[en] Naphthenic acids (NA) are used in a variety of commercial and industrial applications, and are primary toxic components of oil sands wastewater. We investigated developmental and metabolic responses of tadpoles exposed to sub-lethal concentrations of a commercial NA blend throughout development. We exposed Lithobates pipiens tadpoles to 1 and 2 mg/L NA for 75 days and monitored growth and development, condition factor, gonad and liver sizes, and levels of liver glucose, glycogen, lipids and cholesterol following exposure. NA decreased growth and development, significantly reduced glycogen stores and increased triglycerides, indicating disruption to processes associated with energy metabolism and hepatic glycolysis. Effects on liver function may explain reduced growth and delayed development observed in this and previous studies. Our data highlight the need for greater understanding of the mechanisms leading to hepatotoxicity in NA-exposed organisms, and indicate that strict guidelines may be needed for the release of NA into aquatic environments. -- Highlights: ► We exposed Lithobates pipiens tadpoles to 1–2 mg/L NA in the laboratory. ► We monitored survival, growth and development for 75 days. ► We measured liver glycogen, glucose, triglycerides, and cholesterol levels. ► NA significantly reduced growth and development compared to controls. ► NA significantly reduced glycogen levels and increased triglycerides. -- Leopard frog (Lithobates pipiens) tadpoles chronically exposed to sub-lethal NA concentrations (1–2 mg/L) suffered decreased growth and development and disruption to liver metabolic processes

[en] Concentrations of dissolved and particulate Cd, Cu, Pb and Zn were determined in samples collected in summer 1998 from the lower reaches of six major Eurasian arctic rivers: the Onega, Severnaya Dvina, Mezen, Pechora, Ob and Yenisey. These data comprise some of the earliest measurements of trace metals in Eurasian arctic rivers above the estuaries using recognized clean techniques. Significant (α = 0.05) differences were observed among mean concentrations of particulate metals in the individual rivers (F ≤ 0.006), with highest levels overall observed in the Severnaya Dvina and Yenisey. No significant differences were observed among mean concentrations of dissolved metals in the individual rivers (F = 0.10-0.84). Contributions from anthropogenic sources are suggested by comparison of trace metal ratios in the samples to crustal abundances. These results establish a baseline for assessing future responses of Eurasian arctic river systems to climate-related environmental changes and shifting patterns of pollutant discharge. - We report some of the earliest reliable trace metal data for major Eurasian arctic rivers.

[en] Highlights: • Characterized NAFCs in natural and opportunistic wetlands in Athabasca oil sands • Collected first profiles of diverse NAFCs across the Athabasca oil sands region • Evidence of bitumen-derived NAFCs in some natural wetlands • Distinct NAFCs in wetlands on or near overburden different from natural bitumen input Classical naphthenic acids (NAs) are known to be primary aquatic toxicants of concern in the Athabasca oil sands region (AOSR), and are a component of naphthenic acid fraction compounds (NAFCs). Recent studies conducted in the AOSR have examined metals and polycyclic aromatic hydrocarbons in regional wetlands. However, few studies have described NAs and/or NAFCs in AOSR wetlands. To address this gap, we examined NAFC profiles in the water of different wetlands in the AOSR, including naturalized borrow pits (i.e., abandoned pits created by excavation of road-building materials), and opportunistically-formed wetlands associated with reclamation activities. For comparison, NAFC profiles from these wetlands were compared to an opportunistic wetland formed from tailings pond dyke seepage. Samples were prepared using solid-phase extraction and analyzed using negative-ion high-resolution Orbitrap mass spectrometry. Principal component analyses (PCA) revealed patterns to the NAFC profiles in the wetlands. The first distinct grouping of wetlands included water bodies associated with reclamation activities that are located on and/or adjacent to mining overburden. One other wetland, HATS5w, separated from all other wetlands during PCA, and had a unique NAFC profile; detailed examination of NAFCs revealed HATS5w contained the heaviest (i.e., high m/z components) and most unsaturated NAFCs among study locations, demonstrating the usefulness of high-resolution mass spectrometry for characterizing individual wetlands. The NAFCs of HATS5w are also substantially different from bitumen-derived inputs in overburden-adjacent opportunistic wetlands. Collectively, the NAFC profiles presented provide new information on background levels of polar bitumen-derived organics in AOSR wetlands.

[en] Highlights: • The removal rate of the naphthenic acids (NAs) species followed first-order kinetics. • The non-aerated wetland system preferentially removed NAs species of higher carbon numbers. • Constructed wetlands showed practical prospect for the treatment of OSPW-NAs. Large volumes of oil sands process-affected water (OSPW) are generated during the extraction of bitumen from oil sands in the Athabasca region of northeastern Alberta, Canada. As part of the development of treatment technologies, molecular characterization of naphthenic acids (NAs) and naphthenic acid fraction compounds (NAFC) in wetlands is a topic of research to better understand their fate and behavior in aquatic environments. Reported here is the application of high-resolution negative-ion electrospray Orbitrap-mass spectrometry for molecular characterization of NAs and NAFCs in a non-aerated constructed treatment wetland. The effectiveness of the wetlands to remove OSPW-NAs and NAFCs was evaluated by monitoring the changes in distributions of NAFC compounds in the untreated sample and non-aerated treatment system. After correction for measured evapotranspiration, the removal rate of the classical NAs followed approximately first-order kinetics, with higher rates observed for structures with relatively higher number of carbon atoms. These findings indicate that constructed wetland treatment is a viable method for removal of classical NAs in OSPW. Work is underway to evaluate the effects of wetland design on water quality improvement, preferential removal of different NAFC species, and reduction in toxicity.

[en] Highlights: • Treatment of oil sands process waters varied with constructed wetland design. • Efficiency evaluated through analytical chemistry, rates, extents, and toxicity. • Constructed wetlands with aquatic Sedges more effective than Cattail or Bulrush. • Treatment was associated with plant type and evapotranspiration. Constructed wetland treatment systems (CWTS)s can be used to treat various wastewaters. The main constituent in oil sands process-affected water (OSPW) with uncertain treatment by CWTS are naphthenic acid fraction compounds (NAFC)s. The NAFCs are also among the primary contributors of toxicity to aquatic organisms. While there is preliminary evidence that some CWTSs are capable of treating OSPW for future potential discharge, there is little information comparing the effectiveness and efficiencies of different CWTS designs. Obtaining large volumes of OSPW for testing can be difficult, and while it is known that synthetic NAFCs are simpler and have different toxicity than OSPW-NAFCs, it is unknown whether they could serve as a proxy for optimization of CWTS design and operation. This study presents a comprehensive comparison of CWTS performance operated with both synthetic OSPW and OSPW for four CWTS designs differing in plant type, aeration, flow path, water depth, and substrate type. This study evaluated the potential biodegradation of NAFCs including: (1) decrease in total NAFC concentration, (2) shifts in O_x-NAFC fractions from O₂- to O₃-, O₄-, and O₅-NAFC, (3) decrease in carbon number, (4) decrease of the double bond equivalencies (DBE), and (5) change in toxicity of the waters to test organisms. CWTS planted with Sedge achieved the greatest extent of NAFC treatment and detoxification regardless of design. Although CWTSs planted with Cattail and Bulrush also degraded NAFCs and decreased toxicity, a greater hydraulic retention time was required, and the total extent of treatment was less than the CWTSs planted with Sedge. While synthetic OSPW was more toxic and experienced faster degradation rates, it showed similar trends to OSPW in terms of CWTS design efficiencies and function. Although synthetic OSPW would not be appropriate for modelling or scaling of CWTSs, it can be useful for testing designs and operating conditions.