Application of persulfate-releasing barrier to remediate MTBE and benzene contaminated groundwater

The objective of this study was to assess the potential of using an in situ oxidation barrier system to remediate gasoline-contaminated groundwater. The passive remedial system included a persulfate-releasing barrier containing persulfate-releasing materials to release persulfate for contaminant oxidation. Bench experiments were performed to determine the components and persulfate-releasing rate of the persulfate-releasing materials. Column experiments were conducted to evaluate the effectiveness of the designed persulfate-releasing materials on the control of petroleum-hydrocarbon plume. In this study, methyl tert-butyl ether (MTBE) and benzene were used as the target compounds. The optimal persulfate releasing rate was obtained when the mass ratio of persulfate/cement/sand/water was 1/1/0.16/0.5, and the rate varied from 31 to 8 mg persulfate per day per g of material. Significant amounts of MTBE and benzene were removed through the oxidation process due to the release of persulfate, and the produced tert-butyl formate (TBF) and tert-butyl alcohol (TBA), byproducts of MTBE, were further oxidized in the system. Results suggest that the oxidation rate would be affected by the oxidant reduction potential and concentrations of ferrous iron and persulfate.     

Influence of inorganic ions on MTBE degradation by Fenton's reagent

The effect of selected inorganic anions on the effectiveness of the Fenton advanced oxidative treatment of waters contaminated with methyl t-butyl ether (MTBE) was examined. With respect to the chloride or phosphate ions used, inhibition of oxidation was clearly in evidence, whereas addition of sulfates or perchlorates influenced these rates to a much smaller extent. Anions suppress MTBE decomposition in the following sequence: ClO4- 相似文献   

Uptake, metabolism, and toxicity of methyl tert-butyl ether (MTBE) in weeping willows

Methyl tert-butyl ether (MTBE) is a high volume production chemical and the most commonly used gasoline oxygenate. Uptake, metabolism and toxicity of MTBE in trees were investigated in this study. Pre-rooted weeping willows (Salix babylonica L.) were exposed to hydroponic solution spiked with MTBE and incubated at 25.0+/-1 degrees C for 168 h. The normalized relative transpiration (NRT) rate of weeping willows was used to determine toxicity. MTBE and possible intermediate tert-butyl alcohol (TBA) in solution, tissues of aerial parts of plants, and air were analyzed. Results from the toxicity test showed that severe signs of toxicity (the reduction of the NRT >or=35%) were only found at the treatment group with high doses of MTBE 400 mg L(-1). Neither chlorosis of leaves nor large reduction in the NRT was observed at MTBE exposure to weeping willows 相似文献   

Method detection limit determination and application of a convenient headspace analysis method for methyl tert-butyl ether in water

Methyl tert-butyl ether (MTBE) is a common groundwater contaminant, introduced to the environment by leaking petroleum storage tanks, urban runoff, and motorized watercraft. In this study. a simplified (static) headspace analysis method was adapted for determination of MTBE in water samples and soil water extracts. The MDL of the headspace method was calculated to be 2.0 microg L(-1) by the EPA single-concentration design method(1) and 1.2 microg L(-1) by a calibration method developed by Hubaux and Vos (Hubaux, A.; Vos, G. Anal. Chem. 1970,42, 849-855). The MDL calculated with the Hubaux and Vos method was favored because it considers both a true positive and a false positive. The static headspace method was applied to analysis of a tap water sample and a monitoring well sample from a gasoline service station, a river sample, and aqueous extracts from soil excavated during removal of a leaking underground storage tank (LUST). The water samples examined in this study had MTTBE concentrations ranging from 6 to 19 microg L(-1). Aqueous extracts of a soil sample taken from the LUST site had 8 microg L(-1) MTBE.     

大粒径由羧基修饰的交联聚苯乙烯微球的制备与表征

以分散聚合法制得的聚苯乙烯微球为种子,以1,2-二氯乙烷为溶胀剂、己二酸二辛脂(DOA)为助溶胀剂、二乙烯基苯(DVB)为交联剂及甲基丙烯酸(MAA)或丙烯酸(AA)为水溶性功能性单体,采用活性溶胀聚合法成功制得大粒径由羧基修饰的交联聚苯乙烯微球.研究了溶胀剂种类及活性种球粒径对交联聚苯乙烯羧基微球最大平均粒径及粒径分...     

17O quantitative nuclear magnetic resonance spectroscopy of gasoline and oxygenated additives

17O Nuclear magnetic resonance (NMR) spectroscopy allows exclusive detection and direct quantification of oxygenates in gasoline unaffected by its hydrocarbon content, using the internal standard quantitative NMR (QNMR) method. Chemical shifts of 24 oxygen-containing compounds as potential additives and contaminants have been measured in gasoline and corrected values of deltaO 18.1 and 3.9 determined for neat methyl tert-butyl ether (MTBE) and neat di-n-butyl ether, respectively. Quantification of ethanol in gasoline can be readily achieved by 17O QNMR with dimethyl sulfone as an internal standard reference material, at the levels currently used in retail gasolines (1-20%). In addition, the simultaneous detection and quantification of the oxygenates methanol, ethanol, 2-propanol, tert-butyl alcohol, and MTBE in gasoline has been established to further demonstrate the specificity of the method. 17O NMR has distinct advantages over 1H and 13C QNMR methods, and although it cannot reliably differentiate 1-propanol, 1-butanol, 1-pentanol, and isopentyl alcohol, 17O NMR does allow the rapid and unambiguous identification of unexpected oxygenates such as acetates and ketones found as contaminants in some retail gasoline.     

Biodegradation of methyl tert-butyl ether (MTBE) by Enterobacter sp. NKNU02

We previously isolated and identified Enterobacter sp. NKNU02 as a methyl tert-butyl ether (MTBE)-degrading bacterial strain from gasoline-contaminated water. In this study, tert-butyl alcohol, acetic acid, 2-propanol, and propenoic acid were detected using gas chromatography/mass spectrometry when MTBE was degraded by rest cells of Enterobacter sp. NKNU02 cells. We also found that biodegradation of MTBE was decreased, but not totally inhibited in mixtures of benzene, toluene, ethylbenzene and xylene. The effects of MTBE on the biology of Enterobacter sp. NKNU02 were elucidated using 2D proteomic analysis. The cytoplasmic proteins isolated from these MTBE-treated and -untreated cells were carried out for proteomic analysis. Results showed that there were 6 differential protein spots and 8 differential protein spots, respectively, as compared to their corresponding control (without MTBE addition), at the indicated incubation times when 40% and 60% of 100 mg/L of MTBE had been removed, Among these proteins, nine were successfully identified with matrix-assisted laser desorption ionization-time of flight-mass spectrometry. Proteins identified included extracellular solute-binding protein, periplasmic-binding protein ytfQ, cationic amino acid ABC transporter, isocitrate dehydrogenase, cysteine synthase A, alkyl hydroperoxide reductase (AhpC), transaldolase, and alcohol dehydrogenase. Based on these differential proteins, we discuss the bacterial responses to MTBE at the molecular level.     

Adsorption of MTBE from contaminated water by carbonaceous resins and mordenite zeolite

Equilibrium and kinetic adsorption of methyl tert-butyl ether (MTBE) onto two carbonaceous resins and one zeolite was elucidated in this study. The Freundlich isotherm is adequate for describing the adsorption equilibrium of MTBE onto all the tested adsorbents in deionized water and natural waters. The resins of Ambersorb 563 and 572 have the highest adsorption capacity and almost twice the capacity of mordenite in deionized water. A different extent of NOM competition with MTBE was found for the carbonaceous resins in natural waters. For mordenite, no competitive adsorption was observed in natural water. The ideal adsorbed solution theory combined with equivalent background compound (IAST-EBC) model successfully described and predicted the adsorption of MTBE onto the carbonaceous resins in natural waters. The pore diffusion and micropore diffusion model fit the experimental data fairly well and successfully predicted the transport of MTBE within the adsorbent under different operating conditions. The small tortuosity factor between 1.2 and 2.3 of the resins for the diffusion of MTBE was observed, indicating a superior transport property for the carbonaceous resins in natural waters. The intracrystalline diffusivity of MTBE in natural water was much slower than that in deionized water, only 1/10 in STL and 1/3 in FS natural water, since the aperture entrances of mordenite was appreciably hindered by NOM.     

Measurement of aqueous Henry's law constants for oxygenates and aromatics found in gasolines by the static headspace method

A simple equilibrium vessel made from a large stopcock was used in conjunction with the static headspace method to measure the aqueous Henry's law constants for methyl tert-butyl ether (MTBE) and other potential oxygenates as well as certain of the aromatics found in gasoline. The present method involves using only one aqueous solution whose concentration is not necessarily known. The only quantity that must be known is the phase ratio. Plotting a series of peak areas of the analyte in the headspace after each equilibrium change against the initial peak area of the analyte found in the headspace leads to a linear relationship whose slope is dependent on the analyte's unitless Henry's law constant and the phase ratio. This new method is found to yield unitless aqueous Henry's law constants in the range from 0.02 to 0.2, which are especially applicable to the oxygenates and aromatics found in gasolines.     

Trace analysis of ethanol, MTBE, and related oxygenate compounds in water using solid-phase microextraction and gas chromatography/mass spectrometry

Solid-phase microextraction (SPME) and gas chromatography/mass spectrometry have been combined for trace-level determination of very polar compounds in water, including the widely used gasoline oxygenates ethanol and methyl tert-butyl ether (MTBE). A relatively simple extraction method using a divinylbenzene/Carboxen/poly(dimethylsiloxane) SPME fiber was optimized for the routine analysis of ethanol and MTBE in groundwater and reagent water. A sodium chloride concentration of 25% (w/w) combined with an extraction time of 25 min provided the greatest sensitivity while maintaining analytical efficiency. Replicate analyses in fortified reagent and groundwater spiked with microgram per liter concentrations of ethanol and MTBE indicate quantitative and reproducible recovery of these and related oxygenate compounds. Method detection limits were 15 microg L(-1) for ethanol, 1.8 microg L(-1) for tert-butyl alcohol, 0.038 microg L(-1) for tert-amyl methyl ether, 0.025 microg L(-1) for ethyl-tert-butyl ether, and 0.008 microg L(-1) for MTBE.     

Study of electron transfer across the liquid/ice-like matrix interface by scanning electrochemical microscopy

In this work, we report the findings of a study on scanning electrochemical microscopy (SECM) to investigate the interfacial electron-transfer (ET) reaction between the 7,7,8,8-tetracyanoquinodimethane radical anion (TCNQ*-) in 1,2-dichloroethane and ferricyanide in an ice-like matrix (a mixture of insulting ice and conductive liquid) under low temperatures. Experimental results indicate that the formed liquid/ice-like matrix interface is superficially similar in electrochemical characteristics to a liquid/liquid interface at temperatures above -20 degrees C. Furthermore, imaging data show that the surface of the ice-like matrix is microscopically flat and physically stable and can be applied as either a conductive or an insulting substrate for SECM studies. Perchlorate ion was selected as the common ion in both phases, the concentrations of which controlled the interfacial potential difference. The effect of perchlorate concentration in the DCE phase on interfacial reactions has been studied in detail. The apparent heterogeneous rate constants for TCNQ*- oxidation by Fe(CN)6(3-) in another phase under different temperatures have been calculated by a best-fit analysis, where the experimental approach curves are compared with the theoretically derived relationships. Reaction rate data obey Butler-Volmer formulation before and after the freezing point, which is similar to most other known cases of ET reactions at liquid/liquid interfaces. However, there is a sharp change observed for heterogeneous rate constants around the freezing point of the aqueous phase, which reflects the phase transition. At temperatures below -20 degrees C, surface-confined voltammograms for the reduction of ferricyanide were obtained, and the ice-like matrix became an insulating one, which indicates that the aqueous phase is really a frozen phase.     

Photocatalytic degradation of methyl tert-butyl ether in the gas-phase: a kinetic study

Methyl tert-butyl ether (MTBE) is the basic oxygenated motor fuel additive in Europe and is included in volatile organic compounds (VOCs), which can produce photochemical oxidants. In the present study the gas-phase photocatalytic oxidation (PCO) of MTBE over illuminated titanium dioxide was carried out at ambient temperature in a plug flow reactor. The intermediates detected are mainly tert-butyl formate and acetone, while the final products are CO(2) and water. The system was sensitive to the oxygen concentration, for concentrations up to 15% (v/v). Moisture had a positive effect on the reaction, obtaining an optimum value near 45% relative humidity for 200ppmv MTBE initial concentration. A reaction scheme has been proposed for the interpretation of the experimental results and a kinetic study was conducted, using the Langmuir-Hinshelwood kinetics equation. The MTBE rate constant was 1.545 x 10(-6)Ms(-1)g(cat)(-1) for the reaction without moisture and 2.46 x 10(-6)Ms(-1)g(cat)(-1) for the reaction in the presence of moisture and the adsorption constant was 2.187 x 10(5)M(-1) independent of humidity.     

Detection of the gasoline components methyl tert-butyl ether,benzene, toluene,and m-xylene using ion mobility spectrometers with a radioactive and UV ionization source

For the first time, ion mobility spectrometers (IMS) with radioactive and UV ionization sources in combination with multicapillary columns (MCCs) have been used to determine methyl tert-butyl ether (MTBE), a gasoline additive, in water and nitrogen as well as the monoaromatic compounds benzene, toluene, and m-xylene (BTX). A membrane extraction unit was set up to extract the substances from water, which is simple, effective, and easy to automate for further applications. Thus, the detection of MTBE and BTX of gasoline vapors was accomplished after a preliminary silicone membrane extraction. Two-dimensional data analyses of IMS-chromatograms allow us to separate these substances clearly according to their different retention and drift times. Method detection limits for MTBE were 2 microg/L (UV) and 30 pg/L (63Ni) in nitrogen and 20 mg/L (UV) and 1 microg/L (63Ni) in water. Rather a good reproducibility was achieved with relative standard deviations of between 2.9 and 9%. The method presented in this article has been proven to be suitable for nearly real-time monitoring as the total analysis time is less than 90 s. As an example of application, the detection of MTBE and BTX in a mixture of volatile organic compounds of pure gasoline using the 2-D IMS-chromatogram is presented.     

Benzene and toluene biodegradation down gradient of a zero-valent iron permeable reactive barrier

This study simulated benzene and toluene biodegradation down gradient of a zero-valent iron permeable reactive barrier (ZVI PRB) that reduces trichloroethylene (TCE). The effects of elevated pH (10.5) and the presence of a common TCE dechlorination by product [cis-1,2-dichloroethene (cis-1,2-DCE)] on benzene and toluene biodegradation were evaluated in batch experiments. The data suggest that alkaline pH (pH 10.5), often observed down gradient of ZVI PRBs, inhibits Fe(III)-mediated biotransformation of both benzene and toluene. Removal was reduced by 43% for benzene and 26% for toluene as compared to the controls. The effect of the addition of cis-1,2-DCE on benzene and toluene biodegradation was positive and resulted in removal that was greater than or equal to the controls. These results suggest that, at least for cis-1,2-DCE, its formation may not be toxic to iron-reducing benzene and toluene degrading bacteria; however, for microbial benzene and toluene removal down gradient of a ZVI PRB, it may be necessary to provide pH control, especially in the case of a biological PRB that is downstream from a ZVI PRB.     

Studies of electron-transfer and charge-transfer coupling processes at a liquid/liquid interface by double-barrel micropipet technique

Investigation of a heterogeneous electron-transfer (ET) reaction at the water/1,2-dichloroethane interface employing a double-barrel micropipet technique is reported. The chosen system was the reaction between Fe(CN)63- in the aqueous phase (W) and ferrocene in 1,2-dichloroethane (DCE). According to the generation and the collection currents as well as collection efficiency, the ET-ion-transfer (IT) coupling process at such an interface and competing reactions with the organic supporting electrolyte in the organic phase can be studied. In addition, this technique has been found to be an efficient method to distinguish and measure the charge-transfer coupling reaction between two ions (IT-IT) processes occurring simultaneously at a liquid/liquid interface. On this basis, the formal Gibbs energies of transfer of some ions across the W/DCE interface, such as NO3-, NO2-, Cl-, COO-, TBA+, TPAs+, Cs+, Rb+, K+, Na+, and Li+, for which their direct transfers are usually difficult to obtain because of the IT-IT coupling processes, were quantitatively evaluated.     

Identification and elimination of polysiloxane curing agent interference encountered in the quantification of low-picogram per milliliter methyl tert-butyl ether in blood by solid-phase microextraction headspace analysis

Widespread use of the gasoline additive methyl tert-butyl ether (MTBE) and the subsequent human exposure that follows have led to the need to quantify MTBE in a variety of complex biological matrixes. In this work, we demonstrate our latest MTBE quantification assay for whole blood and uncover previously unidentified contamination sources that prevented routine quantification in the low picogram per milliliter (parts per trillion, ppt) range despite a sensitive and selective analytical approach. The most significant and unexpected sources of contamination were found in reagents and laboratory materials most relevant to sample preparation and quantification. In particular, significant levels of MTBE were identified in sample vial septa that use poly(dimethylsiloxane) (PDMS)-based polymers synthesized with peroxide curing agents having tert-butyl side groups. We propose that MTBE is one of the byproducts of these curing agents, which cross-link PDMS via the methyl side groups. Residual MTBE levels of approximately 20 microg/septa are seen in septa whose formulations use these curing agents. Fortunately, these levels can be significantly reduced (i.e., <0.2 ng/septa) by additional processing. Performance achieved with this sample preparation approach is demonstrated using a mass spectrometry-based method to quantify blood MTBE levels in the low-ppt range.     

Long term studies on the anaerobic biodegradability of MTBE and other gasoline ethers

Anaerobic biodegradation of methyl tert-butyl ether (MTBE) using electron acceptors such as nitrate, Fe(III), sulfate and bicarbonate, may be more cost effective and feasible compared to aerobic treatment methods, for dealing with the MTBE problem. Currently, there are a few reports in the literature which have documented anaerobic biodegradation of MTBE in batch studies. However, some of the reports have been controversial, additionally many other studies have failed to document anaerobic biodegradation. Experiments were conducted over a long term period in both batch and continuous reactors to investigate the anaerobic biodegradability of MTBE and other gasoline ethers. Inoculums collected from various environments were used, along with different electron acceptors. Only one set of the batch experiments showed a 30-60% conversion of MTBE to tert-butyl alcohol under Fe(III)-reducing conditions, using complexed Fe(III). The use of complexed Fe(III) created an initial low pH of 1-2 in these batches due to its acidic nature, therefore, the removal may be due to acid hydrolysis rather than biological processes. Based on the findings obtained, caution should be applied in the interpretation of experimental data in which complexed Fe(III) is used for bioremediation of MTBE.     

Natural attenuation of chlorinated organics in a shallow sand aquifer

This work presents the second phase of a groundwater remediation program for the migration control of a 1,2-dichloroethane (1,2-DCA) contaminated plume which includes natural attenuation at a distance downgradient from the source area. The conceived system for the plume migration control, implemented just after a major accidental release of 1,2-DCA in the soil, included a 300 m long physical barrier (cement-bentonite diaphragm wall) and 12 extraction wells. Results of field investigations have provided evidence that 1,2-DCA was naturally biodegrading into vinyl chloride as well as ethene under the natural anaerobic-reducing conditions at the site. In that case, source control measures were implemented to accelerate the overall remediation process. Although the results are favorable, the natural degradation of the 1,2-DCA does not guarantee acceptable levels of concentrations. Therefore, a pilot test to evaluate the enhancement of these processes is being carried out through the use of a biosparging system. This test is being implemented near the source to achieve sequential aerobic–anaerobic treatment zones.     

Intramolecular carbon and nitrogen isotope analysis by quantitative dry fragmentation of the phenylurea herbicide isoproturon in a combined injector/capillary reactor prior to GC separation

Potentially, compound-specific isotope analysis may provide unique information on source and fate of pesticides in natural systems. Yet for isotope analysis, LC-based methods that are based on the use of organic solvents often cannot be used and GC-based analysis is frequently not possible due to thermolability of the analyte. A typical example of a compound with such properties is isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea), belonging to the worldwide extensively used phenylurea herbicides. To make isoproturon accessible to carbon and nitrogen isotope analysis, we developed a GC-based method during which isoproturon was quantitatively fragmented to dimethylamine and 4-isopropylphenylisocyanate. Fragmentation occurred only partially in the injector but was mainly achieved on a heated capillary column. The fragments were then chromatographically separated and individually measured by isotope ratio mass spectrometry. The reliability of the method was tested in hydrolysis experiments with three isotopically different batches of isoproturon. For all three products, the same isotope fractionation factors were observed during conversion and the difference in isotope composition between the batches was preserved. This study demonstrates that fragmentation of phenylurea herbicides does not only make them accessible to isotope analysis but even enables determination of intramolecular isotope fractionation.     

Kinetics and products of reactions of MTBE with ozone and ozone/hydrogen peroxide in water.

Methyl-t-butyl-ether (MTBE) has become a prevalent groundwater pollutant due to its high volume use as a nationwide gasoline additive. Given its physicochemical properties, it requires new treatment approaches. Both aqueous O(3) and a combination of O(3)/H(2)O(2), which gives *OH, can remove MTBE from water, making use of O(3) a viable technology for remediation of groundwater from fuel contaminated sites. Rate constants and temperature dependencies for reactions of MTBE with O(3) or with *OH at pH 7.2, in a range of 21-45 degrees C (294-318K) were measured. The second-order rate constant for reaction of MTBE with O(3) is 1.4 x 10(18)exp(-95.4/RT) (M(-1)s(-1)), and for reaction of MTBE with *OH produced by the combination of O(3)/H(2)O(2) is 8.0 x 10(9)exp(-4.6/RT) (M(-1)s(-1)), with the activation energy (kJ mol(-1)) in both cases. At 25 degrees C, this corresponds to a rate constant of 27 M(-1)s(-1) for ozone alone, and 1.2 x 10(9) M(-1)s(-1) for O(3)/H(2)O(2). The concentration of *OH was determined using benzene trapping. Products of reactions of O(3) and O(3)/H(2)O(2) with MTBE, including t-butyl-formate (TBF), t-butyl alcohol (TBA), methyl acetate, and acetone, were determined after oxidant depletion. A reaction pathway for mineralization of MTBE was also explored. Under continuously stirred flow reactor (CSTR) conditions, addition of H(2)O(2) markedly increases the rate and degree of degradation of MTBE by O(3).