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  1. The West Florida Shelf (WFS) is oligotrophic, with inorganic N and P concentrations typically at or below detection limits, and yet significant rates of primary productivity, including blooms of the cyanobacterial diazotroph Trichodesmium spp. as well as the harmful algal species Karenia brevis, are observed there. Consequently, dissolved organic nitrogen (DON) and dissolved organic phosphorus (DOP) are thought to be the primary sources of assimilative nutrients on the WFS. Here we report measurements of total dissolved nitrogen (TDN) and total dissolved phosphorus (TDP) concentrations made on samples collected on a cruise in July of 2023 aboard the R/V Endeavor. Elevated concentrations of TDN (>12 µM) and TDP (>0.5 µM) were observed in the shallow, nearshore region, while to the west concentrations of both TDN and TDP decreased to values typically associated with oligotrophic North Atlantic waters (4 to 5 µM TDN and 0.05 to 0.1 µM TDP). 
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  2. The West Florida Shelf (WFS) is oligotrophic, with inorganic N and P concentrations typically at or below detection limits, and yet significant rates of primary productivity, including blooms of the cyanobacterial diazotroph Trichodesmium spp. as well as the harmful algal species Karenia brevis, are observed there. Consequently, dissolved organic nitrogen (DON) and dissolved organic phosphorus (DOP) are thought to be the primary sources of assimilative nutrients on the WFS. Here we report measurements of total dissolved nitrogen (TDN) and total dissolved phosphorus (TDP) concentrations made on samples collected quarterly from rivers draining onto the WFS as well as from submarine groundwater wells on three transects extending from the Florida Nature Coast in the north to Venice Headland in the south. Elevated concentrations of TDN (>12 µM) and TDP (>0.5 µM) were observed in riverine and groundwater samples, as well as in the shallow, nearshore region, while to the west concentrations of both TDN and TDP decreased to values typically associated with oligotrophic North Atlantic waters (4 to 5 µM TDN and 0.05 to 0.1 µM TDP). 
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  3. The West Florida Shelf (WFS) is oligotrophic, with inorganic N and P concentrations typically at or below detection limits, and yet significant rates of primary productivity, including blooms of the cyanobacterial diazotroph Trichodesmium spp. as well as the harmful algal species Karenia brevis, are observed there. Consequently, dissolved organic nitrogen (DON) and dissolved organic phosphorus (DOP) are thought to be the primary sources of assimilative nutrients on the WFS. Here we report measurements of total dissolved nitrogen (TDN) and total dissolved phosphorus (TDP) concentrations made on samples collected on a cross-shelf cruise in Feb-Mar 2023 aboard the R/V Atlantic Explorer. Elevated concentrations of TDN (>12 µM) and TDP (>0.5 µM) were observed in the shallow, nearshore region, while to the west concentrations of both TDN and TDP decreased to values typically associated with oligotrophic North Atlantic waters (4 to 5 µM TDN and 0.05 to 0.1 µM TDP). 
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  4. Specific activities of long-lived dissolved radium (Ra-226, Ra-228), collected from U.S. Geological Survey small boat operations in the West Florida Shelf from November 2022 to March 2024. Small boat samples include surface water, bottom water, and submarine groundwaters from three well transects along Nature Coast, Indian Rocks Beach, and Venice Headlands. This project investigates how boundary sources, including rivers and submarine groundwater discharge, deliver important nutrients and metals to the coastal ecosystems of the West Florida Shelf. Here, dissolved radium isotopes have been measured to trace boundary sources of nutrients and metals entering the West Florida Shelf. 
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  5. This dataset includes the specific activities of dissolved radon-222 collected from grab samples during STING I cruise AE2305 on R/V Atlantic Explorer (February to March 2023) and STING II cruise EN704 on R/V Endeavor in the Gulf of Mexico (June to July 2023). Additional data collected from underway samples during STING II are provided in the related dataset. This project investigates how boundary sources, including rivers and submarine groundwater discharge, deliver important nutrients and metals to the coastal ecosystems of the West Florida Shelf. Here, dissolved radon-222 has been measured to trace boundary sources of nutrients and metals entering the West Florida Shelf, including submarine groundwater discharge. 
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  6. Activities of dissolved radium (Ra-223, Ra-224, Ra-226, Ra-228), Th-228, and Ac-227, collected on two cruises in the Gulf of Mexico. STING I cruise AE2305 on R/V Atlantic Explorer was deployed from February to March 2023. STING II consisted of EN704 on R/V Endeavor and U.S. Geological Survey small boat surveys and took place from June to July 2023. This project investigates how boundary sources, including rivers and submarine groundwater discharge, deliver important nutrients and metals to the coastal ecosystems of the West Florida Shelf. Here, dissolved radium and parent isotopes have been measured to trace boundary sources of nutrients and metals entering the West Florida Shelf. 
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  7. 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. 
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  8. Surface ocean marine dissolved organic matter (DOM) serves as an important reservoir of carbon (C), nitrogen (N), and phosphorus (P) in the global ocean, and is produced and consumed by both autotrophic and heterotrophic communities. While prior work has described distributions of dissolved organic carbon (DOC) and nitrogen (DON) concentrations, our understanding of DOC:DON:DOP stoichiometry in the global surface ocean has been limited by the availability of DOP concentration measurements. Here, we estimate mean surface ocean bulk and semi‐labile DOC:DON:DOP stoichiometry in biogeochemically and geographically defined regions using newly available marine DOM concentration databases. Global mean surface ocean bulk (C:N:P = 387:26:1) and semi‐labile (C:N:P = 179:20:1) DOM stoichiometries are higher than Redfield stoichiometry, with semi‐labile DOM stoichiometry similar to that of global mean surface ocean particulate organic matter (C:N:P = 160:21:1) reported in a recent compilation. DOM stoichiometry varies across ocean basins, ranging from 251:17:1 to 638:43:1 for bulk and 83:15:1 to 414:49:1 for semi‐labile DOM C:N:P, respectively. Surface ocean DOP concentration exhibits larger relative changes than DOC and DON, driving surface ocean gradients in DOC:DON:DOP stoichiometry. Inferred autotrophic consumption of DOP helps explain intra‐ and inter‐basin patterns of marine DOM C:N:P stoichiometry, with regional patterns of water column denitrification and iron supply influencing the biogeochemical conditions favoring DOP use as an organic nutrient. Specifically, surface ocean marine DOM exhibits increasingly P‐depleted stoichiometries from east to west in the Pacific and from south to north in the Atlantic, consistent with patterns of increasing P stress and alleviated iron stress. 
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  9. The spatial distribution of marine di-nitrogen (N2) fixation informs our understanding of the sensitivities of this process as well as the potential for this new nitrogen (N) source to drive export production, influencing the global carbon (C) cycle and climate. Using geochemically-derived δ15N budgets, we quantified rates of N2fixation and its importance for supporting export production at stations sampled near the southwest Pacific Tonga-Kermadec Arc. Recent observations indicate that shallow (<300 m) hydrothermal vents located along the arc provide significant dissolved iron to the euphotic zone, stimulating N2fixation. Here we compare measurements of water column δ15NNO3+NO2with sinking particulate δ15N collected by short-term sediment traps deployed at 170 m and 270 m at stations in close proximity to subsurface hydrothermal activity, and the δ15N of N2fixation. Results from the δ15N budgets yield high geochemically-based N2fixation rates (282 to 638 µmol N m-2d-1) at stations impacted by hydrothermal activity, supporting 64 to 92% of export production in late spring. These results are consistent with contemporaneous15N2uptake rate estimates and molecular work describing highTrichodesmiumspp. and other diazotroph abundances associated with elevated N2fixation rates. Further, the δ15N of sinking particulate N collected at 1000 m over an annual cycle revealed sinking fluxes peaked in the summer and coincided with the lowest δ15N, while lower winter sinking fluxes had the highest δ15N, indicating isotopically distinct N sources supporting export seasonally, and aligning with observations from most other δ15N budgets in oligotrophic regions. Consequently, the significant regional N2fixation input to the late spring/summer Western Tropical South Pacific results in the accumulation of low-δ15NNO3+NO2in the upper thermocline that works to lower the elevated δ15NNO3+NO2generated in the oxygen deficient zones in the Eastern Tropical South Pacific. 
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  10. Marine dissolved organic carbon and nitrogen (DOC and DON) are major global carbon and nutrient reservoirs, and their characterization relies on extraction methods for preconcentration and salt removal. Existing methods optimize for capturing and describing DOC. Here, we report an optimized analytical strategy to recover marine DON for subsequent molecular characterization. Retention efficiencies between 5% and 95% are reported for seven solid phase extraction (SPE) sorbents, with PPL recovering 23% of marine DON compared to 95% recovered with C18. Additional comparisons of the effect of varying sample volumes and elution speed, and the resulting molecular composition of DON extracts, were investigated using C18 and PPL sorbents. Sample volumes > 200 mL decreased DON retention efficiency independent of SPE sorbent, and gravity elution recovered 1.7- to 4.2-fold more DON compared to vacuum elution. Characterization of extracted DON by negative-ion electrospray ionization Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) highlights compositional differences between DON species recovered by each method. DON isolated with optimized methods includes low molecular weight (< 600 Da) peptide-like compounds with low O:C ratios (0.2 to 0.5) that are not detected by other SPE sorbents (e.g., PPL). The majority of additional DON isolated with this approach was undetectable by direct infusion negative mode FT-ICR MS analysis. 
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