13C/12C and 15N/14N Isotope Analysis To Characterize Degradation of Atrazine: Evidence from Parent and Daughter Compound Values

Atrazine (Atz) and its metabolite desethylatrazine (DEA) frequently occur in the environment. Conclusive interpretation of their transformation is often difficult. This study explored evidence from C-13/C-12 and N-15/N-14 isotope trends in parent and daughter compounds when Atz was dealkylated by (i) permanganate and (ii) the bacterium Rhodococcus sp. NI86/21. In both transformations, C-13/C-12 ratios of atrazine increased strongly (epsilon(carbon/permanganate) = -4.6 +/- 0.6 parts per thousand and epsilon(carbon/Rhodoccoccus) = -3.8 +/- 0.2 parts per thousand), whereas nitrogen isotope fractionation was small. C-13/C-12 ratios of DEA showed the following trends. (i) When DEA was formed as the only product (Atz + permanganate), C-13/C-12 remained constant, close to the initial value of Atz, because the carbon atoms involved in the reaction step are not present in DEA. (ii) When DEA was formed together with desisopropylatrazine (biodegradation of Atz), C-13/C-12 in creased but only within 2 parts per thousand. (iii) When DEA was further biodegraded, C-13/C-12 increased by up to 9 parts per thousand giving strong testimony of the metabolite's breakdown. Two lines of evidence emerge. (a) Enrichment of C-13/C-12, in DEA, compared to initial Atz, may contain evidence of further DEA degradation. (b) Dual element (N-15/N-14 versus C-13/C-12) isotope plots for dealkylation of atrazine agree with indirect photodegradation but differ from direct photolysis and biotic hydrolysis. Trends in multielement isotope data of atrazine may, therefore, decipher different degradation pathways.