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The marine biological carbon pump is driven by sinking particulate organic matter (POM). Sinking speed and remineralization rate determine flux attenuation in the mesopelagic. Since the fate of all marine organic matter is either complete remineralization or transformation to more stable products, diagenetic modifications impact carbon dioxide sequestration time from the atmosphere. To investigate particle transformation at the molecular level, we characterize the water-extractable organic matter (WEOM) fraction of sinking particles from dominant biogeochemical environments using ultrahigh-resolution mass spectrometry. We find distinct, inverse associations in molecular-level nitrogen content and degree of transformation (i.e., “stability”) of organic matter across a productivity gradient from coastal upwelling to oligotrophic conditions. Nitrogen enrichment and low stability were observed at the coastal upwelling site and persisted to depths >400 m. Further, carbon flux is strongly correlated with the relative abundance of stable WEOM (“Island of Stability” molecular formulae) across productivity regimes and depth. This suggests emergent patterns in epi- and mesopelagic diagenesis, highlighting that the molecular composition of sinking organic matter exiting the euphotic zone varies more across regions than as a function of depth. This is attributed to highly variable sinking rates and the microbial diagenetic histories within the euphotic zone. The stability–flux relationship is considered a “diagenetic clock” relative to organic matter formation where the relative abundance of Island of Stability molecular formulae describes the degree of departure from the organic matter molecular-level composition at formation. This ubiquitous trajectory of the diagenetic clock further underpins a global ocean molecular signature of sinking POM. 

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. 

Abstract Dissolved organic phosphorus (DOP) concentration distributions in the global surface ocean inform our understanding of marine biogeochemical processes such as nitrogen fixation and primary production. The spatial distribution of DOP concentrations in the surface ocean reflect production by primary producers and consumption as an organic nutrient by phytoplankton including diazotrophs and other microbes, as well as other loss processes such as photolysis. Compared to dissolved organic carbon and nitrogen, however, relatively few marine DOP concentration measurements have been made, largely due to the lack of automated analysis techniques. Here we present a database of marine DOP concentration measurements (DOPv2021) that includes new (n = 730) and previously published (n = 3140) observations made over the last ~30 years (1990–2021), including 1751 observations in the upper 50 m. This dataset encompasses observations from all major ocean basins including the poorly represented Indian, South Pacific, and Southern Oceans and provides insight into spatial distributions of DOP in the ocean. It is also valuable for researchers who work on marine primary production and nitrogen fixation. 

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