Biological responses to contaminants in darters (Etheostoma spp.) collected from rural and urban regions of the Grand River, ON, Canada.

Urban and agricultural activities may introduce chemical stressors, including contaminants of emerging concern (CECs) and current use pesticides (CUPs) into riverine systems. The objective of this study was to determine if fish collected from various sites in the Grand River, ON, Canada show biomarkers of exposure to these classes of contaminants, and if the biomarker patterns vary in fish collected from urbanized and agricultural sites. Female rainbow darters (Etheostoma caeruleum) and female fantail darters (Etheostoma flabellare) were collected from the Grand River in June, 2014 for biomarker analysis from two urbanized sites and three agricultural sites. Over the same period of time, Polar Organic Chemical Integrative Samplers (POCIS) were deployed for 2weeks at each site to monitor for the presence of CUPs and CECs. Data on the liver somatic index for darters indicate site-specific differences in this condition factor (p<0.05). Significant differences in the levels of thiobarbituric acid reactive substances (TBARS) in gill tissue (p<0.05) of darters collected from the various sites indicate site-specific differences in oxidative stress. The activities of ethoxyresorufin-O-deethylase (EROD) in the liver tissue of rainbow darters were significantly different between sites (p<0.05), indicating differences in exposure to chemicals that induce or inhibit CYP450 1A metabolic activity. Finally, acetylcholinesterase (AChE) activity in brain tissue was significantly different between rainbow darters collected from rural and urban sites (p<0.05). These data showing different impacts from chemical inputs related to land uses in the watershed may be useful in developing mitigation strategies to reduce impacts on fish and other aquatic organisms in receiving environments.

Occurrence and removal of frequently prescribed pharmaceuticals and corresponding metabolites in wastewater of a sewage treatment plant.

The present study determines removal rates (RR) of 56 pharmaceuticals and metabolites, respectively, in an urban sewage treatment plant using mass flow analysis by comparing influent and effluent loads over a consecutive ten-day monitoring period. Besides well investigated compounds like carbamazepine and metoprolol, less researched targets, such as topiramate, pregabalin, telmisartan, and human metabolites of pharmaceuticals were included. Another aim was to determine the ratio of pharmaceuticals and corresponding metabolites in raw wastewater. Valsartan and gabapentin were detected at the highest average concentrations in influent (c(val) = 29.7 (± 8.1) µg/L, c(gab) = 13.2 (± 3.3) µg/L) and effluent (c(val) = 22.1 (± 5.1) µg/L, c(gab) = 12.1 (± 2.6) µg/L) samples. The comparison of mass loads in influent and effluent showed a significant removal (p<0.1) for 20 compounds but only enalapril, eprosartan, losartan, pregabalin, and quetiapine were removed from the aqueous phase by more than 50%. Another 20 compounds were determined without significant difference and for five compounds (clindamycin, lamotrigine, oxcarbazepine, O-desmethyl venlafaxine, triamterene), a significant higher mass load in the effluent than in the influent was observed. It has to be noticed that metabolites like 10,11-dihydro-10-hydroxy carbamazepine (MHD) are found in higher mass loads than the corresponding parent compound in the sewage samples. Furthermore, metabolites and parent compound behave differently in the sewage treatment process. While MHD (RR = 15.1%) was detected with lower mass load in the effluent than in the influent, oxcarbazepine (RR = -73.2%) showed the contrary pattern. When comparing expected and measured ratios of parent compound and metabolite in raw sewage, citalopram/N-desmethyl citalopram for example, showed good results. However, a major problem exists due to insufficient data regarding metabolism and excretion of many pharmaceuticals. This complicates the prediction of relevant metabolites and further efforts are needed to overcome this problem.