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This presentation is a review of the chemistries of redox sensitive elements within suboxic regions of extreme oxygen minimum zones. Suboxic regions are defined as extreme oxygen minimum zones with dissolved oxygen < 10 µmol kg-1 (and likely 10 µmol kg-1 or N* values of _10 µmol kg-1. Suboxic regions predictably occur in the tropical and subtropical eastern Pacific and the Arabian Sea. These suboxic zones are important in the global biogeochemistry of nitrogen and act as an important sink for fixed nitrogen. Minor and trace element redox couples such as iodate/iodide and leachable particulate Mn/dissolved Mn undergo complete reduction within suboxic regions and clearly define suboxic zones in the water column. Other trace element redox couples such as Cr(VI)/Cr(III) and Se(VI)/Se(IV)/Se(-II) undergo partial reduction and are more complicated due to the chemistries of the different redox species. Iron does not appear to undergo in-situ reduction within suboxic waters, but when the suboxic waters overly shelf sediments dissolved Fe(II) can be supplied to the suboxic water column from the anoxic sediments and be partially stabilized with respect to oxidation to Fe(III) in these suboxic waters.El presente trabajo corresponde a una revisión de la química de los elementos afectados por procesos redox en áreas subóxicas de las Zonas de Mínimo Oxígeno. Las áreas subóxicas están definidas como zonas extremas de mínimo oxígeno, con concentraciones de oxígeno disuelto inferiores a 10 µmol kg-1 (posiblemente < 5 µmol kg-1) y con evidencias claras de reducción de nitrato, pero no de reducción de sulfato. Estas áreas presentan un déficit de nitrato >10 µmol kg-1, o valores de N* de - 10 µmol kg-1. Las zonas subóxicas ocurren previsiblemente en el Pacífico tropical y subtropical oriental, así como en el Mar Arábico. Pares redox de elementos menores y traza, tales como IO3-/I-y Mn particulado/Mn disuelto, definen claramente las zonas subóxicas en la columna de agua. Otros pares redox de elementos traza, tales como Cr(VI)/Cr(III) y Se(VI)/Se(IV)/Se(-II), son reducidos parcialmente y son más complejos debido a la química de las diferentes formas redox. Aparentemente, el hierro no presenta reducción in situ en aguas subóxicas. Sin embargo, cuando la columna de agua presenta condiciones subóxicas sobre los sedimentos de la plataforma continental, los sedimentos pueden actuar como fuente de Fe(II) disuelto hacia la columna de agua subóxica, donde puede ser estabilizado parcialmente con respecto a Fe(III).

Abstract: Coastal upwelling in the central California Current System (cCCS) delivers macro and micronutrients to the surface ocean that fuel biological productivity. Variations in upwelling strength and continental shelf width affect trace metal sources seasonally. The purpose of this study was to investigate various sources and distributions for a suite of dissolved trace metals (Mn, Fe, Co, Ni, Cu, Zn, and Cd) in the cCCS (34–41°N) as well as to determine the effects of biological uptake, physical advection, and mixing processes on trace metal concentrations during the spring and summer upwelling season. Continental shelf sediments did not substantially affect upwelled concentrations of Ni, Zn, and Cd — three typical nutrient-type trace metals. However, shelf sediments provided a significant external source for Mn, Fe, Co, and Cu — scavenged and hybrid-type trace metals. There was no clear seasonal trend in benthic boundary layer (BBL) Fe concentrations; however, higher concentrations of Mn and Co together with lower O2 concentrations were found in the BBL in the late summer compared to early spring. Conversely, there was a higher sedimentary Cu source to the BBL in the early spring before O2 concentrations dropped. Surface transect samples along the Big Sur Coast (May, 2010) and North Coast (August, 2011) demonstrated both mixing and biological assimilation of NO3 − and trace metals. Iron and Zn showed accelerated drawdown relative to NO3 − during both seasons suggesting an increased metal to nitrogen drawdown ratio at higher dissolved metal concentrations. Surface Mn and Co concentrations were higher in the late summer and both showed evidence for accelerated drawdown relative to NO3 −. Cadmium and Ni were strongly correlated with NO3 − indicating that both are affected by a combination of assimilation and regeneration at a constant rate relative to NO3 −; however, Cd showed slightly increased drawdown in aged upwelled waters during the late summer when Zn and Fe concentrations were low. This study provides field trace metal and macronutrient data supporting past laboratory studies suggesting that complex biological interactions are a key control on trace metal distributions and marine biogeochemical cycles. [Copyright &y& Elsevier]

Abstract: The influence of the Columbia River plume on the distributions of nitrate and iron and their sources to coastal and shelf waters were examined. In contrast to other large estuaries, the Columbia River is a unique study area as it supplies very little nitrate (5 μM) and iron (14–30 nM) at salinities of 1–2 to coastal waters. Elevated nitrate and dissolved iron concentrations (as high as 20 μM and 20 nM) were observed, however, in the near field Columbia River plume at salinities of 20. Surface nitrate concentrations were higher than observed in the Columbia River itself and therefore must be added by entrainment of higher nitrate concentrations from subsurface coastal waters. Tidal flow was identified as an important factor in determining the chemical constituents of the Columbia River plume. During the rising flood tide, nitrate and iron were entrained into the plume waters resulting in concentrations of 15 μM and 6 nM, respectively. Conversely, during the ebb tide the concentrations of nitrate and total dissolved iron were reduced to 0.3–3 μM and 1–2 nM, respectively, with a concomitant increase in chlorophyll a concentrations. As these plume waters moved offshore the plume drifted directly westward, over a nitrate depleted water mass (<0.2 μM). The plume water was also identified to move southwards and offshore during upwelling conditions and nitrate concentrations in this far field plume were also depleted. Iron concentrations in the near-field Columbia River plume are sufficient to meet the biological demand. However, due to the low nitrate in the Columbia River itself, nitrate in the plume is primarily dependent on mixing with nitrate rich, cold, high salinity subsurface waters. Without such an additional source the plume rapidly becomes nitrate limited. [Copyright &y& Elsevier]

Abstract: Coastal waters in the northern Gulf of Alaska (GoA) are considered iron-rich and nitrate-poor, in contrast to the iron-poor, high-nitrate, low chlorophyll (HNLC) waters of the central GoA. The degree of mixing between these two regimes, enhanced by mesoscale eddies, is essential to the high productivity observed in the region. As part of a study on iron delivery to the central GoA via mesoscale eddies, extensive work was focused on characterizing the coastal endmember, the Alaska Coastal Current. In surface Alaskan coastal waters between Yakutat and the Kenai Peninsula, dissolved iron concentrations ranged from 0.5 to 4.1nM with an average of ∼2nM. In contrast, leachable particulate iron concentrations were much higher and more variable, ranging from over 1μM in the Alsek River plume to less than 5nM at the base of Cook Inlet. Cross-shelf transport of both surface and subsurface dissolved iron and leachable particulate iron was observed. Throughout the study area, leachable particulate iron values were at least an order of magnitude higher than dissolved values, suggesting that the system''s ability to solubilize this large concentration of leachable particulate iron is overwhelmed by the massive input of glacial-derived particulate iron. Nevertheless, suspended leachable particulate iron remains available for exchange to the dissolved phase and is suggested to maintain a relatively constant (∼2nM) source of dissolved iron in the coastal GoA. [Copyright &y& Elsevier]

Abstract: Distributions of iron and nitrate in the central California Current System upwelling regime (cCCS) from 34 to 41°N were determined during cruises in May 2010 and August 2011. High spatial and temporal resolution data for dissolved Fe and (nitrate+nitrite) in the cCCS from this study greatly expands upon previous studies that were narrower in scope (e.g., focused on just the Monterey Bay region). Shelf sediments from mid-shelf mud belts in this region provide the dominant source of Fe, and there are areas in the cCCS where insufficient Fe is upwelled to accompany elevated levels of other macronutrients (nitrate, phosphate, silicate) to fuel extensive diatom blooms. Surface dissolved Fe concentrations were related to continental shelf width and upwelling strength, and surface Fe concentrations tended to be lower in the late summer than early spring. We present extensive benthic boundary layer (BBL) dissolved and leachable particulate Fe data from both seasons in the mid-shelf region along the central California coast. Leachable particulate Fe concentrations were strongly related to the width of the mid-shelf mud belts (i.e., the continental shelf between the 50 and 90m isobaths). Dissolved Fe concentrations in the BBL over the mid-shelf were generally highest in wide mud belt areas as well as in areas with very low dissolved oxygen concentrations but did not show a clear seasonal trend. Evidence for probable Fe limitation in upwelled waters was found by using surface dissolved Fe: ratios and the estimated specific growth rate of coastal diatoms based on either Fe or concentrations. Several coastal upwelling regions with only moderate to narrow continental shelves (Pt. Arena to Cape Mendocino and the Big Sur Coast) exhibited evidence for Fe limitation in both the spring and summer upwelling seasons. [Copyright &y& Elsevier]