Linear free energy relationships for the biotic and abiotic reduction of nitroaromatic compounds

Nitroaromatic compounds (NACs) are ubiquitous environmental contaminants that are susceptible to biological and abiotic reduction. Prior works have found that for the abiotic reduction of NACs, the logarithm of the NACs rate constants correlate with one-electron reduction potential values of the NACs (EH,NAC) according to linear free energy relationships (LFERs). Here, we extend the application of LFERs to the bioreduction of NACs and to the abiotic reduction of NACs by bioreduced (and pasteurized) iron-bearing clay minerals. A linear correlation (R² = 0.96) was found between the NACs bioreduction rate constants (k_obs) and EH,NAC1 values. The LFER slope of log k_obs versus EH,NAC1(2.303RT/F) was close to one (0.97), which implied that the first electron transfer to the NAC was the rate-limiting step of bioreduction. LFERs were also established between NAC abiotic reduction rate constants by bioreduced iron-bearing clay minerals (montmorillonite SWy-2 and nontronite NAu-2). The second-order NAC reduction rate constants (k) by bioreduced SWy-2 and NAu-2 were well correlated to EH,NAC1 (R² = 0.97 for both minerals), consistent with bioreduction results. However, the LFER slopes of log k versus EH,NAC1/(2.303RT/F) were significantly less than one (0.48-0.50) for both minerals, indicating that the first electron transfer to the NAC was not the rate-limiting step of abiotic reduction. Finally, we demonstrate that the rate of 4-acetylnitrobenzene reduction by bioreduced SWy-2 and NAu-2 correlated to the reduction potential of the clay (E_H,clay, R² = 0.95 for both minerals), indicating that the clay reduction potential also influences its reactivity.