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The speciation of most biologically active trace metals in seawater is dominated by complexation by organic ligands. This review traces the history of work in this area, from the early observations that showed surprisingly poor recoveries using metal preconcentration protocols to the present day, where advances in mass spectroscopy and stable isotope geochemistry are providing new insights into the structure, origin, fate, and biogeochemical impact of organic ligands. Many long-standing hypotheses about the specific biological origin of ligands such as siderophores in seawater are finally being validated. This work has revealed the complexity of organic complexation, with multiple ligands and, in some cases, timescales of ligand exchange that are much slower than originally thought. The influence of organic complexation on scavenging is now a key parameter in biogeochemical models of biologically essential metals, especially iron. New insights about the sources and sinks of ligands are required to enhance the usefulness of these models.

Expected final online publication date for the Annual Review of Marine Science, Volume 16 is January 2024. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates. 

Copper (Cu) is an important micronutrient for marine organisms, which can also be toxic at elevated concentrations. Here, we present a new model of global ocean Cu biogeochemical cycling, constrained by GEOTRACES observations, with key processes including sources from rivers, dust, and sediments, biological uptake and remineralization of Cu, reversible scavenging of Cu onto sinking particles, conversion of Cu between labile and inert species, and ocean circulation. In order for the model to match observations, in particular the relatively small increase in Cu concentrations along the global “conveyor belt,” we find it is necessary to include significant external sources of Cu with a magnitude of roughly 1.3 Gmol yr⁻¹, having a relatively stronger impact on the Atlantic Ocean, though the relative contributions of river, dust, and sediment sources are poorly constrained. The observed nearly linear increase in Cu concentrations with depth requires a strong benthic source of Cu, which includes the sedimentary release of Cu that was reversibly scavenged from the water column. The processes controlling Cu cycling in the Arctic Ocean appear to be unique, requiring both relatively high Cu concentrations in Arctic rivers and reduced scavenging in the Arctic. Observed partitioning of Cu between labile and inert phases is reproduced in the model by the slow conversion of labile Cu to inert in the whole water column with a half‐life of ∼250 years, and the photodegradation of inert Cu to labile in the surface ocean with a minimum half‐life of ∼2 years at the equator.

 

Nitrite is a key intermediate during fixed nitrogen loss in the ocean, and it accumulates within marine Oxygen Deficient Zones (ODZ). ODZs are vast subsurface regions where nitrate is the dominant electron acceptor, and these regions host approximately 50% of the fixed nitrogen loss in the world's oceans. Nitrite accumulates in these waters, and recent research has discovered substantial reoxidation of nitrite back to nitrate, a significant process in the global nitrogen cycle. Partitioning between reduction and oxidation determines if marine fixed nitrogen is lost or recycled. Investigations into nitrite oxidation typically rely on results from incubations, which limits the spatiotemporal sampling coverage. Using basin‐scale data, we analyzed the ratios of nutrient regeneration within the three water masses that feed the Eastern Tropical North Pacific (ETNP) ODZ. Deviations in the ratios of nutrient regeneration from Redfield stoichiometry indicated prolific nitrite reoxidation across this region. We estimate that 79 ± 7% of the nitrite produced in the ODZ between the 26.2 and 26.4 kg m⁻³isopycnals is reoxidized, whereas 54 ± 2% of the nitrite produced between the 26.7 and 26.9 kg m⁻³isopycnals is reoxidized. Our analysis also illustrates discrete “metabolic switching points” from primarily aerobic to primary anaerobic processes, which occur in each water mass. We applied water mass analysis to repeat cruises on the WOCE P18 line from Baja California to 10°N, which revealed high spatiotemporal variability in nitrite reoxidation. These results confirm previous measurements of significant fixed nitrogen recycling across the ETNP; however, our analysis enables high‐resolution estimates of this process.

 

Widespread hypoxia occurs seasonally across the Oregon continental shelf, and the duration, intensity, and frequency of hypoxic events have increased in recent years. In hypoxic regions, iron reduction can liberate dissolved Fe(II) from continental shelf sediments. Fe(II) was measured in the water column across the continental shelf and slope on the Oregon coast during summer 2022 using both a trace metal clean rosette and a high‐resolution benthic gradient sampler. In the summer, Fe(II) concentrations were exceptionally high (40–60 nM) within bottom waters and ubiquitous across the Oregon shelf, reflecting the low oxygen condition (40–70 μM) at that time. The observed inverse correlation between Fe(II) and bottom water oxygen concentrations is in agreement with expectations based on previous work that demonstrates oxygen is a major determinant of benthic Fe fluxes. Rapid attenuation of Fe(II) from the benthic boundary layer (within 1 m of the seafloor) probably reflects efficient cross‐shelf advection. One region, centered around Heceta Bank (~ 44°N) acts a hotspot for Fe release on the Oregon continental shelf, likely due to its semi‐retentive nature and high percent mud content in sediment. The results suggest that hypoxia is an important determinant of the inventory of iron is Oregon shelf waters and thus ultimately controls the importance of continental margin‐derived iron to the interior of the North Pacific Basin.

 

The distributions of iodate and iodide were measured along the GEOTRACES GP15 meridional transect at 152°W from the shelf of Alaska to Papeete, Tahiti. The transect included oxygenated waters near the shelf of Alaska, the full water column in the central basin in the North Pacific Basin, the upper water column spanning across seasonally mixed regimes in the north, oligotrophic regimes in the central gyre, and the equatorial upwelling. Iodide concentrations are highest in the permanently stratified tropical mixed layers, which reflect accumulation due to light‐dependent biological processes, and decline rapidly below the euphotic zone. Vertical mixing coefficients (K_z), derived from complementary⁷Be data, enabled iodide oxidation rates to be estimated at two stations. Iodide half‐lives of 3–4 years show the importance of seasonal mixing processes in explaining north‐south differences in the transect, and also contribute to the decrease in iodide concentrations with depth below the mixed layer. These estimated half‐lives are consistent with a recent global iodine model. No evidence was found for significant inputs of iodine from the Alaskan continental margin, but there is a significant enrichment of iodide in bottom waters overlying deep sea sediments from the interior of the basin.

 

Oxygen‐deficient zones (ODZs) play an important role in the distribution and cycling of trace metals in the ocean, as important sources of metals including Fe and Mn, and also as possible sinks of chalcophile elements such as Cd. The Eastern Tropical North Pacific (ETNP) ODZ is one of the three largest ODZs worldwide. Here, we present results from two sectional surveys through the ETNP ODZ conducted in 2018, providing high‐resolution concentrations of several metals, along with complimentary measurements of nutrients and iodine speciation. We show that samples obtained from the ship's regular rosette are clean for Cd, Mn, Ni, and light rare earth elements, while uncontaminated Fe, Zn, Cu, and Pb samples cannot be obtained without a special trace‐metal clean sampling system. Our results did not show evidence of Cd sulfide precipitation, even within the most oxygen‐depleted water mass. High Mn and Ce concentrations and high Ce anomalies were observed in low‐oxygen seawater. These maxima were most pronounced in the upper water column below the oxycline, coincident with the secondary nitrite maxima and the lowest oxygen concentrations, in what is generally considered the most microbially active part of the water column. High Mn and Ce features were also coincident with maxima in excess iodine, a tracer of shelf sediment sources. Mn and Ce maxima were most prominent within the 13°C water mass, spanning a density horizon that enhances isopycnal transport from the shelf sediments, resulting in transport of Mn and Ce at least 2500 km offshore.