Hydrolysis rate constants for 18 chlorinated methanes, ethanes, ethenes, and propanes have been measured in dilute aqueous solutions within the temperature range of 0-180 "C and at pH values of 3-14. Arrhenius parameters were determined for both neutral and alkaline hydrolysis reactions. Reactivity of these compounds in basic solutions increases in accord with the expected acidity of the most reactive hydrogen atom in the molecule. Neutral hydrolysis appears to depend on both the C-Cl bond strength and the degree of steric hindrance a t the reaction site. Only a neutral hydrolysis process occurs for CC14, l,l,ltrichloroethane, and 2,2-dichloropropane. The chlorinated ethenes and hexachloroethane react only with hydroxide under severe conditions and exhibit no neutral hydrolysis. Some of these compounds eliminate HCl, whereas others substitute OH for C1 to form alcohols that may react further to give aldehydes or carboxylic acids as products. Environmental hydrolysis half-lives (25 OC, pH 7) range from 36 h for 2,2-dichloropropane to 1850 years for CHC13 and to over lo6 years for C&16 and the ethenes.
Serial analysis of gene expression was used to profile transcript levels in Arabidopsis roots and assess their responses to 2,4,6-trinitrotoluene (TNT) exposure. SAGE libraries representing control and TNT-exposed seedling root transcripts were constructed, and each was sequenced to a depth of roughly 32,000 tags. More than 19,000 unique tags were identified overall. The second most highly induced tag (27-fold increase) represented a glutathione S-transferase. Cytochrome P450 enzymes, as well as an ABC transporter and a probable nitroreductase, were highly induced by TNT exposure. Analyses also revealed an oxidative stress response upon TNT exposure. Although some increases were anticipated in light of current models for xenobiotic metabolism in plants, evidence for unsuspected conjugation pathways was also noted. Identifying transcriptome-level responses to TNT exposure will better define the metabolic pathways plants use to detoxify this xenobiotic compound, which should help improve phytoremediation strategies directed at TNT and other nitroaromatic compounds.
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