used to assess the extent of pool oxidation. Before and after the oxidant flush, the quasi-steady state dissolution from the PCE pool was evaluated. Additionally, tracer studies were completed to assess changes in the flow field due to the oxidation process. At the termination of the experiment nine soil cores extracted from the model were used to detect the presence of MnO2 deposits and to quantify the mass of PCE remaining in the system. Excavation of the remaining material in the model revealed that the MnO2 distribution throughout the model was consistent with that observed in the cores. The oxidant flush was concluded before all of the pure phase PCE had been completely oxidized; however, approximately 45% of the PCE mass was removed, resulting in a fourfold decrease in the quasi-steady state aqueous phase mass loading of PCE from the pool. Measurements of chloride during the oxidant flush and of PCE in the soil cores suggested that the oxidation reaction occurred primarily at the upgradient edge of the PCE pool. MnO2 deposits within the model aquifer decreased the velocity of water directly above the pool, and the overall mass transfer from the remaining PCE pool. The results of this experimental study indicate that ISCO using permanganate is capable of removing substantial mass from a DNAPL pool; however, the performance of ISCO as a pool removal technology will be limited by the formation and precipitation of hydrous MnO2 that occurs during the oxidation process.     

Photolytic degradation of quinalphos in natural waters and on soil matrices under simulated solar irradiation

The photochemical persistence of quinalphos, one of the most widely used organophosphorous insecticides, was investigated in a variety of environmental matrices such as natural waters and soils of different composition. Simulated solar irradiation was obtained using a xenon arc lamp (Suntest CPS+ apparatus) giving an irradiation intensity of 750 W m(-2) equivalent to a light dose per hour of irradiation of 2,700 kJ m(-2). The phototransformation rates were determined using solid-phase microextraction (SPME) and ultrasonic extraction (USE) coupled to GC-FTD, while the identification of photoproducts was carried out by GC-MS. In water samples, the degradation kinetics followed a pseudo-first-order reaction and photolysis half-lives ranged between 11.6 and 19.0 h depending on the constitution of the irradiated media. Dissolved organic matter (DOM) has a predominant retarding effect, while nitrate ions accelerated the photodegradation kinetics. In soil samples, the degradation kinetics was monitored on 1mm soil layer prepared on glass TLC plates. The kinetic behaviour of quinalphos was complex and characterized by a double step photoreaction, fast in the first 4h of irradiation followed by a slow degradation rate up to 64 h. The photolysis half-life of quinalphos was shorter in sandy soil compared to the rest of the soil samples, varying between 16.9 and 47.5 h, and showing a strong dependence on the composition of the irradiated media. Among the transformation products formed mainly through photohydrolysis and photoisomerization processes, some photoproduct structures were proposed according to their mass spectral information.     

A comparison of two techniques for studying sediment desorption kinetics of hydrophobic pollutants

A comparison of two techniques (gaseous purge and vial desorption) for studying the kinetics of desorption of hydrophobic pollutants from natural sediments was conducted using identical, pre-equilibrated pollutant-sediment suspensions. Desorption profiles for the two techniques [for Lindane, Aldrin, 2,2'-dichlorobiphenyl (2,2'-DCB), 4,4'-dichlorobiphenyl (4,4'-DCB), and 2,2',6,6'-tetrachlorobiphenyl (TCB)] were then compared, based on the distribution of pollutant mass between the labile (fast) and non-labile (slow) desorption phases and the release rate constants for each phase of release. The vial desorption technique shows many practical advantages over the gaseous purge technique, including its more realistic mixing conditions, the use of an independent sample for each data point (as opposed to a calculation of a cumulative mass purged at each time point), the fact that the vials constitute a closed system and are therefore less subject to ambient contamination, and the relatively low demands of time and money for the vial technique. No consistent trends in labile rate constants or in pollutant distribution between the labile and non-labile phase were observed between the two techniques. A comparison of kinetic parameters shows much faster non-labile rate constants for the gaseous purge technique, attributed to the violent, continuous agitation employed, which likely disrupted sediment aggregates and oxidized the natural organic matter associated with the sediment. Non-labile rate constants have implications for the long-term fate of compounds adsorbed to repetitively disturbed sediments. This study suggests that the traditionally less popular vial desorption technique may yield more realistic non-labile desorption rate constants.