Fate and Effect of Quaternary Ammonium Compounds in Biological Systems

Quaternary ammonium compounds (QACs) are organic molecules that are extensively used in domestic, agricultural, healthcare, and industrial applications as surfactants, emulsifiers, fabric softeners, disinfectants, pesticides, corrosion inhibitors, and personal care products. As a result, QACs are ubiquitous contaminants found worldwide in both engineered and natural systems. QACs are toxic to aquatic organisms and cause co-selection for antibiotic resistance, thus providing a reservoir of antibiotic-resistant bacteria, as well as antibiotic resistance genes in QAC-polluted environments. The objectives of the research presented here were to: (a) systematically assess the fate and toxicity of QACs using quantitative structure-activity relationships (QSAR); (b) evaluate the biotransformation potential of QACs under aerobic, anoxic and anaerobic conditions; and (c) assess the potential toxicity of QACs biotransformation products. Nine QACs, belonging to three homologous groups---monoalkonium, dialkonium and benzalkonium chlorides---were the target QACs. The QACs critical micelle concentration (CMC) was determined. Then, the CMC was used as a descriptor to derive relationships between QAC structure and partitioning to biosolids as well as acute Microtox RTM toxicity. QACs with low CMCs had a relatively high adsorption affinity for biosolids and a lower toxicity than QACs with higher CMCs, which suggests that QACs that are more mobile and more (bio)available are more toxic. The biotransformation potential of benzalkonium chlorides (BAC)---the most commonly used QACs found in engineered and natural biological systems---under aerobic, methanogenic, nitrate reducing, and fermentative conditions was evaluated using bioenergetics and batch bioassays. The aerobic BAC biotransformation involved sequential dealkylation and debenzylation steps resulting in the formation of benzyl dimethyl amine, and dimethyl amine, respectively. The bacterial community involved in the aerobic BAC degradation was mainly composed of species belonging to the Pseudomonas genus. All QACs tested were recalcitrant under methanogenic conditions and inhibited methanogenesis at and above 25 mg QAC/L. Under nitrate reducing and fermentative conditions, BAC was transformed to alkyldimethyl amines via an abiotic reaction known as modified Hofmann degradation and a biotic reaction known as fumarate addition, respectively. Both reactions are based on a mechanism known as nucleophilic substitution. The discovery of BAC transformation by the above mentioned two reactions is the first ever report to document QAC transformation under anoxic/anaerobic conditions and delineate the transformation pathway. This research contributes to a better understanding of the environmental and human health risks associated with QACs by providing systematic information on physical, chemical and biological processes that determine the fate and effect of QACs in engineered and natural systems.