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.
Morphological studies of large impact structures on Mercury, Venus, Mars, and the Moon suggest that volcanism within impact craters may not be confined to the shock melting of target rocks. This possibility prompted reinvestigation of the 1.85 Ga subaqueous Sudbury impact structure, specifically its 1.5 km thick immediate basin fill (Onaping Formation). Historically, breccias of this formation were debated in the context of an endogenic versus an impact‐fallback origin. New field, petrographic, and in situ geochemical data document an array of igneous features, including vitric shards, bombs, sheet‐like intrusions, and peperites, preserved in exquisite textural detail. The geochemistry of vitric materials is affected by alteration, as expected for subaqueous magmatic products. Earlier studies proposed an overall andesitic chemistry for all magmatic products, sourced from the underlying impact melt sheet. The new data, however, suggest progressive involvement of an additional, more magnesian, and volatile‐rich magma source with time. We propose a new working model in which only the lower part of the Onaping Formation was derived by explosive “melt‐fuel‐coolant interaction” when seawater flooded onto the impact melt sheet in the basin floor. By contrast, we suggest that the upper 1000 m were deposited during protracted submarine volcanism and sedimentary reworking. Magma was initially sourced from the impact melt sheet and up stratigraphy, from reservoirs at greater depth. It follows that volcanic deposits in large impact basins may be related to magmatism caused by the impact but not directly associated with the impact‐generated melt sheet.
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