Marine oxygen production and open water supported an active nitrogen cycle during the Marinoan Snowball Earth

The Neoproterozoic Earth was punctuated by two low-latitude Snowball Earth glaciations. Models permit oceans with either total ice cover or substantial areas of open water. Total ice cover would make an anoxic ocean likely, and would be a formidable barrier to biologic survival. However, there are no direct data constraining either the redox state of the ocean or marine biological productivity during the glacials. Here we present iron-speciation, redox-sensitive trace element, and nitrogen isotope data from a Neoproterozoic (Marinoan) glacial episode. Iron-speciation indicates deeper waters were anoxic and Fe-rich, while trace element concentrations indicate surface waters were in contact with an oxygenated atmosphere. Furthermore, synglacial sedimentary nitrogen is isotopically heavier than the modern atmosphere, requiring a biologic cycle with nitrogen fixation, nitrification and denitrification. Our results indicate significant regions of open marine water and active biologic productivity throughout one of the harshest glaciations in Earth history

Enhanced carbon pump inferred from relaxation of nutrient limitation in the glacial ocean

The modern Eastern Equatorial Pacific (EEP) Ocean is a large oceanic source of carbon to the atmosphere. Primary productivity over large areas of the EEP is limited by silicic acid and iron availability, and because of this constraint the organic carbon export to the deep ocean is unable to compensate for the outgassing of carbon dioxide that occurs through upwelling of deep waters. It has been suggested that the delivery of dust-borne iron to the glacial ocean, could have increased primary productivity and enhanced deep-sea carbon export in this region, lowering atmospheric carbon dioxide concentrations during glacial periods. Such a role for the EEP is supported by higher organic carbon burial rates documented in underlying glacial sediments but lower opal accumulation rates cast doubts on the importance of the EEP as an oceanic region for significant glacial carbon dioxide drawdown. Here we present a new silicon isotope record that suggests the paradoxical decline in opal accumulation rate in the glacial EEP results from a decrease in the silicon to carbon uptake ratio of diatoms under conditions of increased iron availability from enhanced dust input. Consequently, our study supports the idea of an invigorated biological pump in this region during the last glacial period that could have contributed to glacial carbon dioxide drawdown. Additionally, using evidence from silicon and nitrogen isotope changes, we infer that, in contrast to the modern situation, the biological productivity in this region is not constrained by the availability of iron, silicon and nitrogen during the glacial period. We hypothesize that an invigorated biological carbon dioxide pump constrained perhaps only by phosphorus limitation was a more common occurrence in low-latitude areas of the glacial ocean

No iron fertilization in the equatorial Pacific Ocean during the last ice age

The equatorial Pacific Ocean is one of the major high-nutrient, low-chlorophyll regions in the global ocean. In such regions, the consumption of the available macro-nutrients such as nitrate and phosphate is thought to be limited in part by the low abundance of the critical micro-nutrient iron1. Greater atmospheric dust deposition2 could have fertilized the equatorial Pacific with iron during the last ice age—the Last Glacial Period (LGP) but the effect of increased ice-age dust fluxes on primary productivity in the equatorial Pacific remains uncertain. Here we present meridional transects of dust (derived from the 232Th proxy), phytoplankton productivity (using opal, 231Pa/230Th and excess Ba), and the degree of nitrate consumption (using foraminifera-bound δ15N) from six cores in the central equatorial Pacific for the Holocene (0–10,000 years ago) and the LGP (17,000–27,000 years ago). We find that, although dust deposition in the central equatorial Pacific was two to three times greater in the LGP than in the Holocene, productivity was the same or lower, and the degree of nitrate consumption was the same. These biogeochemical findings suggest that the relatively greater ice-age dust fluxes were not large enough to provide substantial iron fertilization to the central equatorial Pacific. This may have been because the absolute rate of dust deposition in the LGP (although greater than the Holocene rate) was very low. The lower productivity coupled with unchanged nitrate consumption suggests that the subsurface major nutrient concentrations were lower in the central equatorial Pacific during the LGP. As these nutrients are today dominantly sourced from the Subantarctic Zone of the Southern Ocean, we propose that the central equatorial Pacific data are consistent with more nutrient consumption in the Subantarctic Zone, possibly owing to iron fertilization as a result of higher absolute dust fluxes in this region7,8. Thus, ice-age iron fertilization in the Subantarctic Zone would have ultimately worked to lower, not raise, equatorial Pacific productivity

Isotopic fractionation of carbon during uptake by phytoplankton across the South Atlantic subtropical convergence

The stable isotopic composition of particulate organic carbon (δ13CPOC) in the surface waters of the global ocean can vary with the aqueous CO2 concentration ([CO2(aq)]) and affects the trophic transfer of carbon isotopes in the marine food web. Other factors such as cell size, growth rate and carbon concentrating mechanisms decouple this observed correlation. Here, the variability in δ13CPOC is investigated in surface waters across the south subtropical convergence (SSTC) in the Atlantic Ocean, to determine carbon isotope fractionation (ϵp) by phytoplankton and the contrasting mechanisms of carbon uptake in the subantarctic and subtropical water masses. Our results indicate that cell size is the primary determinant of δ13CPOC across the Atlantic SSTC in summer. Combining cell size estimates with CO2 concentrations, we can accurately estimate "p within the varying surface water masses in this region. We further utilize these results to investigate future changes in "p with increased anthropogenic carbon availability. Our results suggest that smaller cells, which are prevalent in the subtropical ocean, will respond less to increased [CO2(aq)] than the larger cells found south of the SSTC and in the wider Southern Ocean. In the subantarctic water masses, isotopic fractionation during carbon uptake will likely increase, both with increasing CO2 availability to the cell, but also if increased stratification leads to decreases in average community cell size. Coupled with decreasing δ13C of [CO2(aq)] due to anthropogenic CO2 emissions, this change in isotopic fractionation and lowering of δ13CPOC may propagate through the marine food web, with implications for the use of δ13CPOC as a tracer of dietary sources in the marine environment

Changes in ocean denitrification during Late Carboniferous glacial–interglacial cycles

Denitrification (the process by which nitrate and nitrite are reduced to nitrogen gas) in the oxygen-minimum zones of modern oceans is an important part of the global nitrogen cycle. Variations in rates of denitrification over Quaternary glacial-interglacial timescales may have affected global climate. Evidence of denitrification has been reported from some older marine systems, but it is unclear whether denitrification rates varied during pre-Quaternary glacial cycles. Here we present ratios of organic carbon to nitrogen and nitrogen isotope data from the Upper Carboniferous black shales of the North American mid-continent. In these cyclic deposits, we find evidence of variations in the intensity of denitrification in the eastern tropical Panthalassic Ocean associated with glacially driven sea-level changes. Sedimentary 15N increases during the interval of rapid sea-level rise in each cycle, indicative of intensified denitrification, before returning to background levels as sea level stabilized during the interglacial phase. Nearly identical patterns of denitrification have been observed in the eastern tropical Pacific during the Quaternary period. We therefore conclude that ice ages have produced similar oceanographic conditions and nitrogen cycle dynamics in these regions over the past 300 million years. © 2008 Macmillan Publishers Limited

The impact of ocean deoxygenation on iron release from continental margin sediments

In the oceans’ high-nitrate–low-chlorophyll regions, such as the Peru/Humboldt Current system and the adjacent eastern equatorial Pacific1, primary productivity is limited by the micronutrient iron. Within the Peruvian upwelling area, bioavailable iron is released from the reducing continental margin sediments2. The magnitude of this seafloor source could change with fluctuations in the extension or intensity of the oxygen minimum zones3, 4. Here we show that measurements of molybdenum, uranium and iron concentrations can be used as a proxy for sedimentary iron release, and use this proxy to assess iron release from the sea floor beneath the Peru upwelling system during the past 140,000 years. We observe a coupling between levels of denitrification, as indicated by nitrogen isotopes, trace metal proxies for oxygenation, and sedimentary iron concentrations. Specifically, periods with poor upper ocean oxygenation are characterized by more efficient iron retention in the sediment and a diminished iron supply to the water column. We attribute efficient iron retention under more reducing conditions to widespread sulphidic conditions in the surface sediment and concomitant precipitation of iron sulphides. We argue that iron release from continental margin sediments is most effective in a narrow redox window where neither oxygen nor sulphide is present. We therefore suggest that future deoxygenation in the Peru upwelling area would be unlikely to result in increased iron availability, whereas in weaker oxygen minimum zones partial deoxygenation may enhance the iron supply