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Transformation Pathway (transformation + pathway)
Selected AbstractsComputational chemistry study of the environmentally important acid-catalyzed hydrolysis of atrazine and related 2-chloro- s -triazinesPEST MANAGEMENT SCIENCE (FORMERLY: PESTICIDE SCIENCE), Issue 8 2002Phillip Sawunyama Abstract Many chlorine-containing pesticides, for example 2-chloro- s -triazines, are of great concern both environmentally and toxicologically. As a result, ascertaining or predicting the fate and transport of these compounds in soils and water is of current interest. Transformation pathways for 2-chloro- s -triazines in the environment include dealkylation, dechlorination (hydrolysis), and ring cleavage. This study explored the feasibility of using computational chemistry, specifically the hybrid density functional theory method, B3LYP, to predict hydrolysis trends of atrazine (2-chloro- N4 -ethyl- N6 -isopropyl-1,3,5-triazine-2,4-diamine) and related 2-chloro- s -triazines to the corresponding 2-hydroxy- s -triazines. Gas-phase energetics are described on the basis of calculations performed at the B3LYP/6-311++G(d,p)//B3LYP/6-31G* level of theory. Calculated free energies of hydrolysis (,hG298) are nearly the same for simazine (2-chloro- N4,N6 -diethyl-1,3,5-triazine-2,4-diamine), atrazine, and propazine (2-chloro- N4,N6 -di-isopropyl-1,3,5-triazine-2,4-diamine), suggesting that hydrolysis is not significantly affected by the side-chain amine-nitrogen alkyl substituents. High-energy barriers also suggest that the reactions are not likely to be observed in the gas phase. Aqueous solvation effects were examined by means of self-consistent reaction field methods (SCRF). Molecular structures were optimized at the B3LYP/6-31G* level using the Onsager model, and solvation energies were calculated at the B3LYP/6-311++G(d,p) level using the isodensity surface polarizable continuum model (IPCM). Although the extent of solvent stabilization was greater for cationic species than neutral ones, the full extent of solvation is underestimated, especially for the transition state structures. As a consequence, the calculated hydrolysis barrier for protonated atrazine is exaggerated compared with the experimentally determined one. Overall, the hydrolysis reactions follow a concerted nucleophilic aromatic substitution (SNAr) pathway. Published in 2002 for SCI by John Wiley & Sons, Ltd [source] Anaerobic transformation of compounds of technical toxaphene.ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 11 2003Abstract Technical toxaphene (Melipax) and the single compounds of technical toxaphene (CTTs) 2,2,5- endo, 6- exo, 8,8,9,10- octachlorobornane (B8-806), 2,2,5- endo, 6- exo, 8,9,9,10-octachlorobornane (B8-809), 2,2,5,5,8,9,9,10,10-nonachlorobornane (B9- 1025), 2- endo, 3- exo, 5- endo, 6- exo, 8,8,9,10,10-nonochlorobornane (B9-1679), 2- endo, 3- exo, 5- endo, 6- exo, 8,9,10,10-octachlorobornane (B8-1414), 2- endo, 3- exo, 5- endo, 6- exo, 8,8,9,10-octachlorobornane (B8-1412), and 2- exo, 3- endo, 5- exo, 9,9,10,10-heptachlorobornane (B7-1453) were treated with suspensions of the anaerobic bacterium Dehalospirillum multivorans. After 7 d, more than 50% of technical toxaphene was transformed, and the relative amount of early eluting CTTs increased. After 16 d, only 2- exo, 3- endo, 6- exo, 8,9,10-hexachlorobornane (B6-923), 2- endo, 3- exo, 5- endo, 6- exo, 8,9,10-heptachlorobornane (B7-1001), and a few minor penta- and hexachloro-CTTs were detected in the samples. The result of the transformation was comparable with observations in naturally contaminated sediments and soil. However, the performance with D. multivorans was more simple and reproducible, as well as faster, than use of soil, sediment, or anaerobic sewage sludge. In agreement with reports in the literature, reductive dechlorination at geminal chlorine atoms (gem -Cls) was found to be the major CTT transformation pathway. Experiments conducted with CTTs and gem -Cls at both primary and secondary carbons clarified that the initial Cl -> H substitution takes place at the secondary carbon C2. Furthermore, the 2- endo -Cl position was preferably substituted with hydrogen. In the case of B8-806, the dechlorination at the secondary carbon C2 was approximately 20-fold faster than the subsequent, slow reduction at the primary carbon C8. The three different formerly unknown heptachloro-CTTs, 2- exo, 3- endo, 6- exo, 8,9,9,10-heptachlorobornane (B7-1473), 2- exo, 3- endo, 6- endo, 8,9,9,10-hepatchlorobornane (B7-1461), and 2- exo, 3- endo, 6- exo, 8,8,9,10-heptachlorobornane (B7-1470) were found as intermediates of the B8-806/809 transformation. Treatment of B9-1679 with D. multivorans indicated that gem -Cls on the bridge (C8 and C9) are dechlorinated faster than gem -Cls on the bridgehead (C10). [source] Characterizing nitrogen dynamics, retention and transport in a tropical rainforest stream using an in situ15N additionFRESHWATER BIOLOGY, Issue 1 2002Jeffrey L. Merriam 1.,This study was part of the Lotic Intersite Nitrogen eXperiment (LINX); a series of identical 15NH4 tracer additions to streams throughout North America. 15NH4Cl was added at tracer levels to a Puerto Rican stream for 42 days. Throughout the addition, and for several weeks afterwards, samples were collected to determine the uptake, retention and transformation pathways of nitrogen in the stream. 2.,Ammonium uptake was very rapid. Nitrification was immediate, and was a very significant transformation pathway, accounting for over 50% of total NH4 uptake. The large fraction of NH4 uptake accounted for by nitrification (a process that provides energy to the microbes involved) suggests that energy limitation of net primary production, rather than N limitation, drives N dynamics in this stream. 3.,There was a slightly increased 15N label in dissolved organic nitrogen (DON) the day after the 15NH4 addition was stopped. This DO15N was < 0.02% of DON concentration in the stream water at the time, suggesting that nearly all of the DON found in-stream is allochthonous, or that in-stream DON production is very slow. 4.,Leptophlebiidae and Atya appear to be selectively feeding or selectively assimilating a very highly labelled fraction of the epilithon, as the label found in the consumers became much higher than the label found in the food source. 5.,A large spate (>20-fold increase in discharge) surprisingly removed only 37% of in-stream fine benthic organic matter (FBOM), leaves and epilithon. The fraction that was washed out travelled downstream a long distance (>220 m) or was washed onto the stream banks. 6.,While uptake of 15NH4 was very rapid, retention was low. Quebrada Bisley retained only 17.9% of the added 15N after 42 days of 15N addition. Most of this was in FBOM and epilithon. Turnover rates for these pools were about 3 weeks. The short turnover times of the primary retention pools suggest that long-term retention (>1 month) is minimal, and is probably the result of N incorporation into shrimp biomass, which accounted for < 1% of the added 15N. [source] Stromelysin-3 expression is an early event in human oral tumorigenesisINTERNATIONAL JOURNAL OF CANCER, Issue 2 2003Shilpi Soni Abstract Stromelysin-3 (ST3/MMP11) is associated with human tumour progression. To determine the clinical significance of ST3 in oral tumorigenesis, its expression was analysed in different stages of tobacco-associated oral cancer. Immunohistochemical analysis of ST3 expression in 79 oral precancerous lesions, 177 SCCs and 35 histologically normal oral tissues was carried out and corroborated by immunoblotting and RT-PCR. ST3/MMP11 protein expression was observed in 45/79 (57%) precancerous lesions [28/48 (58%) with hyperplasia and 17/31 (55%) with dysplasia] and in 123/177 (70%) oral SCCs. In precancerous lesions, ST3 expression was higher compared to normal oral tissues (p = 0.000) and associated with MVD (p = 0.05), a marker for angiogenesis. ST3 was also expressed in cells cultured from precancerous and cancerous lesions that had undergone epithelial-to-mesenchymal transition. In oral cancer patients, ST3 positivity was associated with lymph node involvement (p = 0.025) and increased intratumoral MVD (p = 0.009). Ninety-eight oral SCC patients were followed up for a period of 94 months (median 22.5 months). Kaplan-Meier survival analysis showed that ST3 expression was not a significant prognostic indicator. ST3 expression in oral hyperplastic and dysplastic lesions suggests its association with progression of phenotypic alterations acquired early during the malignant transformation pathway of oral epithelium and implicates it not only in angiogenesis and invasion but also in tumorigenesis. Thus, ST3 may serve as a potential target for developing molecular therapeutics for early intervention in oral tumorigenesis. © 2003 Wiley-Liss, Inc. [source] Mercury speciation by CE: An updateELECTROPHORESIS, Issue 1 2009Petr Kubán Abstract This review provides an update on mercury speciation by CE. It includes a brief discussion on physicochemical properties, toxicity and transformation pathways of mercury species (i.e. methyl-, ethyl-, phenyl- and inorganic mercury) and outlines recent trends in Hg speciation by CE. CE is presented as a complementary technique to chromatographic separation techniques, especially in cases when speed, high efficiency and low sample volumes are required. The development of suitable sample preconcentration/isolation (sample stacking, ion exchange, liquid,liquid,liquid extraction, dual-cloud point extraction) to achieve low LODs for analysis of trace concentrations of mercury species in real samples is emphasized. Hyphenation of CE to element specific detectors (i.e. electrothermal atomic absorption spectrometry, atomic fluorescence spectrometry, inductively coupled plasma-optical emission spectrometry, inductively coupled plasma-mass spectrometry) is discussed as well as a potential of CE in interaction studies that may provide useful information on interaction of various Hg species with selected bio-macromolecules. [source] Characterizing nitrogen dynamics, retention and transport in a tropical rainforest stream using an in situ15N additionFRESHWATER BIOLOGY, Issue 1 2002Jeffrey L. Merriam 1.,This study was part of the Lotic Intersite Nitrogen eXperiment (LINX); a series of identical 15NH4 tracer additions to streams throughout North America. 15NH4Cl was added at tracer levels to a Puerto Rican stream for 42 days. Throughout the addition, and for several weeks afterwards, samples were collected to determine the uptake, retention and transformation pathways of nitrogen in the stream. 2.,Ammonium uptake was very rapid. Nitrification was immediate, and was a very significant transformation pathway, accounting for over 50% of total NH4 uptake. The large fraction of NH4 uptake accounted for by nitrification (a process that provides energy to the microbes involved) suggests that energy limitation of net primary production, rather than N limitation, drives N dynamics in this stream. 3.,There was a slightly increased 15N label in dissolved organic nitrogen (DON) the day after the 15NH4 addition was stopped. This DO15N was < 0.02% of DON concentration in the stream water at the time, suggesting that nearly all of the DON found in-stream is allochthonous, or that in-stream DON production is very slow. 4.,Leptophlebiidae and Atya appear to be selectively feeding or selectively assimilating a very highly labelled fraction of the epilithon, as the label found in the consumers became much higher than the label found in the food source. 5.,A large spate (>20-fold increase in discharge) surprisingly removed only 37% of in-stream fine benthic organic matter (FBOM), leaves and epilithon. The fraction that was washed out travelled downstream a long distance (>220 m) or was washed onto the stream banks. 6.,While uptake of 15NH4 was very rapid, retention was low. Quebrada Bisley retained only 17.9% of the added 15N after 42 days of 15N addition. Most of this was in FBOM and epilithon. Turnover rates for these pools were about 3 weeks. The short turnover times of the primary retention pools suggest that long-term retention (>1 month) is minimal, and is probably the result of N incorporation into shrimp biomass, which accounted for < 1% of the added 15N. [source] Effect of H2 and Redox Condition on Biotic and Abiotic MTBE TransformationGROUND WATER MONITORING & REMEDIATION, Issue 4 2006P.M. Bradley Laboratory studies conducted with surface water sediment from a methyl tert -butyl ether (MTBE)-contaminated site in South Carolina demonstrated that, under methanogenic conditions, [U- 14C] MTBE was transformed to 14C tert -butyl alcohol (TBA) with no measurable production of 14CO2. Production of TBA was not attributed to the activity of methanogenic microorganisms, however, because comparable transformation of [U- 14C] MTBE to 14C-TBA also was observed in heat-sterilized controls with dissolved H2 concentrations > 5 nM. The results suggest that the transformation of MTBE to TBA may be an abiotic process that is driven by biologically produced H2 under in situ conditions. In contrast, mineralization of [U- 14C] MTBE to 14CO2 was completely inhibited by heat sterilization and only observed in treatments characterized by dissolved H2 concentrations < 2 nM. These results suggest that the pathway of MTBE transformation is influenced by in situ H2 concentrations and that in situ H2 concentrations may be an useful indicator of MTBE transformation pathways in ground water systems. [source] | ||||||||||