Ultra-trace (<1 ng g -1 ) rare earth elements and yttrium (REE+Y) and high field strength element (HFSE) geochemistry of freshwater can constrain element sources, aqueous processes in hydrologic catchments, and the signature of dissolved terrestrial fluxes to the oceans. This study details an adapted method capable of quantifying ≥38 elements (including all REE+Y, Nb, Ta, Zr, Hf, Mo, W, Th, U) with minimal sample preparation in natural water aliquots as low as ≤2 mL. The method precision and accuracy are demonstrated using measurement of the National Research Council -Conseil national de recherches Canada (NRC-CNRC) river water certified reference material (CRM) SLRS-6 sampled from the Ottawa River (OR).Data from SLRS CRM are compared to those of new, filtered (<0.45 µm) stream water samples from the central Ottawa River basin (ORB), and discussed in terms of processes and geochemical signatures inherited from the highly evolved igneous/metamorphic Archean and Proterozoic bedrock in the catchment. The ORB waters have significantly LREE>HREE-enriched REE+Y patterns, small natural positive Y and Gd anomalies, and negative Eu and Ce anomalies. These REE+Y features are coherent downstream in the OR apart from amplification of Eu and Ce anomalies during REE removal/dilution. The OR samples capture a downstream decrease in sparingly soluble HFSE (Th, Nb, Ta, Zr, Hf), presumably related to their colloid-particulate removal from the dissolved load, accompanied by crustal Zr/Hf (32.5 ± 5.1) and supercrustal Nb/Ta (25.1 ± 7.7) ratios. Subcrustal Th/U (0.17-0.96) and supercrustal Mo/W (12.0-74.5) ratios in all ORB waters indicate preferential release and aqueous solubility of U>Th and Mo>W, with the latter attributed primarily to preferential W adsorption on soil or upstream aquatic (oxy)(hydr)oxide surfaces.
Isotope systematics of the redox sensitive and chalcophile element selenium (Se) were investigated on exhumed parts of subducted oceanic lithosphere to provide new constraints on slab dehydration conditions during subduction. The samples show increasing δ 82/76 Se NIST3149 with higher abundances of fluid mobile elements, comprising a larger range (−1.89 to þ0.48 ‰) than that of mantle (−0.13 ± 0.12 ‰) and altered ocean crust (−0.35 to −0.07 ‰). Our data point to pronounced, local scale redox variations within the subducting crust, wherein oxidative fluids dissolve sulfides and mobilise oxidised Se species. Subsequently recrystallising sulfides preferentially incorporate isotopically lighter, reduced Se, which shifts evolving fluids and late stage sulfides to higher δ 82/76 Se NIST3149. Redistribution of Se by repeated cycles of sulfide reworking within the subducted crust can be reconciled with episodes of oxidised fluid pulses from underlying slab mantle in modern subduction zones.
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