Maria G. Prokopenko

Multiple B-vitamin depletion in large areas of the coastal ocean

B vitamins are some of the most commonly required biochemical cofactors in living systems. Therefore, cellular metabolism of marine vitamin-requiring (auxotrophic) phytoplankton and bacteria would likely be significantly compromised if B vitamins (thiamin B1, riboflavin B2, pyridoxine B6, biotin B7, and cobalamin B12) were unavailable. However, the factors controlling the synthesis, ambient concentrations, and uptake of these key organic compounds in the marine environment are still not well understood. Here, we report vertical distributions of five B vitamins (and the amino acid methionine) measured simultaneously along a latitudinal gradient through the contrasting oceanographic regimes of the southern California-Baja California coast in the Northeast Pacific margin. Although vitamin concentrations ranged from below the detection limits of our technique to 30 pM for B2 and B12 and to ∼500 pM for B1, B6, and B7, each vitamin showed a different geographical and depth distribution. Vitamin concentrations were independent of each other and of inorganic nutrient levels, enriched primarily in the upper mesopelagic zone (depth of 100–300 m), and associated with water mass origin. Moreover, vitamin levels were below our detection limits (ranging from ≤0.18 pM for B12 to ≤0.81 pM for B1) in extensive areas (100s of kilometers) of the coastal ocean, and thus may exert important constraints on the taxonomic composition of phytoplankton communities, and potentially also on rates of primary production and carbon sequestration.

Nitrogen losses in anoxic marine sediments driven by Thioploca-anammox bacterial consortia

Ninety per cent of marine organic matter burial occurs in continental margin sediments, where a substantial fraction of organic carbon escapes oxidation and enters long-term geologic storage within sedimentary rocks. In such environments, microbial metabolism is limited by the diffusive supply of electron acceptors. One strategy to optimize energy yields in a resource-limited habitat is symbiotic metabolite exchange among microbial associations. Thermodynamic and geochemical considerations indicate that microbial co-metabolisms are likely to play a critical part in sedimentary organic carbon cycling. Yet only one association, between methanotrophic archaea and sulphate-reducing bacteria, has been demonstrated in marine sediments in situ, and little is known of the role of microbial symbiotic interactions in other sedimentary biogeochemical cycles. Here we report in situ molecular and incubation-based evidence for a novel symbiotic consortium between two chemolithotrophic bacteria—anaerobic ammonium-oxidizing (anammox) bacteria and the nitrate-sequestering sulphur-oxidizing Thioploca species—in anoxic sediments of the Soledad basin at the Mexican Pacific margin. A mass balance of benthic solute fluxes and the corresponding nitrogen isotope composition of nitrate and ammonium fluxes indicate that anammox bacteria rely on Thioploca species for the supply of metabolic substrates and account for about 57 ± 21 per cent of the total benthic N2 production. We show that Thioploca–anammox symbiosis intensifies benthic fixed nitrogen losses in anoxic sediments, bypassing diffusion-imposed limitations by efficiently coupling the carbon, nitrogen and sulphur cycles.

Low rates of nitrogen fixation in eastern tropical South Pacific surface waters.

Significance We present direct, field-based measurements of low nitrogen fixation rates in the eastern tropical South Pacific (ETSP) Ocean demonstrating that N2 fixation plays a minor role supporting export production regionally. These results are in contrast to indirect estimates that the highest global rates of N2 fixation occur in the ETSP. The low N2-fixation rates occur in a region with relatively high surface ocean phosphate concentrations (and low nitrate concentrations) but where atmospheric iron deposition rates are diminishingly low. Consequently, these results indicate that the ETSP hosts a minor fraction of global N2-fixation fluxes and that low nitrate to phosphate concentration ratios alone are insufficient to support high N2-fixation fluxes. An extensive region of the Eastern Tropical South Pacific (ETSP) Ocean has surface waters that are nitrate-poor yet phosphate-rich. It has been proposed that this distribution of surface nutrients provides a geochemical niche favorable for N2 fixation, the primary source of nitrogen to the ocean. Here, we present results from two cruises to the ETSP where rates of N2 fixation and its contribution to export production were determined with a suite of geochemical and biological measurements. N2 fixation was only detectable using nitrogen isotopic mass balances at two of six stations, and rates ranged from 0 to 23 µmol N m−2 d−1 based on sediment trap fluxes. Whereas the fractional importance of N2 fixation did not change, the N2-fixation rates at these two stations were several-fold higher when scaled to other productivity metrics. Regardless of the choice of productivity metric these N2-fixation rates are low compared with other oligotrophic locations, and the nitrogen isotope budgets indicate that N2 fixation supports no more than 20% of export production regionally. Although euphotic zone-integrated short-term N2-fixation rates were higher, up to 100 µmol N m−2 d−1, and detected N2 fixation at all six stations, studies of nitrogenase gene abundance and expression from the same cruises align with the geochemical data and together indicate that N2 fixation is a minor source of new nitrogen to surface waters of the ETSP. This finding is consistent with the hypothesis that, despite a relative abundance of phosphate, iron may limit N2 fixation in the ETSP.

Nitrous oxide cycling in the water column and sediments of the oxygen minimum zone, eastern subtropical North Pacific, Southern California, and Northern Mexico (23°N–34°N)

Identifying sources and sinks of N2O can illuminate N cycling processes in marine systems, particularly where changes in dissolved O2 can lead to changes in N cycling pathways (i.e., nitrification versus denitrification). We measured N2O and NO3− concentration and their stable isotope ratios (δ15N and δ18O) in the water column and sediments of the oxygen minimum zone in the nearshore eastern subtropical North Pacific (23°N–34°N). Atmospheric efflux of N2O ranged from 2.2 to 17.9 μmol m−2 d−1 or about 2–20 times higher than in oxygenated regions of the North Pacific. Surface waters were a source of 15N-depleted and 18O-enriched N2O to the atmosphere, indicating a bacterial, not archaeal, nitrification N2O source. Stable isotopes indicated that nitrification in both surface and intermediate waters (∼0–200 m) was the major source of N2O in this study area, with denitrification acting as a small N2O sink in strongly O2-depleted waters. Denitrification had a larger impact on observed patterns of N2O and NO3− concentrations and isotope ratios in the southern oxygen minimum zone. Sediments were generally neutral or a weak sink for N2O, with only one site (Soledad basin) showing a positive efflux of +3.5 ± 1.0 μmol N2O-N m−2 d−1. Sediment fluxes of N2O at all sites were several orders of magnitude smaller than fluxes of dinitrogen, nitrate, and ammonium measured in previous studies and did not appear to impact water column N2O concentrations. N2O was less than 0.1% of the N2 efflux from sedimentary denitrification.

Deep-sea coral evidence for lower Southern Ocean surface nitrate concentrations during the last ice age

Significance The concentration of atmospheric carbon dioxide (pCO2) varies by 80–100 ppm on glacial–interglacial timescales, with lower pCO2 during the ice ages. In the modern Southern Ocean, the surface nutrients are not fully consumed by phytoplankton, resulting in leakage of deeply sequestered CO2 to the atmosphere. It has been suggested that more complete nutrient consumption in the Southern Ocean would have caused the lower pCO2 during the ice ages. Here, we provide the most spatially comprehensive evidence to date in support of the proposal that the entire Southern Ocean was nutrient-depleted during the last ice age relative to modern conditions. These data are consistent with the hypothesis that Southern Ocean changes contributed to the lower atmospheric pCO2 of the ice ages. The Southern Ocean regulates the ocean’s biological sequestration of CO2 and is widely suspected to underpin much of the ice age decline in atmospheric CO2 concentration, but the specific changes in the region are debated. Although more complete drawdown of surface nutrients by phytoplankton during the ice ages is supported by some sediment core-based measurements, the use of different proxies in different regions has precluded a unified view of Southern Ocean biogeochemical change. Here, we report measurements of the 15N/14N of fossil-bound organic matter in the stony deep-sea coral Desmophyllum dianthus, a tool for reconstructing surface ocean nutrient conditions. The central robust observation is of higher 15N/14N across the Southern Ocean during the Last Glacial Maximum (LGM), 18–25 thousand years ago. These data suggest a reduced summer surface nitrate concentration in both the Antarctic and Subantarctic Zones during the LGM, with little surface nitrate transport between them. After the ice age, the increase in Antarctic surface nitrate occurred through the deglaciation and continued in the Holocene. The rise in Subantarctic surface nitrate appears to have had both early deglacial and late deglacial/Holocene components, preliminarily attributed to the end of Subantarctic iron fertilization and increasing nitrate input from the surface Antarctic Zone, respectively.

Annual Cyclicity in Export Efficiency in the Inner Southern California Bight

The balance of marine autotrophy and heterotrophy regulates the oceans ability to serve as a CO2 sink, as organic material produced by autotrophs sinks into the ocean interior to drive the biological pump. Marine ecosystems over the continental margins, especially coastal upwelling regions, account for a disproportionate amount of carbon export, thus even small fluctuations in export in these regions can have a large impact on the global carbon cycle. In this study, we estimated the rate of gross oxygen production (GOP), stoichiometrically related to gross primary production, by combining measurements of the triple isotope composition of dissolved oxygen with estimates of vertical advection, eddy diffusion and air-sea gas exchange in a one-dimensional two-box non-steady state model of the euphotic zone. Net oxygen production (NOP) estimates based on O2/Ar were then combined with GOP to estimate the NOP/GOP ratio, or potential export efficiency, out of the euphotic zone at the San Pedro Ocean Time series (SPOT) during an 18-month period between January 2013 and June 2014. GOP estimates ranged from 161 ± 44 to 477 ± 155 mmol m−2 d−1 during this period, peaking in May each year, and NOP/GOP ratios ranged from 0.05 ± 0.10 to 0.65 ± 0.28. The highest export efficiency occurred in late February/early March, following the onset of spring upwelling, declining as the upwelling season continued. This study demonstrates that export efficiency changes through time in this temperate coastal upwelling region on a repeated annual cycle and the magnitude of export efficiency suggests efficient photosynthetic energy conversion by phytoplankton in spring.

Estimates of vertical turbulent mixing used to determine a vertical gradient in net and gross oxygen production in the oligotrophic South Pacific Gyre

Mixed layer (ML) gross (GOP) and net (NOP) oxygen production rates based on in situ mass balances of triple oxygen isotopes (TOI) and O2/Ar are influenced by vertical transport from below, a term traditionally difficult to constrain. Here, we present a new approach to estimate vertical eddy diffusivity (Kz) based on density gradients in the upper thermocline and wind-speed based rates of turbulent shear at the ML depth. As an example, we use this Kz, verified by an independent 7Be-based estimate, in an O2/TOI budget at a site in the oligotrophic South Pacific Gyre (SPG). NOP equaled 0.31 ± 0.16 mmol m-2 d-1 in the ML (~55-65 m depth) and 1.2 ± 0.4 mmol m-2 d-1 (80%) beneath the ML, while GOP equaled 74 ± 27 mmol m-2 d-1 (86%) in the ML and 12 ± 4 mmol m-2 d-1 (14%) below, revealing a vertical gradient in production rates unquantifiable without the Kz estimate.

Particulate δ15N in laminated marine sediments as a proxy for mixing between the California Undercurrent and the California Current: A proof of concept

The measurements of particulate δ15N in coastal marine laminated sediments provide a high-resolution proxy for fluctuations in the intensity of denitrification in the water column. In the eastern tropical North Pacific oxygen minimum zone, this denitrification signal is transported northward by the California Undercurrent, thus serving as a tracer of ocean circulation. This is verified through comparisons between salinity in the thermocline off Southern California (Santa Monica Basin) and the difference between δ15Nsed within age equivalent sediments from a southern (Pescadero Slope) and northern (Santa Monica Basin) site. Trends in this parameter, Δδ15Nsed, relate to Pacific Decadal Oscillation (PDO) phase changes between 1900 and 1990. We hypothesize that the decline in Δδ15Nsed during warm PDO phases is due to a strengthening of the California Undercurrent transporting 15N-enriched nitrate from the eastern tropical North Pacific northward. The deviation from this trend after 1990 suggests recent changes in circulation and/or California Current water nutrient biogeochemistry.

Eastern Tropical South Pacific Nitrogen fixation

15N2 incubation-based N2 fixation rates, nitrate plus nitrite concentration and d15N, sediment trap PN mass flux and isotopic composition from the Eastern Tropical South Pacific, 2010 and 2011