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The West Florida Shelf (WFS) in the Gulf of America (formerly the Gulf of Mexico) is oligotrophic, with inorganic nitrogen (N) and phosphorus (P) concentrations typically at or below detection limits, and yet significant rates of primary productivity, including blooms of the harmful algal species Karenia brevis, are observed there. Additionally, multiple clades of the cyanobacterial diazotroph Trichodesmium spp. are endemic on the WFS. Consequently, dissolved organic nitrogen (DON) and dissolved organic phosphorus (DOP) are thought to be the primary sources of assimilative macro nutrients on the WFS. Here we present results from a multidisciplinary study conducted on spring and summer 2023 cruises that 1) quantified rates of N2 fixation on the WFS; 2) characterized the diazotroph community composition; 3) measured dissolved inorganic and organic and suspended particulate organic nutrient concentrations and isotopic compositions; 4) measured trace element concentrations, speciation, and isotopic composition; 5) characterized dissolved organic matter chemical composition; and, 6) quantified fluxes of these elements from submarine groundwater discharge using a radium isotope mass balance model. Additionally, quarterly sampling of the geochemistry of riverine and submarine groundwater wells defined the chemical composition of margin (i.e., riverine and submarine groundwater) inputs. Together, we use these results to understand whether submarine groundwater discharge is the dominant source of bioavailable DON, DOP, dissolved iron, and iron-binding ligands on the WFS. Additionally, we use the results to ask whether the abundance of Karenia brevis and Trichodesmium spp. are associated with enhanced submarine groundwater inputs, and whether rates of N2 fixation carried out by two different Trichodesmium spp. are associated with enhanced submarine groundwater inputs.more » « less
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Abstract Nickel stable isotopes (δ60Ni) provide insight to Ni biogeochemistry in the modern and past oceans. Here, we present the first Pacific Ocean high‐resolution dissolved Ni concentration and δ60Ni data, from the US GEOTRACES GP15 cruise. As in other ocean basins, increases in δ60Ni toward the surface ocean are observed across the entire transect, reflecting preferential biological uptake of light Ni isotopes, however the observed magnitude of fractionation is larger in the tropical Pacific than the North Pacific Subtropical Gyre. Such surface ocean fractionation by phytoplankton should accumulate isotopically lighter Ni in the deep Pacific, yet we find that North Pacific deep ocean δ60Ni is similar to previously reported values from the deep Atlantic. Finally, we find that seawater dissolved δ60Ni in regions with hydrothermal input can be either higher or lower than background deep ocean δ60Ni, depending on vent geochemistry and proximity.more » « less
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Abstract Hydrogen sulfide is produced by heterotrophic bacteria in anoxic waters and via carbonyl sulfide hydrolysis and phytoplankton emissions under oxic conditions. Apparent losses of dissolved cadmium (dCd) and zinc (dZn) in oxygen minimum zones (OMZs) of the Atlantic and Pacific Oceans have been attributed to metal‐sulfide precipitation formed via dissimilatory sulfate reduction. It has also been argued that such a removal process could be a globally important sink for dCd and dZn. However, our studies from the North Pacific OMZ show that dissolved and particulate sulfide concentrations are insufficient to support the removal of dCd via precipitation. In contrast, apparent dCd and dZn deficits in the eastern tropical South Pacific OMZ do reside in the oxycline with particulate sulfide maxima, but they also coincide with the secondary fluorescence maxima, suggesting that removal via sulfide precipitation may be due to a combination of dissimilatory and assimilatory sulfate reduction. Notably, dCd loss via precipitation with sulfide from assimilatory reduction was found in upper oxic waters of the North Pacific. While dissimilatory sulfate reduction may explain local dCd and dZn losses in some OMZs, our evaluation of North Pacific OMZs demonstrates that dCd and dZn losses are unlikely to be a globally relevant sink. Nevertheless, metal sulfide losses due to assimilatory sulfate reduction in surface waters should be considered in future biogeochemical models of oceanic Cd (and perhaps Zn) cycling.more » « less
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Abstract Atmospheric deposition is an important source of iron (Fe) and perhaps zinc (Zn) to the oceans. We present total and water‐soluble aerosol Fe and Zn isotopic compositions, size‐fractionated aerosol Fe isotopic compositions, and aerosol enrichment factors from the North Pacific GEOTRACES GP15 section (Alaska‐Tahiti) during the low dust season. We found distinct bulk aerosol provinces along this latitudinal transect: Asian aerosols (especially crustal dust) dominate at higher latitudes (52–32°N) while North American heavier‐than‐crustal wildfire aerosols dominate in Equatorial Pacific deployments (20°N to 20°S). Soluble aerosol Fe was isotopically lighter‐than‐crustal along the full transect, strongly indicative of a pervasive anthropogenic Fe contribution to the Pacific. Comparison to a global aerosol deposition model corroborates that an isotopically heavy endmember is required for wildfire Fe, attributed to pyroconvective entrainment of soil particles. For Zn, the entire GP15 section is dominated by non‐crustal anthropogenic sources, reflected by light isotopic compositions (bulk: −0.12 ± 0.08‰ and soluble: −0.17 ± 0.14‰).more » « less
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