The chemistry of copper (Cu) in seawater is well known to be dominated by complexation with organic ligands. The prevailing paradigm is that Cu forms strong but labile complexes. Recently, a novel procedure revealed that only a small fraction of dissolved Cu exists as labile complexes. The majority is present as a fraction that is relatively inert on timescales of weeks or more and probably does not participate in coordination exchange reactions, including biologically mediated processes. Samples collected from the 2018 GEOTRACES GP15 cruise show that throughout the interior of the Pacific Ocean, this inert fraction comprises about 90% of the dissolved Cu. Labile Cu accumulates in surface waters, probably arising from photochemical decomposition of the inert fraction. There is also a modest accumulation of labile Cu near deep sea sediments and along the Alaskan shelf and slope. The results have important implications for Cu transport and biological availability. Inert Cu may influence Cu transport throughout the water column and contribute to the linear increase in Cu with depth, a distribution which is hard to explain for a biologically active trace metal. The origins of inert Cu are unknown. It may be produced slowly within the water column on the timescale of meridional overturning circulation. In the Columbia River, between 92% and 98% of the dissolved Cu is in the inert fraction, suggesting a possible terrestrial source of inert Cu to the ocean.
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Biogeochemical cycling of Cd, Mn, and Ce in the Eastern Tropical North Pacific oxygen‐deficient zone
Abstract 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.
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Abstract 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. -
Abstract The distributions of iodate (IO3−), iodide (I−), nitrite (NO2−), and oxygen (O2) were determined on two zonal transects and one meridional transect in the Eastern Tropical North Pacific (ETNP) in 2018. Iodine is a useful tracer of in situ redox transformations and inputs within the water column from continental margins. In oxygenated waters, iodine is predominantly present as oxidized iodate. In the oxygen deficient zone (ODZ) in the ETNP, a substantial fraction is reduced to iodide, with the highest iodide concentrations coincident with the secondary nitrite maxima. These features resemble ODZs in the Arabian Sea and Eastern Tropical South Pacific (ETSP). Maxima in iodide and nitrite were associated with a specific water mass, referred to as the 13 °C Water, the same water mass that contains the highest concentrations of iodide within the ETSP. Physical processes leading to patchiness in the 13 °C Water relative to other water masses could account for the patchiness frequently observed in iodide and nitrite, probably reflecting subsurface mesoscale features such as eddies. Throughout much of the ETNP ODZ, iodine concentrations were higher than the mean oceanic value. This “excess iodine” is attributed to lateral inputs from sedimentary margins. Excess iodine maxima are centered within a potential density of 26.2–26.6 kg/m3, a density range that intersects with reducing shelf sediments and is almost identical to the ETSP. Evidently, margin input processes are significant throughout the basin and can influence the nitrogen and iron cycles as well, as in the ETSP.
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Abstract Oceanic oxygen deficient zones (ODZs) influence global biogeochemical cycles in a variety of ways, most notably by acting as a sink for fixed nitrogen (Codispoti et al. 2001). Optimum multiparameter analysis of data from two cruises in the Eastern Tropical North Pacific (ETNP) was implemented to develop a water mass analysis for the large ODZ in this region. This analysis reveals that the most pronounced oxygen deficient conditions are within the 13°C water (13CW) mass, which is distributed via subsurface mesoscale features such as eddies branching from the California Undercurrent. Nitrite accumulates within these eddies and slightly below the core of the 13CW. This water mass analysis also reveals that the 13CW and deeper Northern Equatorial Pacific Intermediate Water (NEPIW) act as the two Pacific Equatorial source waters to the California Current System. The Equatorial Subsurface Water and Subtropical Subsurface Water are synonymous with the 13CW and this study refers to this water mass as the 13CW based on its history. Since the 13CW has been found to dominate the most pronounced oxygen deficient conditions within the Eastern Tropical South Pacific ODZ and the Peru‐Chile Undercurrent, the 13CW and the NEPIW define boundaries for oxygen minimum conditions across the entire eastern Pacific Ocean.