Impacts of bioreactor operating parameters on removal efficiency, biodegradation rate, molecular distribution, and toxicity of commercial naphthenic acids.

Effects of naphthenic acids (NAs) concentration (50-200 mg NA L-1; 35-140 mg TOC L-1) and loading rate (1.4-1249 mg NA L-1 h-1; 1-874 mg TOC L-1 h-1) on removal efficiency, removal rate, and molecular distribution of NAs, and effluent toxicity were evaluated for biodegradation of commercial NAs mixture in circulating packed bed bioreactors (CPBBs). Increase of NAs concentration and loading rate (shorter residence times) increased the removal rate, while removal efficiency initially declined and then stabilized. The maximum biodegradation rates for 50, 100, 150, and 200 mg NA L-1 were 128.0, 321.7, 430.2, and 630.0 mg TOC L-1 h-1 at loading rates of 218.5, 455.6, 673.5 and 874.0 mg TOC L-1 h-1, respectively, with removal efficiencies of 58.6, 70.6, 63.9 and 72.1%. Analysis of influent and treated effluents with gas chromatography-mass spectrometry showed that molecular weight and cyclicity (C and Z numbers) affected the biodegradation, with low molecular weight acyclic NAs (C = 6-12) were the most amenable to biodegradation and those with intermediate and high molecular weights (C = 13-22) and moderate cyclicity (Z = - 4, - 6) were the most recalcitrant. In the biofilm, Proteobacteria and Actinobacteria were the most abundant phyla, and Alphaproteobacteria, Betaproteobacteria, and Gammaproteobacteria were the dominant classes. Toxicity analyses with Artemia salina and Vibrio fischeri (Microtox) showed that high influent concentrations and loading rates (short residence times) led to higher NAs residual concentration and effluent toxicity. To design and operate large-scale CPBBs, intermediate loading rates and residence times that result in high removal efficiency, reasonable removal rates, and low toxicity are recommended.