Biological productivity in the ocean directly influences the partitioning of carbon between the atmosphere and ocean interior. Through this carbon cycle feedback, changing ocean productivity has long been hypothesized as a key pathway for modulating past atmospheric carbon dioxide levels and hence global climate. Because phytoplankton preferentially assimilate the light isotopes of carbon and the major nutrients nitrate and silicic acid, stable isotopes of carbon (C), nitrogen (N), and silicon (Si) in seawater and marine sediments can inform on ocean carbon and nutrient cycling, and by extension the relationship with biological productivity and global climate. Here we compile water column C, N, and Si stable isotopes from GEOTRACES-era data in four key ocean regions to review geochemical proxies of oceanic carbon and nutrient cycling based on the C, N, and Si isotopic composition of marine sediments. External sources and sinks as well as internal cycling (including assimilation, particulate matter export, and regeneration) are discussed as likely drivers of observed C, N, and Si isotope distributions in the ocean. The potential for C, N, and Si isotope measurements in sedimentary archives to record aspects of past ocean C and nutrient cycling is evaluated, along with key uncertainties and limitations associated with each proxy. Constraints on ocean C and nutrient cycling during late Quaternary glacial-interglacial cycles and over the Cenozoic are examined. This review highlights opportunities for future research using multielement stable isotope proxy applications and emphasizes the importance of such applications to reconstructing past changes in the oceans and climate system.

Phytoplankton productivity and export sequester climatically significant quantities of atmospheric carbon dioxide as particulate organic carbon through a suite of processes termed the biological pump. How the biological pump operated in the past is therefore important for understanding past atmospheric carbon dioxide concentrations and Earth’s climate history. However, reconstructing the history of the biological pump requires proxies. Due to their intimate association with biological processes, several bioactive trace metals and their isotopes are potential proxies for past phytoplankton productivity, including: iron, zinc, copper, cadmium, molybdenum, barium, nickel, chromium, and silver. Here we review the oceanic distributions, driving processes, and depositional archives for these nine metals and their isotopes based on GEOTRACES-era datasets. We offer an assessment of the overall maturity of each isotope system to serve as a proxy for diagnosing aspects of past ocean productivity and identify priorities for future research. This assessment reveals that cadmium, barium, nickel, and chromium isotopes offer the most promise as tracers of paleoproductivity, whereas iron, zinc, copper, and molybdenum do not. Too little is known about silver to make a confident determination. Intriguingly, the elements that are least sensitive to productivity may be used to trace other aspects of ocean chemistry, such as nutrient sources, particle scavenging, organic complexation, and ocean redox state. These complementary sensitivities suggest new opportunities for combining perspectives from multiple proxies that will ultimately enable painting a more complete picture of marine paleoproductivity, biogeochemical cycles, and Earth’s climate history.

During Marine Isotope Stage 3 (MIS-3; 57–29 ka) Antarctic ice cores reveal a glacial climate state punctuated by millennial-scale warming events and pulses of CO2. Changes in iron-fertilised export production and ocean circulation/upwelling, interpreted from South Atlantic sediment cores, suggest that the Southern Ocean is a conduit for the storage and release of CO2 from the deep ocean. However, it is unclear whether this occurs throughout the Southern Ocean as these processes have not previously been investigated in the southwest Pacific . Here we describe localised iron limitation linked to glaciation changes in New Zealand, which reduced export production during early MIS-3 (60–48 ka) and caused decreases/increases in export production during late MIS-3 (48–29 ka) millennial-scale warming/cooling. Consistent decreases in foraminifera-bound δ15N during all MIS-3 warming events may reflect changes in the supply of nitrate to the subantarctic Pacific, possibly from increased wind-driven upwelling in the Antarctic and northward eddy-driven transport and/or shifting SO fronts. Concomitant decreases in bottom water oxygen and increases in the 14C age of deep waters suggest that old, nutrient-rich waters influenced upper circumpolar deep water in the southwest Pacific during warming events. This signature may reflect an expansion of Pacific Deep Water into the Southern Ocean as Southern Ocean overturning strengthens. Iron-limitation of export production, the expansion of Pacific Deep water, and increased wind-driven upwelling would all work to contribute to increasing atmospheric CO2 through reduced drawdown, and increased outgassing from the Pacific carbon reservoir during the millennial-scale warming events of MIS-3.

Coastal tropical waters are experiencing rapid increases in anthropogenic pressures, yet coastal biogeochemical dynamics in the tropics are poorly studied. We present a multi-year biogeochemical time series from the Singapore Strait in Southeast Asia’s Sunda Shelf Sea. Despite being highly urbanised and a major shipping port, the strait harbours numerous biologically diverse habitats, and is a valuable system for understanding how tropical marine ecosystems respond to anthropogenic pressures. Our results show strong seasonality driven by the semi-annual reversal of ocean currents: dissolved inorganic nitrogen (DIN) and phosphorus varied from ≤0.05 µmol l-1 during the intermonsoons to ≥4 µmol l-1 and ≥0.25 µmol l-1, respectively, during the southwest monsoon. Si(OH)4 exceeded DIN year-round. Based on nutrient concentrations, their relationships to salinity and coloured dissolved organic matter, and the isotopic composition of NOx-, we infer that terrestrial input from peatlands is the main nutrient source. This input delivered dissolved organic carbon (DOC) and nitrogen, but was notably depleted in dissolved organic phosphorus. In contrast, particulate organic matter showed little seasonality, and the δ13C of particulate organic carbon (-21.0 ± 1.5‰) is consistent with a primarily autochthonous origin. Diel changes in dissolved O2 varied seasonally with a pattern that suggests that light availability controls primary productivity more than nutrient concentrations. However, diel changes in pH were greater during the southwest monsoon, when remineralisation of terrestrial DOC lowers the seawater buffer capacity. We conclude that terrestrial input results in mesotrophic conditions, and that the strait might be vulnerable to further eutrophication if nutrient inputs increase during seasons when light availability is high. Moreover, the seasonality of diel pH variation suggests that coral reefs exposed to terrestrial organic matter in the Sunda Shelf may be at significant risk from future ocean acidification.