tosylarginine-methyl-ester and ethyl-tert-butyl-ether

Although the uniform initial hydroxylation of methyl tert-butyl ether (MTBE) and other oxygenates during aerobic biodegradation has already been proven by molecular tools, variations in carbon and hydrogen enrichment factors (ε(C) and ε(H)) have still been associated with different reaction mechanisms (McKelvie et al. Environ. Sci. Technol. 2009, 43, 2793-2799). Here, we present new laboratory-derived ε(C) and ε(H) data on the initial degradation mechanisms of MTBE, ethyl tert-butyl ether (ETBE), and tert-amyl methyl ether (TAME) by chemical oxidation (permanganate, Fenton reagents), acid hydrolysis, and aerobic bacteria cultures (species of Aquincola, Methylibium, Gordonia, Mycobacterium, Pseudomonas, and Rhodococcus). Plotting of Δδ(2)H/ Δδ(13)C data from chemical oxidation and hydrolysis of ethers resulted in slopes (Λ values) of 22 ± 4 and between 6 and 12, respectively. With A. tertiaricarbonis L108, R. zopfii IFP 2005, and Gordonia sp. IFP 2009, ε(C) was low (<|-1|‰) and ε(H) was insignificant. Fractionation obtained with P. putida GPo1 was similar to acid hydrolysis and M. austroafricanum JOB5 and R. ruber DSM 7511 displayed Λ values previously only ascribed to anaerobic attack. The fractionation patterns rather correlate with the employment of different P450, AlkB, and other monooxygenases, likely catalyzing ether hydroxylation via different transition states. Our data questions the value of 2D-CSIA for a simple distinguishing of oxygenate biotransformation mechanisms, therefore caution and complementary tools are needed for proper interpretation of groundwater plumes at field sites.

Topics: Bacteria, Aerobic; Biodegradation, Environmental; Ethyl Ethers; Hydrochloric Acid; Hydrogen Peroxide; Hydrolysis; Iron; Manganese Compounds; Methyl Ethers; Oxidation-Reduction; Oxides; Tosylarginine Methyl Ester

The use of ETBE (ethyl-tert-butylether) as gasoline additive has recently grown rapidly. Contamination of aquatic systems is well documented for MTBE (methyl-tert-butylether), but less for other gasoline additives. Due to their mobility they may easily reach drinking water collection areas. Odour and flavour thresholds of MTBE are known to be low, but for ETBE and TAME (methyl-tert-amylether) hardly information is available. The objective here is to determine these thresholds for MTBE, ETBE and TAME, and relate these to concentrations monitored in thousands of samples from Dutch drinking water collection areas. For ETBE odour and flavour thresholds are low with 1-2microgL(-1), for MTBE and TAME they range from 7 to 16microg L(-1). In most groundwater collection areas MTBE concentrations are below 0.1microg L(-1). In phreatic groundwaters in sandy soils not covered by a protective soil layer, occasionally MTBE occurs at higher concentrations. For surface water collection areas a minority of the locations is free of MTBE. For river bank and dune infiltrates, at a few locations the odour and flavour threshold is exceeded. For ETBE fewer monitoring data are available. ETBE was found in 2 out of 37 groundwater collection areas, in concentrations below 1microgL(-1). In the surface water collection areas monitored ETBE was found in concentrations near to the odour and flavour thresholds. The low odour and flavour thresholds combined with the high mobility and persistence of these compounds, their high production volumes and their increased use may yield problems with future production of drinking water.

Topics: Drinking; Ethyl Ethers; Gasoline; Methyl Ethers; Netherlands; Odorants; Taste; Tosylarginine Methyl Ester; Water; Water Pollutants, Chemical; Water Supply

Methyl tert-butyl ether (MTBE) is the most widely used oxygenate in gasoline blending and has become one of the world's most widespread groundwater and surface water pollutants. Alternative oxygenates to MTBE, namely ethyl tert-butyl ether (ETBE), tert-amyl ether (TAME) and diisopropyl ether (DIPE) have been hardly studied yet. The solubility of these chemicals is a key thermodynamic information for the assessment of the fate and transport of these pollutants. This work reports experimental data of water solubility at the range from 278.15 to 313.15K and atmospheric pressure of ethers used in fuels (MTBE, ETBE, TAME and DIPE) due to the strong influence of temperature on its trend. From the experimental data, temperature dependent polynomials were fitted, thermodynamic parameters were calculated and theoretical models were used for prediction. Finally, the tert-butyl alcohol (TBA) influence in the solubility of MTBE and ETBE in aqueous media was studied.

Topics: Ethers; Ethyl Ethers; Gasoline; Methyl Ethers; Solubility; Temperature; tert-Butyl Alcohol; Tosylarginine Methyl Ester; Water Pollutants, Chemical

Methyl tert-butylether (MTBE) used as fuel oxygenate poses problems for water suppliers since it is persistent in the aquatic environment and the removal efficiency by conventional water treatment methods (aeration or activated carbon filtration) is rather low. Substitution by other ether compounds such as ethyl tert-butylether (ETBE), tert-amylmethylether (TAME) or di-isopropylether (DIPE) is discussed, however, their environmental behaviour is similar to that of MTBE. Experiments investigating the elimination efficiency of AOP were carried out in tap water and water from Lake Constance. The elimination efficiency for all treatment processes was found to follow the order: MTBE << TAME approximately equal ETBE < DIPE For all compounds under investigation, neither pure ozonation nor UV irradiation yield a considerable concentration decline. Only the formation of highly reactive OH radicals shows a potential for removing the ethers from water. Therefore the addition of H2O2 in equimolar ratio prior to ozone admixing proved to be quite efficient. The application of combined UV/H2O2 showed good results in all cases; the best concentration decline was achieved with UV/ozone. The rate of elimination of the three substitutes for MTBE (ETBE, TAME and DIPE) is higher in all processes; nevertheless, no complete removal could be achieved. Therefore, from the point of view of water suppliers, the use of other ethers as substitute for MTBE is posing the same problems as MTBE.

Topics: Energy-Generating Resources; Esters; Ethyl Ethers; Hydrogen Peroxide; Methyl Ethers; Minerals; Oligopeptides; Oxygen; Ozone; Tosylarginine Methyl Ester; Ultraviolet Rays; Water

Experimental and occupational inhalational exposure to oxygenate fuel additives in reformulated gasoline has been reported to induce neurological symptoms (e.g., headache, nausea, dizziness). We reported previously that the ether additives (methyl-t-butyl ether (MTBE), t-amyl-methyl ether (TAME) and ethyl-t-butyl ether (ETBE)) and their metabolites (t-amyl alcohol (TAA), t-butyl alcohol (TBA) and ethanol) alter the binding of [3H]t-butylbicycloorthobenzoate ([3H]TBOB), a ligand for the gamma-aminobutyric acidA (GABAA) receptor in rat brain membrane preparations. To more directly assess the effects of the ethers and their alcohol precursors on GABAA receptor function, the uptake of 36Cl- was measured in synaptoneurosomes, a preparation of closed membrane sacs comprised of pre- and postsynaptic membranes from adult rat cerebral cortex. Each of the compounds caused a concentration-dependent enhancement of muscimol-stimulated uptake of 36CI-, which diminished with further increasing concentrations. The potency of the enhancement by the compounds was in the rank order: MTBE = TAME > TAA = ETBE > TBA > ethanol. The half-maximally effective concentration (EC50) for the facilitation of muscimol-stimulated 36Cl- uptake ranged from 0.06 to 3 mM, and that for the higher-dose inhibitory effect (IC50) ranged from 3 to 50 mM. The facilitatory concentrations of the compounds are in the range of the blood concentrations reported in experimental animals after exposures known to induce CNS effects such as ataxia. The results suggest a potential role of the GABAA receptor in some of the reported neurotoxic effects of gasoline additives.

Topics: Air Pollutants; Animals; Brain; Chlorides; Dose-Response Relationship, Drug; Ethyl Ethers; Gasoline; In Vitro Techniques; Male; Methyl Ethers; Rats; Rats, Sprague-Dawley; Receptors, GABA; Structure-Activity Relationship; Synaptosomes; Tosylarginine Methyl Ester

Aerobic degradation of ethyl tert-butyl ether (ETBE), Methyl tert-butyl ether (MTBE) and tert-amyl methyl ether (TAME), as tertiary-substrates, was studied in a continuous upflow fixed-bed reactor (UFBR) using an external oxygenator and sintered glass rings as biomass carriers. The UFBR has been shown to be an effective system for the simultaneous and continuous long-term degradation of the three-oxygenates mixture as sole source of carbon and energy. Therefore, the oxygenates feed concentration must be related in conjunction with the hydraulic retention time "HRT" and vice versa. The permissible feed concentration of both MTBE and TAME to achieve more than 99% removal efficiency is about 80 mg L-1 at a constant HRT of 24 h. The same performance can be obtained if the HRT kept at a value equal or above to 15 h for a feed concentration of about 80 mg L-1 of both MTBE and TAME. However, the ETBE removal efficiency was always greater than 99% whatever the ETBE concentration feed (between 10 and 100 mg L-1 at a constant HRT of 24 h) and the HRT (between 24 and 13 h at a constant concentration feed of about 80 mg L-1) tested in this study. The highest ETBE, MTBE and TAME removal rates achieved throughout the UFBR runs, with efficiency better than 99%, were 140 +/- 5, 132 +/- 2 and 135 +/- 2 mg L-1 d-1, respectively. No metabolic intermediates including tert-butyl alcohol (TBA), tert-butyl formate (TBF) and tert-amyl alcohol (TAA) were detected in the effluent during all the reactor runs. Furthermore, based on the chemical oxygen demand balance, all the removed oxygenates were completely metabolized. The results of this study suggest that the higher resistance to biodegradation exhibited by the MTBE and the TAME is probably due to the steric hindrance for the attacking enzyme(s); and the major limiting step to the oxygenate degradation maybe the accessibility and the cleavage of the ether bond, but not the assimilation of their major metabolites such as TBA, TBF and TAA. These results were concomitant with the batch tests using the reactor's immobilized biomass as inoculum.

Topics: Bacteria; Biodegradation, Environmental; Bioreactors; Ethyl Ethers; Methyl Ethers; Oxygen; Tosylarginine Methyl Ester

Two bacterial strains, E1 and E2, isolated from gasoline-polluted soil completely degraded ethyl tert-butyl ether (ETBE), as the sole source of carbon and energy, at specific rates of about 80 mg g(-1) and 58 mg g(-1) of cell protein day(-1), respectively. On the basis of morphological and phenotypic characteristics, strain E1 was tentatively identified as Comamonas testosteroni and strain E2 as belonging to Centre for Disease Control group A-5. The inhibitory effect of metyrapone on the degradative ability of both strains was the first evidence indicating the involvement of a soluble cytochrome P-450 in the cleavage of the ETBE ether bond. This observation was confirmed by spectrophotometric analysis of reduced cell extracts that gave, in the presence of carbon monoxide, a major absorbance peak at about 450 nm. Both strains were also able to degrade, as the sole source of carbon and energy, ETBE's major metabolic intermediates (tert-butyl alcohol and tert-butyl formate) and other gasoline oxygenates (methyl tert-butyl ether and tert-amyl methyl ether). The degradation rates varied considerably, with both strains exhibiting a preferential activity for ETBE's metabolic intermediates.

Topics: Air Pollutants; Bacteria, Aerobic; Cytochrome P-450 Enzyme System; Ethyl Ethers; Formates; Methyl Ethers; Metyrapone; Soil Microbiology; Soil Pollutants; tert-Butyl Alcohol; Time Factors; Tosylarginine Methyl Ester

The biotransformation of methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), and tert-amyl methyl ether (TAME) was studied in humans and in rats after inhalation of 4 and 40 ppm of MTBE, ETBE, and TAME, respectively, for 4 hours, and the biotransformation of MTBE and TAME was studied after ingestion exposure in humans to 5 and 15 mg in water. tert-Butyl alcohol (TBA), a TBA conjugate, 2-methyl-1,2-propanediol, and 2-hydroxyisobutyrate were found to be metabolites of MTBE and ETBE. tert-Amyl alcohol (TAA), free and glucuronidated 2-methyl-2,3-butanediol (a glucuronide of TAA), 2-hydroxy-2-methyl butyrate, and 3-hydroxy-3-methyl butyrate were found to be metabolites of TAME. After inhalation, MTBE, ETBE, and TAME were rapidly taken up by both rats and humans; after termination of exposure, clearance from blood of the ethers by exhalation and biotransformation to urinary metabolites occurred with half-times of less than 7 hours in rats and humans. Biotransformation of MTBE and ETBE was similar in humans and rats after inhalation exposure. 2-Hydroxyisobutyrate was recovered as a major product in urine. All metabolites of MTBE and ETBE excreted with urine were eliminated with half-times of less than 20 hours. Biotransformation of TAME was qualitatively similar in rats and humans, but the metabolic pathways were different. In humans, 2-methyl-2,3-butanediol, 2-hydroxy-2-methyl butyrate, and 3-hydroxy-3methyl butyrate were recovered as major urinary products. In rats, however, 2-methyl-2,3-butanediol and its glucuronide were major TAME metabolites recovered in urine. After ingestion of MTBE and TAME, both compounds were rapidly absorbed from the gastrointestinal tract. Hepatic first-pass metabolism of these ethers was not observed, and a significant part of the administered dose was transferred into blood and cleared by exhalation. Metabolic pathways for MTBE and TAME and kinetics of excretion were identical after ingestion and inhalation exposures. Results of studies presented here suggest (1) that excretion of MTBE, ETBE, and TAME in rats and humans is rapid, (2) that biotransformation and excretion of MTBE and ETBE are identical in rats, and (3) that biotransformation and excretion of TAME is quantitatively different in rats and humans.

Topics: Administration, Oral; Adult; Air Pollutants; Animals; Biomarkers; Biotransformation; Ethyl Ethers; Female; Humans; Inhalation Exposure; Kinetics; Male; Methyl Ethers; Rats; Rats, Inbred F344; Tosylarginine Methyl Ester

Alkylphenols and fuel oxygenates are important environmental pollutants produced by the petrochemical industry. A batch biodegradability test was conducted with selected ortho-substituted alkylphenols (2-cresol, 2,6-dimethylphenol and 2-ethylphenol), fuel oxygenates (methyl tert-butyl ether, ethyl tert-butyl ether and tert-amylmethyl ether) and tert-butyl alcohol (TBA) as model compounds. The ortho-substituted alkylphenols were not biodegraded after 100 days of incubation under methanogenic, sulfate-, or nitrate-reducing conditions. However, biodegradation of 2-cresol and 2-ethylphenol (150 mg l(-1)) was observed in the presence of Mn (IV) as electron acceptor. The biodegradation of these two compounds took place in less than 15 days and more than 90% removal was observed for both compounds. Mineralization was indicated since no UV-absorbing metabolites accumulated after 23 days of incubation. These alkylphenols were also slowly chemically oxidized by Mn (IV). No biodegradation of fuel oxygenates or TBA (1 g l(-1)) was observed after 80 or more days of incubation under methanogenic, Fe (III)-, or Mn (IV)-reducing conditions, suggesting that these compounds are recalcitrant under anaerobic conditions. The fuel oxygenates caused no toxicity towards acetoclastic methanogens activity in anaerobic granular sludge.

Topics: Anaerobiosis; Bacteria, Anaerobic; Biodegradation, Environmental; Cresols; Environmental Pollutants; Ethers; Ethyl Ethers; Euryarchaeota; Methane; Methyl Ethers; Nitrates; Oxidation-Reduction; Phenols; Sulfates; tert-Butyl Alcohol; Tosylarginine Methyl Ester; Xylenes