Selective biodegradation of naphthenic acids and a probable link between mixture profiles and aquatic toxicity

The toxicity of oil sands process-affected waters (OSPW) from the Athabasca Oil Sands (AOS) in northern Alberta, Canada, is related to a relatively persistent group of dissolved organic acids known as naphthenic acids (NAs). Naphthenic acids are a complex mixture of carboxylic acids, with a general formula C(n)H(2n+Z)O2, where n indicates the carbon number and Z specifies the number of rings in the molecule. The present study is the first to evaluate the potential for the selective biodegradation of NAs and the associated reduction in aquatic toxicity of 2 OSPWs, maintained under 2 different hydraulic retention times and increased nutrient availability (nitrate and phosphate), using flow-through laboratory wetland microcosms over a 52-wk test period. High-performance liquid chromatography/quadrupole time of flight-mass spectrometry analysis was used to track the changes in NA mixture profiles, or "fingerprints," in each treatment over time. Based on first-order degradation kinetics, more rapid degradation was observed for NAs that had lower carbon numbers and fewer degrees of cyclization (NA congeners with carbon numbers 11-16 and Z series -2 to -4; half-lives between 19 and 28 wk). Within the NA mixture fingerprints, the 2 most persistent groups of homologues were also identified (NAs with carbon numbers 17-20 and Z series -6 to -12; half-lives between 37 and 52 wk). The persistence of this group of NAs may aid in explaining the residual chronic toxicological response as measured by the Microtox bioassay (effective concentration for 20%), after the degradation of the more labile fractions of NA mixtures in OSPW.