Search for: All records

Marine dissolved organic matter (DOM) is a major reservoir that links global carbon, nitrogen, and phosphorus. DOM is also important for marine sulfur biogeochemistry as the largest water column reservoir of organic sulfur. Dissolved organic sulfur (DOS) can originate from phytoplankton-derived biomolecules in the surface ocean or from abiotically “sulfurized” organic matter diffusing from sulfidic sediments. These sources differ in 34S/32S isotope ratios (δ34S values), with phytoplankton-produced DOS tracking marine sulfate (21‰) and sulfurized DOS mirroring sedimentary porewater sulfide (∼0 to –10‰). We measured the δ34S values of solid-phase extracted (SPE) DOM from marine water columns and porewater from sulfidic sediments. Marine DOM_SPE δ34S values ranged from 14.9‰ to 19.9‰ and C:S ratios from 153 to 303, with lower δ34S values corresponding to higher C:S ratios. Marine DOM_SPE samples showed consistent trends with depth: δ34S values decreased, C:S ratios increased, and δ13C values were constant. Porewater DOM_SPE was 34S-depleted (∼-0.6‰) and sulfur-rich (C:S ∼37) compared with water column samples. We interpret these trends as reflecting at most 20% (and on average ∼8%) contribution of abiotic sulfurized sources to marine DOS_SPE and conclude that sulfurized porewater is not a main component of oceanic DOS and DOM. We hypothesize that heterogeneity in δ34S values and C:S ratios reflects the combination of sulfurized porewater inputs and preferential microbial scavenging of sulfur relative to carbon without isotope fractionation. Our findings strengthen links between oceanic sulfur and carbon cycling, supporting a realization that organic sulfur, not just sulfate, is important to marine biogeochemistry. 

The >5,000‐year radiocarbon age (¹⁴C‐age) of much of the 630 ± 30 Pg C oceanic dissolved organic carbon (DOC) reservoir remains an enigma in the marine carbon cycle. The fact that DOC is significantly older than dissolved inorganic carbon at every depth in the ocean forms the basis of our current framing of the marine DOC cycle, where some component persists over multiple cycles of ocean mixing. As a result,¹⁴C‐depleted, aged DOC is hypothesized to be present as a uniform reservoir with a constant¹⁴C signature and concentration throughout the water column. However, key requirements of this model, including direct observations of DOC with similar¹⁴C signatures in the surface and deep ocean, have never been met. Despite decades of research, the distribution of Δ¹⁴C values in marine DOC remains a mystery. Here, we applied a thermal fractionation method to compare operationally defined refractory DOC (RDOC) from different depths in the North Pacific Ocean. We found that RDOC shares chemical characteristics (as recorded by OC bond strength) throughout the water column but does not share the same¹⁴C signature. Our results support one part of the current paradigm—that RDOC is comprised of structurally related components throughout the ocean that form a “background” reservoir. However, in contrast to the current paradigm, our results are consistent with a vertical concentration gradient and a vertical and inter‐ocean Δ¹⁴C gradient for RDOC. The observed Δ¹⁴C gradient is compatible with the potential addition of pre‐aged DOC to the upper ocean.

 

In eastern boundary current systems, strong coastal upwelling brings deep, nutrient‐rich waters to the surface ocean, supporting a productive food web. The nitrate load in water masses that supply the region can be impacted by a variety of climate‐related processes that subsequently modulate primary productivity. In this study, two coastal upwelling regimes along central and southern California were sampled seasonally for nitrogen and oxygen stable isotopes of nitrate (i.e., nitrate isotopes) over several years (2010–2016) on 14 California Cooperative Oceanic Fisheries Investigations (CalCOFI) cruises. Seasonal, interannual, and spatial variations in euphotic zone nitrate isotopes were largely driven by the extent of nitrate utilization, sometimes linked to iron limitation of diatom productivity. Pronounced isotopic enrichment developed with the El Niño conditions in late 2015 and early 2016 which likely resulted from increased nitrate utilization linked to reduced nitrate supply to the euphotic zone. Differential enrichment of nitrogen and oxygen isotopes was observed in the surface ocean, suggesting that phytoplankton increased their reliance on locally nitrified (recycled) nitrate during warmer and more stratified periods. Overall, nitrate isotopes effectively differentiated important euphotic zone processes such as nitrate assimilation and nitrification, while archiving the influence of disparate controls such as iron limitation and climatic events through their effects on nitrate utilization and isotopic fractionation.

 

Denitrification in the anoxic sediments of the Santa Barbara Basin has been well documented in the historic and modern record, but the regulation of and frequency with which denitrification occurs in the overlying water column are less understood. Since 2004, the magnitude and speciation of redox active nitrogen species in bottom waters have changed markedly. Most notable are periods of decreased nitrate and increased nitrite concentrations. Here we examine these changes in nitrogen cycling as recorded by the stable isotopes of dissolved nitrate from 2010–2016. When compared to previous studies, our data identify an increase in water column denitrification in the bottom waters of the basin. Observations from inside the basin as well as data from the wider California Current Ecosystem implicate a long‐term trend of decreasing oxygen concentrations as the driver for these observed changes, with ramifications for local benthic communities and regional nitrogen loss.