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This study examines dissolved rhenium (Re) concentrations as a function of water runoff using river samples from two contrasting mountainous watersheds, the Eel and Umpqua Rivers in the Pacific Northwest, USA. These watersheds share many key characteristics in terms of size, discharge, climate, and vegetation, but they have a 15-fold difference in sediment yield due to differences in their tectonic setting and uplift and erosion rates. We evaluate concentration-runoff (C-R) relationships and ratios of coefficients of variation (CVC/CVR) for major cations, anions, dissolved inorganic carbon, selected trace elements including Re, and 87Sr/86Sr ratios. Recent research outlines the potential of Re to serve as a tracer for the oxidation of ancient/fossil organic matter because of its close association with petrogenic carbon (OCpetro) in rocks. In both the Eel and Umpqua Rivers, our measurements show that Re behaves similarly to major weathering derived-solutes corrected for atmospheric input, such as Ca2+*, Mg2+*, and Na+* with modest dilution across all tributaries with increasing runoff. Rhenium behaves dissimilarly from other trace elements, such as Mo and U, and is also dissimilar to biologically-cycled nutrients, such as NO3 – , PO4 3 , and K+*, suggesting differences in sources, solute generation mechanisms, and flowpaths. Rhenium behavior is also distinct from that of colloids, which have increasing concentrations with increasing runoff. We find that Re and sulfate corrected for atmospheric input (SO4 2 *) have distinct CR relationships, in which SO4 2 * undergoes greater dilution with increasing runoff. This implies that Re is not dominantly sourced from sulfide weathering, which leaves primary bedrock minerals and OCpetro hosted in bedrock of these watersheds as the likely dominant sources of dissolved Re release. At mean discharge, Re concentration in the Eel river (3.5 pmol L-1) is more than two times greater than Re concentrations in the Umpqua River (1.5 pmol L-1). Furthermore, comparison of two tributary watersheds with similar bedrock but marked differences in erosion rates show higher Re concentrations in Bull Creek (erosion rate of 0.5 mm yr 1) relative to Elder Creek (erosion rate of 0.2 mm yr 1). The results of this study suggest that dissolved Re in the Eel and Umpqua River basins is likely derived from primary mineral dissolution or OCpetro oxidation, and Re fluxes are higher in areas with higher erosion rates, suggesting that tectonic setting is one factor that controls Re release and therefore OCpetro oxidation.more » « less
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Abstract A full cell chemistry of aqueous dual‐ion battery (DIB) was reported, comprising the graphite cathode and 3,4,9,10‐perylenetetracarboxylic diimide (PTCDI) as the anode. This DIB employed a mixture aqueous electrolyte: 5 mtributylmethylammonium (TBMA) chloride plus 5 mMgCl2, where [MgCl3]−and TBMA+serve as the charge carriers for cathode and anode of the DIB, respectively. This novel full cell exhibited a specific capacity of around 41 mAh g−1based on the total active mass of both electrodes with an average operation voltage of 1.45 V and stable cycling for 400 cycles.more » « less
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Abstract New acceptor‐type graphite intercalation compounds (GICs) offer candidates of cathode materials for dual‐ion batteries (DIBs), where superhalides represent the emerging anion charge carriers for such batteries. Here, the reversible insertion of [LiCl2]−into graphite from an aqueous deep eutectic solvent electrolyte of 20mLiCl+20mcholine chloride is reported. [LiCl2]−is the primary anion species in this electrolyte as revealed by the femtosecond stimulated Raman spectroscopy results, particularly through the rarely observed H–O–H bending mode. The insertion of Li–Cl anionic species is suggested by7Li magic angle spinning nuclear magnetic resonance results that describe a unique chemical environment of Li+ions with electron donors around.2H nuclear magnetic resonance results suggest that water molecules are co‐inserted into graphite. Density functional theory calculations reveal that the anionic insertion of hydrated [LiCl2]−takes place at a lower potential, being more favorable. X‐ray diffraction and the Raman results show that the insertion of [LiCl2]−creates turbostratic structure in graphite instead of forming long‐range ordered GICs. The storage of [LiCl2]−in graphite as a cathode for DIBs offers a capacity of 114 mAh g−1that is stable over 440 cycles.more » « less