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The oil sands region in northeastern Alberta, Canada contain approximately 165 billion barrels of oil making it the third largest oil reserves in the world. However, processing of extracted bitumen generates vast amounts of toxic byproduct known as oil sands process waters. Naphthenic acids and associated sodium naphthenate salts are considered the primary toxic component of oil sands process waters. Although a significant body of work has been conducted on naphthenic acid toxicity at levels comparable to what is observed in current oil sands process waters, it is also important to understand any impacts of exposure to sublethal concentrations. We conducted a microcosm study using the mayfly Hexagenia spp. to identify sublethal impacts of naphthenic acid exposure on the survival, growth, and metabolome across a concentration gradient (0–100 μg L−1) of sodium naphthenate. Nuclear magnetic resonance-based metabolomic analyses were completed on both the polar and lipophilic extracted fractions of whole organism tissue. We observed a positive relationship between sodium naphthenate concentration and mean principal component score of the first axis of the polar metabolome indicating a shift in the metabolome with increasing naphthenic acid exposure. Eleven metabolites correlated with increased naphthenic acid concentration and included those involved in energy metabolism and apoptosis regulation. Survival and growth were both high and did not differ among concentrations, with the exception of a slight increase in mortality observed at the highest concentration. Although lethal concentrations of naphthenic acids in other studies are higher (150–56,200 μg L−1), our findings suggest that physiological changes in aquatic invertebrates may begin at substantially lower concentrations. These results have important implications for the release of naphthenic acids into surface waters in the Alberta oil sands region as an addition of even small volumes of oil sands process waters could initiate chronic effects in aquatic organisms. Results of this research will assist in the determination of appropriate discharge thresholds should oil sands process waters be considered for environmental release.

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Effective modeling and management of phosphorus (P) losses from landscapes to receiving waterbodies requires an adequate understanding of P retention and remobilization along the terrestrial−aquatic continuum. Within aquatic ecosystems, the stream periphyton can transiently store bioavailable P through uptake and incorporation into biomass during subscouring and baseflow conditions. However, the capacity of stream periphyton to respond to dynamic P concentrations, which are ubiquitous in streams, is largely unknown. Our study used artificial streams to impose short periods (48 h) of high SRP concentration on stream periphyton acclimated to P scarcity. We examined periphyton P content and speciation through nuclear magnetic resonance spectroscopy to elucidate the intracellular storage and transformation of P taken up across a gradient of transiently elevated SRP availabilities. Our study demonstrates that the stream periphyton not only takes up significant quantities of P following a 48-h high P pulse but also sustains supplemental growth over extended periods of time (10 days), following the reestablishment of P scarcity by efficiently assimilating P stored as polyphosphates into functional biomass (i.e., phospho-monoesters and phospho-diesters). Although P uptake and intracellular storage approached an upper limit across the experimentally imposed SRP pulse gradient, our findings demonstrate the previously underappreciated extent to which the periphyton can modulate the timing and magnitude of P delivery from streams. Further elucidating these intricacies in the transient storage potential of periphyton highlights opportunities to enhance the predictive capacity of watershed nutrient models and potentially improve watershed P management.

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