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Canadian Water Quality Guidelines for the Protection of Aquatic Life

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Canadian Water Quality Guidelines for the Protection of Aquatic Life Canadian Water Quality Guidelines for the Protection URANIUM of Aquatic Life ranium (U; CASN 7440-61-1) is a heavy Sources to the environment: Anthropogenically, naturally-occurring element (atomic number uranium can be released to the environment through U 92, atomic weight of 238.029 g/mol). It is a uranium mill tailings, mill and refining and conversion member of the actinide series on the periodic plant effluent, and stack emissions. Tailings deposited table and is radioactive; it decays by emitting an alpha on dry land, if not capped with a clean cover, can be () particle (2 neutrons and 2 protons) from its nucleus lifted as dust particles, as with emissions from the (Harley 1996). Elemental uranium has a relatively low stacks, and subsequently deposited or washed out by radioactivity (0.67 Ci for a one gram sample; ASTDR precipitation and reach surface water bodies. Treated 1999), and is not soluble in water. Elemental uranium uranium mill effluent is another possible source of has a boiling point of 4131°C, a melting point of uranium; however, the effluent and the stack emissions 1135°C and a density of 19.1 g·cm-3. are highly monitored and regulated. Uranium is also released into the atmosphere from uranium refining and Not found in elemental form in nature, uranium exists conversion plants in both soluble and insoluble forms. as an important component of about 155 minerals, The effluent of these plants is discharged into the including oxides (e.g., pitchblende and uraninite), aquatic environment via the municipal sanitary sewer phosphates, carbonates, vanadates, silicates, arsenates system, however it has not been identified as a source of and molybdates (Clark et al. 1997). uranium to the aquatic environment (Environment Canada and Health Canada 2003). Uses: Fuel for nuclear reactors is the main use of mined uranium. In Canada, refining and conversion In comparison with other countries, Canada has a high operations produce UO2 for the domestic market (fuel concentration of uranium resources (Clark et al. 1997). for Canadian deuterium uranium reactors) and UF6, the Several areas in Canada, particularly parts of form favoured for enrichment processes, for export. Saskatchewan and Ontario, have naturally high Enrichment does not occur in Canada. concentrations of uranium ore deposits, which has led to past and present mining operations (Environment Small amounts of uranium are used in various other Canada and Health Canada 2003; Giancola 2003). industries and household products (ASTDR 1999; Lide Production in Saskatchewan in 2008 was 9001 tonnes 2002). Uranium dioxide is used in incandescent bulb (CAMECO Corporation 2009; AREVA Resources filaments used in photography and movie projectors; Canada. 2009). uranium nitrate in photography for toning; ammonium diuranate is used as colouring in glass and glaze; Ambient concentrations: The Geological Survey of uranium carbide is used as a catalyst in the production Canada has 36 years of data (1970-2006) concerning of synthetic ammonia; unspecified uranium compounds uranium (total, unfiltered) levels in lakes and stream are used as stains and dyes (leather and wood industries) and as mordants (silk and wood industries) Table 1. Canadian Water Quality Guidelines for (ASTDR 1999; Lide 2002). The production of high- Uranium (Total recoverable, Unfiltered) for the -1 energy x-rays uses uranium metal as x-ray targets Protection of Aquatic Life (µg•L ) (ASTDR 1999; Lide 2002; Bleise et al. 2003). Long-Term Short-Term Historically, uranium has been used in nuclear weapons Exposure Exposure -1 -1 (Whicker and Schultz 1982). Uranium is also present (µg•L ) (µg•L ) as a contaminant in phosphate fertilizers (ASTDR Freshwater 15 33 1999; Chou and Uthe 1995; Federal-Provincial- Marine NRG NRG Territorial Committee on Drinking Water 2001). NRG = no recommended guideline Canadian Environmental Quality Guidelines Canadian Council of Ministers of the Environment, 2011 URANIUM Canadian Water Quality Guidelines for the Protection of Aquatic Life water across Canada (Garrett 2007). As this monitoring low alkalinity (Markich et al. 2000; Reithmuller et al. was done primarily in non-impacted areas, these levels 2001; Gilbin et al. 2003). likely represent the natural background levels of uranium in these regions. These data indicate that the According to the free ion activity model (FIAM) highest concentrations in lakes in Canada (>10 µg·L-1), (Campbell 1995), metal toxicity in aquatic systems is were present in Saskatchewan, Manitoba, Nunavut, and better correlated with the concentration of free ion than Ontario, where the areas are characterized by with total metal concentration, although there are reports uraniferous rocks (Garrett 2007). Stream levels of of apparent exceptions to this model. Markich et al. -1 2+ + uranium across Canada are highest (≥ 100 µg·L ) in (2000) found that both UO2 and UO2OH were British Columbia and the Yukon, and the rocks in the significant predictors of sub-lethal short-term toxic areas sampled are known to have high levels of response, together explaining 97.5% of the variability in uranium (Garrett 2007). In Quebec, levels in streams toxic response, whereas individually, these species are sampled and analyzed with clean techniques for acid- poor predictors of toxic response. These results provide soluble metal range from less than detection evidence of an exception to the FIAM with uranium. (<0.0009 µg·L-1) to a maximum of 3.3 µg·L-1 (Guay Other speciation-based toxicity conclusions assume that 2+ 2009). Much of Canada, however, has very low UO2 is the toxic chemical species, and it is often the reported concentrations of uranium, with 75% of the target concentration to indicate toxicity. At a constant data indicating concentrations lower than about 1 pH and in the presence of three different ligands, the μg·L-1, and in many instances the levels are <0.05 FIAM reliably predicted uranium uptake as free ion, µg·L-1 or below the detection limit (Garrett 2007). suggesting that uranium complexes are not bioavailable These low levels likely represent the natural water under these conditions (Fortin et al. 2004). The concentrations of uranium typical for areas with a low speciation of uranium at the given conditions (e.g., geological presence of uraniferous rocks. Contrary to hardness, pH, temperature, etc.) is more indicative of the freshwater situation, there are very limited data for toxicity than the nominal concentration and form of marine levels. Chen et al. (1986) and Choppin and uranium added to the water (Barata et al. 1998; Franklin Stout (1989) reported the total (unfiltered) et al. 2000; Markich et al. 2000; Charles et al. 2002). concentrations of uranium in seawater of the Atlantic and Pacific oceans to be 3.1 μg·L-1, or when normalized Fate, behaviour and portioning: Uranium tends to for salinity and expressed on a strictly weight basis, partition into sediments (ATSDR 1999), as evidenced -1 3.2 μg·kg . by high partition coefficient (Kd) values between 0.36 and 3.2 x 103 L·kg-1 (Swanson 1985). Sediments have a Speciation: Uranium can exist in more oxidation states cation exchange capacity, which allows reversible than other metal contaminants of concern (Clark et al. binding of trace elements at exchange sites on the 1997). Of the four possible uranium oxidation states, surface (Manahan 1994). Maximum adsorption of 2+ (IV) and (VI) are generally agreed to be the most UO2 to mineral surfaces occurs at near neutral pH, common (Choppin and Stout 1989; Clark et al. 1997), regardless of mineral type (Sylwester et al. 2000). + although Langmuir (1978) suggests that U(V) as UO2 can also have appreciable thermodynamic stability in The primary route of exposure of aquatic organisms to reduced waters with pH < 7. In oxic natural waters, uranium is likely from the water as opposed to through uranium is present mainly in the U(VI) state (oxidized), food (Ahsanullah and Williams 1989). Sediment (Langmuir 1978; Choppin and Stout 1989). Large ingestion is a possible route of exposure, though likely variations in speciation with total uranium are minimal. commonly predicted from speciation models (Barata et al. 1998; Markich et al. 2000). Several studies have Evidence from lake whitefish (Coregonus agreed that under oxidizing conditions, the uranyl ion clupeaformis), round whitefish (Prosopium 2+ 6+ UO2 , as opposed to U , is the dominant “free ion” in cylindraceum), rainbow trout (Oncorhynchus mykiss), aquatic systems (Morse and Choppin 1991; Barata et al. lake trout (Salvelinus namaycush), and northern pike 1998; Sylwester et al. 2000). Although the speciation (Esox lucius) suggests that within fish, uranium of uranium in water is complex, modelling results show concentrations in the gut from food are generally higher that conditions which favour the formation of the free than those in fish tissue, which suggests partitioning of 2+ ion UO2 (uranyl ion) include low pH and low uranium accumulation within fish (Poston 1982; Waite concentrations of natural organic matter, and probably et al. 1988; Waite et al. 1990; Clulow et al. 1998; Cooley and Klaverkamp 2000). Within fish tissue itself, 2 Canadian Water Quality Guidelines URANIUM for the Protection of Aquatic Life uranium tends to accumulate in mineralized tissue, such stages: swim-up fry and two sizes of juveniles. In brook as bone and scales, and to a lesser extent in the kidney trout (Salvelinus fontinalis), the 96-h LC50 has been (Waite et al. 1990; Cooley and Klaverkamp 2000). noted as changing with hardness (Parkhurst et al. 1984). Under some exposure conditions, high concentrations Uranium can affect invertebrates in a myriad of ways; of uranium can accumulate in the gonads (Cooley and effects such as valve closure in bivalves and effects on Klaverkamp 2000). reproduction have been reported, as well as mortality. Ceriodaphnia dubia had reported 48h LC50s of 60-89 The bivalve Corbicula fluminea accumulated more µg U/L (Pickett et al.
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