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.
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.
more » « less- Award ID(s):
- 1736896
- PAR ID:
- 10397007
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Limnology and Oceanography
- Volume:
- 68
- Issue:
- 2
- ISSN:
- 0024-3590
- Page Range / eLocation ID:
- p. 483-497
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Abstract -
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. -
Abstract 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.
-
Abstract Climate change is expected to increase the strength of ocean Oxygen Deficient Zones (ODZs), but we lack a detailed understanding of the temporal or spatial variability of these ODZs. A 50‐year time series in the Eastern Tropical North Pacific (ETNP) ODZ revealed that it has strengthened by 30% from 1994 to 2019. We subdivided the ODZ into a core and a deep layer based on potential density and revealed that different processes control the magnitude of fixed nitrogen loss between these regions. We postulate that the depth of the upper ETNP ODZ water mass, the 13°C Water, influences the organic carbon supply to the core ODZ and therefore its strength. We correlated the maximum fixed nitrogen loss in the core ODZ with a nearby sedimentary nitrogen isotope record and found that this recent increase in the magnitude of fixed nitrogen loss occurred only a few times over the last 1,200 years. Using this correlation, we derived the first confidence interval for the natural variability of the maximum fixed nitrogen loss within the ETNP ODZ, which has a range of 3.3 μmol kg−1(
p = 0.01). While the current increase is only comparable to two previous events, it is within the confidence interval for natural variability (p = 0.03). The deep ODZ also strengthened from 2016 to 2019 by approximately 30%, but this increase occurred more rapidly than the core ODZ, and this dramatic increase was not observed over the rest of the 40 years. Climate‐driven intensification could lead to unprecedented changes in the ETNP ODZ within the next decade. -
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.