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Zinc K -edge X-ray absorption near-edge (XANES) spectroscopy was conducted on 40 zinc mineral samples and organic compounds. The K -edge position varied from 9660.5 to 9666.0 eV and a variety of distinctive peaks at higher post-edge energies were exhibited by the materials. Zinc is in the +2 oxidation state in all analyzed materials, thus the variations in edge position and post-edge features reflect changes in zinc coordination. For some minerals, multiple specimens from different localities as well as pure forms from chemical supply companies were examined. These specimens had nearly identical K -edge and post-edge peak positions with only minor variation in the intensity of the post-edge peaks. This suggests that typical compositional variations in natural materials do not strongly affect spectral characteristics. Organic zinc compounds also exhibited a range of edge positions and post-edge features; however, organic compounds with similar zinc coordination structures had nearly identical spectra. Zinc XANES spectral patterns will allow identification of unknown zinc-containing minerals and organic phases in future studies. 

Trace elements sustain biological productivity, yet the significance of trace element mobilization and export in subglacial runoff from ice sheets is poorly constrained at present. Here, we present size-fractionated (0.02, 0.22, and 0.45 µm) concentrations of trace elements in subglacial waters from the Greenland Ice Sheet (GrIS) and the Antarctic Ice Sheet (AIS). Concentrations of immobile trace elements (e.g., Al, Fe, Ti) far exceed global riverine and open ocean mean values and highlight the importance of subglacial aluminosilicate mineral weathering and lack of retention of these species in sediments. Concentrations are higher from the AIS than the GrIS, highlighting the geochemical consequences of prolonged water residence times and hydrological isolation that characterize the former. The enrichment of trace elements (e.g., Co, Fe, Mn, and Zn) in subglacial meltwaters compared with seawater and typical riverine systems, together with the likely sensitivity to future ice sheet melting, suggests that their export in glacial runoff is likely to be important for biological productivity. For example, our dissolved Fe concentration (20,900 nM) and associated flux values (1.4 Gmol y⁻¹) from AIS to the Fe-deplete Southern Ocean exceed most previous estimates by an order of magnitude. The ultimate fate of these micronutrients will depend on the reactivity of the dominant colloidal size fraction (likely controlled by nanoparticulate Al and Fe oxyhydroxide minerals) and estuarine processing. We contend that ice sheets create highly geochemically reactive particulates in subglacial environments, which play a key role in trace elemental cycles, with potentially important consequences for global carbon cycling.

 

A modification of energy dispersive X‐ray fluorescence (ED‐XRF) for analysis of trace element concentrations in suspended particulate matter (SPM) in seawater and intercomparison with high‐resolution inductively coupled plasma‐mass spectrometry (HR ICP‐MS) is presented. Approximately 250 SPM samples were collected on polycarbonate track‐etched filters in the Indian Ocean during the U.S. CLIVAR/CO₂Repeat Hydrography meridional section I09N cruise in 2007. Samples were first analyzed by ED‐XRF, a nondestructive technique, for Al, P, Ti, Mn, Fe, Ni, Cu, and Zn and subsequently digested and quantified by HR ICP‐MS, creating two blind, basin‐scale data sets used for a paired statistical comparison. Our results found (1) ED‐XRF analysis using thin‐film principles can quantify the elemental composition of SPM at nanomolar concentrations found in the open ocean; (2) there was excellent agreement between ED‐XRF and HR ICP‐MS analyses for Al, Fe, and Mn and good agreement for P and Ti; (3) analytical differences were the largest for Cu, Ni, and Zn; (4) HR ICP‐MS methods have lower detection limits for most elements when compared to the ED‐XRF; (5) ED‐XRF analysis has a closer agreement to reported values for the NIST SRM 2783 standard and lower relative standard deviations when compared to the HR ICP‐MS. We recommend continued refinement of nondestructive ED‐XRF methods as this would allow for the easy exchange of filtered samples between lab groups for intercalibration and intercomparison of basin‐scale hydrographic cruises and archival for future analysis.