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. Constraining how the biological pump operated in the past is 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 trace metals that are least sensitive to productivity may be used to track 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.
Better constraints on the magnitude of particulate export and the residence times of trace elements are required to understand marine food web dynamics, track the transport of anthropogenic trace metals in the ocean, and improve global climate models. While prior studies have been successful in constructing basin‐scale budgets of elements like carbon in the upper ocean, the cycling of particulate trace metals is poorly understood. The238U‐234Th method is used here with data from the GP‐16 GEOTRACES transect to investigate the upper ocean processes controlling the particulate export of cadmium, cobalt, and manganese in the southeastern Pacific. Patterns in the flux data indicated that particulate cadmium and cobalt behave similarly to particulate phosphorus and organic carbon, with the highest export in the productive coastal region and decreasing flux with depth due to remineralization. The export of manganese was influenced by redox conditions at the low oxygen coastal stations and by precipitation and/or scavenging elsewhere. Residence times with respect to export (total inventory divided by particulate flux) for phosphorus, cadmium, cobalt, and manganese in the upper 100 and 200 m were determined to be on the order of months to years. These GEOTRACES‐based synthesis efforts, combining a host of concentration and tracer data with unprecedented resolution, will help to close the oceanic budgets of trace metals.
more » « less- NSF-PAR ID:
- 10374615
- Publisher / Repository:
- DOI PREFIX: 10.1029
- Date Published:
- Journal Name:
- Global Biogeochemical Cycles
- Volume:
- 33
- Issue:
- 1
- ISSN:
- 0886-6236
- Page Range / eLocation ID:
- p. 15-36
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
The stoichiometry of biological components and their influence on dissolved distributions have long been of interest in the study of the oceans. Cobalt has the smallest oceanic inventory of inorganic micronutrients and hence is particularly vulnerable to influence by internal oceanic processes including euphotic zone uptake, remineralization, and scavenging. Here we observe not only large variations in dCo : P stoichiometry but also the acceleration of those dCo : P ratios in the upper water column in response to several environmental processes. The ecological stoichiometry of total dissolved cobalt (dCo) was examined using data from a US North Atlantic GEOTRACES transect and from a zonal South Atlantic GEOTRACES-compliant transect (GA03/3_e and GAc01) by Redfieldian analysis of its statistical relationships with the macronutrient phosphate. Trends in the dissolved cobalt to phosphate (dCo : P) stoichiometric relationships were evident in the basin-scale vertical structure of cobalt, with positive dCo : P slopes in the euphotic zone and negative slopes found in the ocean interior and in coastal environments. The euphotic positive slopes were often found to accelerate towards the surface and this was interpreted as being due to the combined influence of depleted phosphate, phosphorus-sparing (conserving) mechanisms, increased alkaline phosphatase metalloenzyme production (a zinc or perhaps cobalt enzyme), and biochemical substitution of Co for depleted Zn. Consistent with this, dissolved Zn (dZn) was found to be drawn down to only 2-fold more than dCo, despite being more than 18-fold more abundant in the ocean interior. Particulate cobalt concentrations increased in abundance from the base of the euphotic zone to become ∼ 10 % of the overall cobalt inventory in the upper euphotic zone with high stoichiometric values of ∼ 400 µmol Co mol−1 P. Metaproteomic results from the Bermuda Atlantic Time-series Study (BATS) station found cyanobacterial isoforms of the alkaline phosphatase enzyme to be prevalent in the upper water column, as well as a sulfolipid biosynthesis protein indicative of P sparing. The negative dCo : P relationships in the ocean interior became increasingly vertical with depth, and were consistent with the sum of scavenging and remineralization processes (as shown by their dCo : P vector sums). Attenuation of the remineralization with depth resulted in the increasingly vertical dCo : P relationships. Analysis of particulate Co with particulate Mn and particulate phosphate also showed positive linear relationships below the euphotic zone, consistent with the presence and increased relative influence of Mn oxide particles involved in scavenging. Visualization of dCo : P slopes across an ocean section revealed hotspots of scavenging and remineralization, such as at the hydrothermal vents and below the oxygen minimum zone (OMZ) region, respectively, while that of an estimate of Co* illustrated stoichiometrically depleted values in the mesopelagic and deep ocean due to scavenging. This study provides insights into the coupling between the dissolved and particulate phase that ultimately creates Redfield stoichiometric ratios, demonstrating that the coupling is not an instantaneous process and is influenced by the element inventory and rate of exchange between phases. Cobalt's small water column inventory and the influence of external factors on its biotic stoichiometry can erode its limited inertia and result in an acceleration of the dissolved stoichiometry towards that of the particulate phase in the upper euphotic zone. As human use of cobalt grows exponentially with widespread adoption of lithium ion batteries, there is a potential to affect the limited biogeochemical inertia of cobalt and its resultant ecology in the oceanic euphotic zone.more » « less
-
more » « less
Abstract Macronutrients and trace metals are incorporated into phytoplankton during growth and regenerated back into the water column when phytoplankton decay, a process that contributes to the distributions of dissolved trace metals and macronutrients in depth profiles. To study this, we incubated mixed Gulf of Mexico phytoplankton assemblages and monocultures of the diatom
Pseudo‐nitzschia dolorosa and the dinoflagellateKarenia brevis in the dark. Over 6 months, macronutrients (phosphate, silicic acid, nitrate + nitrite, nitrite, ammonium), chlorophyll‐a , particulate organic carbon and nitrogen, and prokaryotes were monitored alongside dissolved manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), cadmium (Cd), and lead (Pb). Results were compared to depth profiles to evaluate the role of regeneration in trace metal cycling. In contrast to water‐column distributions, silicic acid and phosphate were closely coupled in experiments containing diatoms, indicating a shared regeneration pathway. Nitrification and nitrifying prokaryotes were only observed near the end of a subset of the experiments. Of the trace metals, Cd was most tightly coupled with phosphate. Regeneration of Mn was followed by rapid drawdown, consistent with Mn‐oxide formation. Iron (Fe), Cu, and Pb typically remained low until Mn was depleted, suggesting either scavenging to Mn‐oxides or otherwise delayed regeneration of these elements. Cobalt (Co) and Ni were largely conservative, but behaved like nutrients in the experiment using more offshore water low in Cd and Zn. Although experimental conditions were limited in their representation of the water column, these incubations provide novel insight into macronutrient and trace metal regeneration in the oceans. -
more » « less
Abstract In the Southern Ocean, it is well‐known that iron (Fe) limits phytoplankton growth. Yet, other trace metals can also affect phytoplankton physiology. This study investigated feedbacks between phytoplankton growth and dissolved Fe, manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), and cadmium (Cd) concentrations in Southern Ocean shipboard incubations. Three experiments were conducted in September–October 2016 near the West Antarctic Peninsula: Incubations 1 and 3 offshore in the Antarctic Circumpolar Current, and Incubation 2 inshore in Bransfield Strait. Additions of Fe and/or vitamin B12to inshore and offshore waters were employed and allowed assessment of metal (M) uptake relative to soluble reactive phosphorus (P) across a wide range of initial conditions. Offshore, treatments of >1 nmol L−1added Fe were Fe‐replete, whereas inshore waters were already Fe‐replete. Results suggest Mn was a secondary limiting nutrient inshore and offshore. No Fe‐vitamin B12colimitation was observed. Overall, M:P uptake in the incubations was closely related to initial dissolved M:P for Fe, Mn, Co, Ni, and Cd, and for Cu inshore. Final concentrations of Fe and Zn were similar across light treatments of the experiments despite very different phytoplankton responses, and we observed evidence for Co/Cd/Zn substitution and for recycling of biogenic metals as inventories plateaued. In dark bottles, the absence of Mn oxidation may have allowed more efficient recycling of Fe and other trace metals. Our results provide insight into factors governing trace metal uptake, with implications for phytoplankton community composition locally and preformed micronutrient bioavailability in Southern Ocean water masses.
-
more » « less
Abstract Deposition of aerosols to the surface ocean is an important factor affecting primary production in the surface ocean. However, the sources and fluxes of aerosols and associated trace elements remain poorly defined. Aerosol210Pb,210Po, and7Be data were collected on US GEOTRACES cruise GP15 (Pacific Meridional Transect, 152°W; 2018).210Pb fluxes are low close to the Alaskan margin, increase to a maximum at ∼43°N, then decrease to lower values. There is good agreement between210Pb fluxes and long‐term land‐based fluxes during the SEAREX program (1970–1980s), as well as between GP15 and GP16 (East Pacific Zonal Transect, 12°S; 2013) at adjacent stations. A normalized fraction
f (7Be,210Pb) is used to discern aerosols with upper (highf ) versus lower (lowf ) troposphere sources. Alaskan/North Pacific aerosols show significant continental influence while equatorial/South Pacific aerosols are supplied to the marine boundary layer from the upper troposphere. Lithogenic trace elements Al and Ti show inverse correlations withf (7Be,210Pb), supporting a continental boundary layer provenance while anthropogenic Pb shows no clear relationship withf (7Be,210Pb). All but four samples have210Po/210Pb activity ratios <0.2 suggesting short aerosol residence time. Among the four samples (210Po/210Pb = 0.42–0.88), two suggest an upper troposphere source and longer aerosol residence time while the remaining two cannot be explained by long aerosol residence time nor a significant component of dust. We hypothesize that enrichments of210Po in them are linked to Po enrichments in the sea surface microlayer, possibly through Po speciation as a dissolved organic or dimethyl polonide species.
