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Abstract 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. 

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 δ¹⁵N_NO3+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-δ¹⁵N_NO3+NO2in the upper thermocline that works to lower the elevated δ¹⁵N_NO3+NO2generated in the oxygen deficient zones in the Eastern Tropical South Pacific. 

Shallow submarine hydrothermal vents can supply the iron needed to fuel phytoplankton blooms. 

Dissolved organic nitrogen (DON) is the dominant form of bioavailable nitrogen in the euphotic zone of subtropical gyres, where nitrate (NO3-) concentrations are low. However, the spatial distribution of DON production and consumption in the surface ocean remains poorly resolved due to the relatively narrow range in euphotic zone DON concentrations. Recently, the stable isotopic composition (d15N) of DON has been used to identify DON production and consumption in the surface ocean, making isotopic measurements a more sensitive indicator of DON cycling than concentration measurements alone. Here we report DON concentration and d15N measurements in the upper ~300 m from a zonal transect along ~30˚S in the South Pacific (GO-SHIP P06-2017), including samples in the Western South Pacific (154˚E-170˚W), in the oligotrophic South Pacific Subtropical Gyre (110˚W -170˚W), and overlying the Oxygen Deficient Zone (ODZ) in the east (78˚W-110˚W). We observed small variations in surface DON concentrations. Surface DON in Western South Pacific, oligotrophic South Pacific Subtropical Gyre and above the ODZ are 4.6±1.0 µM, 4.3±0.7 µM, and 4.8±0.5 µM, respectively. d15N of DON in the euphotic zone is lower in the west and higher in the east, consistent with distributions of nitrogen fixation and denitrification, respectively, in the South Pacific. Similar decreasing trend in DON d15N in the euphotic zone and subsurface nitrate d15N was observed from the east to the west in the South Pacific, suggesting the d15N in subsurface nitrate could be imprinted in the DON d15N in the euphotic zone. Low surface ocean DON d15N in the Western South Pacific (2.4±1.8 ‰) and oligotrophic South Pacific Subtropical Gyre (2.6±1.6 ‰) compared with surface ocean DON d15N above ODZ (5.4±2.3 ‰) infer significant low-d15N nitrogen is added to the western South Pacific and oligotrophic South Pacific Subtropical Gyre, potentially from N2 fixation. Additionally, high DON d15N at ~180˚ was consistent with entrainment of subsurface NO3- into surface waters due to shallow bathymetry. Together, these observations suggest that DON production and consumption processes operate on timescales adequately fast to produce isotopic gradients across the South Pacific. Comparisons of surface ocean DON d15N with subsurface nitrate d15N constrain the locations and timescales of these processes. 

The western subtropical South Pacific (WSSP) has recently been found to support high rates of di-nitrogen (N2) fixation in association with shallow hydrothermal iron fluxes. While previous 15N2 uptake and short-term d15N budgets have found that high rates of N2 fixation contribute significantly to export production, no longer-term evaluations of N2 fixation’s role in supporting the regional ecosystem were available. Here we present results of an annual d15N budget using the d15N of sinking particles captured in a moored sediment trap deployed at 1000 m from Nov 2019 - Nov 2020. We compare the d15N of the particles collected over this annual cycle with the d15N of subsurface nitrate to evaluate the seasonal and annual importance of N2 fixation for supporting export production. The results indicate that N2 fixation supported up to ~20% of annual export and that N2 fixation was most important during the summer. Notably, the d15N of subsurface nitrate at the trap station was low, 2 to 3 per mil compared to stations further from the vents. We also present some of the region’s first dissolved organic nitrogen (DON) d15N data. The DON samples collected in Nov 2019 and Nov 2020 show similar DON concentrations and d15N between years. However, while DON concentrations in the WSSP, 5 +/- 1 uM, were similar to the eastern tropical South Pacific (ETSP), the d15N of DON in the upper 100 m in the WSSP was between 2 to 4 per mil, which is lower than the ETSP, where DON d15N was between 4 to 6 per mil. Together, the results of the annual d15N budget as well as the low-d15N DON provide a longer-term perspective on the significance of N2 fixation in the WSSP. Additionally, the results suggest that N2 fixation in the WSSP introduces significant low-d15N N to the ocean, offsetting the elevated d15N generated in the oxygen deficient zones of the eastern tropical Pacific. 

Dissolved organic phosphorus (DOP) has a dual role in the surface ocean as both a product of primary production and as an organic nutrient fueling primary production and nitrogen Fixation, especially in oligotrophic gyres. Though poorly constrained, understanding the geographic distribution and environmental controls of surface ocean DOP concentration is critical to estimating distributions and rates of primary production and nitrogen Fixation in the global ocean. Here we pair DOP concentration measurements with a metric of phosphate (PO43-) stress (P*), satellite-based chlorophyll a concentrations, and iron stress estimates to explore their relationship with upper 50 m DOP stocks. Our results show that PO43- and iron stress work together to control surface DOP concentrations at basin scales. SpeciFcally, upper 50 m DOP stocks decrease with increasing phosphate stress, while alleviated iron stress leads to either surface DOP accumulation or loss depending on PO43- availability. Our work suggests an interdependence between DOP concentration, inorganic nutrient ratios, and iron availability, and establishes a predictive framework for DOP distributions in the global surface ocean. 

Significant rates of export production and nitrogen fixation occur in oligotrophic gyres in spite of low inorganic nutrient concentrations in surface waters. Prior work suggests that dissolved organic nitrogen (DON) and dissolved organic phosphorus (DOP) are important nutrient sources when inorganic nutrients are scarce. In particular, DOP has been shown to be an important P source for diazotrophs, which may be better suited to using low concentrations of organic vs. inorganic P. Prior modeling work has also suggested that DOP is important for supporting export production in oligotrophic gyres. However, validation of such models is limited by the number of upper ocean DOP concentration measurements, especially in the South Pacific and Indian Oceans. Here, we present measurements of DOP concentration from the 2016 GO-SHIP I08S and I09N meridional transect in Eastern Indian Ocean, and DON and DOP concentration measurements from the 2017 GO-SHIP P06 zonal transect in the subtropical South Pacific Ocean. Together with DOC and DON concentration measurements from prior occupations of the same GO-SHIP lines we evaluated changes in euphotic zone DOC:DON:DOP stoichiometry. Stoichiometry changes across these two transects are used to infer regions of preferential DON and/or DOP production and consumption. Specifically, north of 36 S in the Indian Ocean an increase in DOC:DON and DOC:DOP concentration ratios, from 11:1 to 14:1 and 118:1 to 190:1, respectively, are observed. Similarly, west of 136 W in the South Pacific Ocean significant increases in DOC:DOP and DON:DOP concentration ratios are observed, from 224:1 to 398:1 and 21:1 to 39:1, respectively. These stoichiometric shifts in upper ocean DOC:DON:DOP concentration ratios are considered in the context of ocean circulation, especially upwelling patterns in the Indian and eastern Pacific Oceans, as well as prior observations of the distribution of nitrogen fixation, especially in the western tropical South Pacific.