1,721,056 research outputs found
Oceanic micronutrients: Trace metals that are essential for marine life
No full textTrace metals are essential for life in the oceans but are present in extremely low concentrations. The availability of trace elements in surface waters frequently regulates the growth of microscopic marine plants called phytoplankton. As phytoplankton are responsible for taking up atmospheric carbon dioxide and exporting this to the deep ocean, trace elements are key components regulating the carbon cycle. New observations of the distribution of trace metals across all ocean basins from the GEOTRACES program have revealed a fascinating story of how the combination of trace metals interact with the ocean to regulate biological activity in new and surprising ways
Importance of vertical mixing for additional sources of nitrate and iron to surface waters of the Columbia River plume: Implications for biology
No full textThe 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.</p
Elevated Fe(II) and dissolved Fe in hypoxic shelf waters off Oregon and Washington: an enhanced source of iron to coastal upwelling regimes
No full textThere has been a growing interest in the cause and impact of hypoxic regions known as "dead zones" that have increasingly appeared along the west coast of the United States and have caused widespread destruction to the crab and fishing industry in this upwelling region. Here, we present results that demonstrate that the hypoxic conditions in the water column over the continental shelf result in a marked increase in iron(II) concentrations, which contribute to elevated dissolved and labile particulate iron concentrations. These elevated dissolved iron(II) concentrations result from two factors: (1) the hypoxic water column allows extremely elevated iron(II) concentrations in reducing porewaters to exist close to the sediment water interface, leading to an increased flux of iron(II) from the sediments; (2) the low oxygen, low pH, and low temperatures within the bottom boundary layer act in concert to markedly slow down the oxidation rate of Fe(II). During upwelling conditions, this process can result in a greatly enhanced source of Fe available to upwell to surface waters, potentially increasing phytoplankton productivity, which can, in turn, lead to enhanced export flux, driving the system further into hypoxic orsuboxic conditions.</p
The oceanic biogeochemistry of nickel and its isotopes: New data from the South Atlantic and the Southern Ocean biogeochemical divide
Full text linkISSN:0012-821XISSN:1385-013XISSN:1385-013
The distribution of reactive iron in northern Gulf of Alaska coastal waters
No full textCoastal 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 4.1. nM with an average of ~. 2. nM. In contrast, leachable particulate iron concentrations were much higher and more variable, ranging from over 1 μM in the Alsek River plume to less than 5. nM 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 (~. 2. nM) source of dissolved iron in the coastal GoA.</p
Direct determination of iron in acidified (pH 1.7) seawater samples by flow injection analysis with catalytic spectrophotometric detection: Application and intercomparison
No full textA sensitive flow injection method for determining iron in seawater developed by Measures et al. (1995) has been substantially modified to allow the direct preconcentration of dissolved iron in acidified seawater samples (pH 1.7) onto a nitrilotriacetic acid (NTA) chelating resin. This removes the need to adjust the pH and buffer samples before the preconcentration step, and the low pH eliminates potential interference from the presence of strong iron-binding organic ligands. As part of an international intercalibration exercise for the Sampling and Analysis of Fe (SAFe), we investigated at sea the precision and accuracy of this flow injection method with its preconcentration step plus catalytic spectrophotometric detection with N,N-dimethyl-p-phenylenediamine dihydrochloride (FI-NTA-DPD). Acidified seawater samples analyzed using FI-NTA-DPD were shown to be in excellent agreement with other ship- and lab-based methods. The acidification of seawater samples to pH 1.7 is an important protocol if total dissolved iron in seawater is to be determined within hours of collection. A ship- and lab-based analytical intercomparison of two flow injection methods (FI-NTA-DPD and FI-NTA-ICP-SFMS) for the determination of total dissolved iron in seawater was carried out on SAFe samples collected from surface waters and at 1000 m depth from the North Pacific Ocean. For the two methods, total dissolved iron concentrations in surface samples were 0.101 ± 0.009 and 0.098 ± 0.009 nM, respectively, and in samples from 1000 m, 0.93 ± 0.04 and 0.92 ± 0.08 nM. No statistical difference between the FI-NTA-DPD and FI-NTA-ICP-SFMS methods was observed (P = 0.05).</p
Leachable particulate iron in the Columbia River, estuary, and near-field plume
No full textThis study examines the distribution of leachable particulate iron (Fe) in the Columbia River, estuary, and near-field plume. Surface samples were collected during late spring and summer of 2004-2006 as part of four River Influence on Shelf Ecosystems (RISE) cruises. Tidal amplitude and river flow are the primary factors influencing the estuary leachable particulate Fe concentrations, with greater values during high flow and/or spring tides. Near the mouth of the estuary, leachable particulate Fe [defined as the particulate Fe solubilized with a 25% acetic acid (pH 2) leach containing a weak reducing agent to reduce Fe oxyhydroxides and a short heating step to access intracellular Fe] averaged 770 nM during either spring tide or high flow, compared to 320 nM during neap tide, low flow conditions. In the near-field Columbia River plume, elevated leachable particulate Fe concentrations occur during spring tides and/or higher river flow, with resuspended shelf sediment as an additional source to the plume during periods of coastal upwelling and spring tides. Near-field plume concentrations of leachable particulate Fe (at a salinity of 20) averaged 660 nM during either spring tide or high flow, compared to 300 nM during neap tide, low flow conditions. Regardless of tidal amplitude and river flow, leachable particulate Fe concentrations in both the river/estuary and near-field plume are consistently one to two orders of magnitude greater than dissolved Fe concentrations. The Columbia River is an important source of reactive Fe to the productive coastal waters off Oregon and Washington, and leachable particulate Fe is available for solubilization following biological drawdown of the dissolved phase. Elevated leachable Fe concentrations allow coastal waters influenced by the Columbia River plume to remain Fe-replete and support phytoplankton production during the spring and summer seasons.</p
Determination of iron and copper in seawater at pH 1.7 with a new commercially available chelating resin, NTA Superflow
No full textThe use of a commercially available chelating resin with NTA-type functional groups for concentration of trace metals from seawater is described. Trace metal recoveries from this NTA Superflow chelating resin are pH dependent. At a pH of ≤2 only iron(III) and copper are quantitatively recovered from the resin. Iron(II) cannot be quantitatively recovered from this resin below a pH of 5. However, oxidation of acidified seawater samples (pH 1.7) with H 2O2 prior to loading onto the resin has been demonstrated to allow quantitative recovery of total dissolved iron. Deferrioxamine and Rhodoturlic Acid, two commercially available siderophores were used to investigate the effect of strong Fe(III)-binding organic ligands on the ability to retain iron at different pH values. Acidification of seawater samples to pH 1.7 dissociates the iron complexed to these organic ligands, thereby allowing total dissolved iron and copper to be determined. Acidified samples from Monterey Bay were analyzed by a flow injection method coupled to ICP-SFMS detection using the NTA Superflow resin in the pre-concentration step. Results from this study show that when seawater samples are stored acidified (pH 1.7) over time, a portion of iron(III) is reduced to iron(II), thus necessitating the use of H2O2 to reoxidize the Fe(II) to Fe(III) prior to analysis. Total dissolved concentrations of iron and copper can be directly obtained on seawater samples at pH 1.7 with this method, eliminating the need to buffer the sample to a higher pH prior to column loading. This resin has the potential to be used in shipboard or in situ flow injection methods.</p
The relationship between zinc, its isotopes, and the major nutrients in the North-East Pacific
No full textTrace metal micronutrients play key roles in photosynthesis by oceanic phytoplankton. Though they are required in much smaller amounts than the major nutrients (P, N, Si), their bioavailable forms are also present in the seawater solution at much lower levels. Relationships between the dissolved chemistry of the nutrient-type trace metals, their stable isotope variations, as well those of the major nutrients, have highlighted the importance of biological and physical processes in the Southern Ocean in controlling their oceanic biogeochemistry. However, the first-order Southern Ocean processes are overprinted by vertical cycling in other parts of the ocean, particularly upwelling regions remote from the Southern Ocean, with the North Pacific standing out in particular. Here we present new zinc (Zn) concentration and isotope, as well as major nutrient data for the NE Pacific, and couple these new data with a compilation of published data from across the region, with the objective of better understanding the impact of this important region on oceanic biogeochemical cycles. The new Zn isotope data for two stations along Line P (P04 and P26) show a large range in δ66Zn in the upper ocean (−0.4‰ up to >1‰), associated with a very small isotope fractionation but extreme depletion of the dissolved pool during photic zone biological uptake, and the regeneration of this cellular Zn at very shallow depths (50 m). Beneath this, the two profiles approach the δ66Zn value of +0.5‰, seen throughout the deep ocean, by about 500 m. The minimum δ66Zn resulting from regeneration is associated with very high Zn concentrations, particularly at the marginal P04 station where diatoms dominate the phytoplankton ecology. Combining the new data with published Zn and major nutrient concentrations from across the North Pacific emphasises the role of vertical biological cycling in controlling regional biogeochemistry in the North Pacific, resulting in the partial overprinting of biogeochemical signatures transported out of the Southern Ocean by the ocean circulation. Zinc isotope data document the uptake of this metal into diatoms and the co-regeneration of Zn with phosphate in the upper water column. Silica in contrast is regenerated at greater depth, resulting in a decoupling of the Zn–Si correlation that is set in the Southern Ocean and that dominates the Atlantic. Previous work has suggested that the decoupling of Zn and Si in the subarctic North Pacific results from removal of Zn (and other metals) to water column particulate sulphide. In our dataset, and in the compilation of data documenting relationships between Zn and the major nutrients across the North Pacific, this decoupling is clearly due to the different lengthscales of regeneration for organic matter (Zn and P) and diatom opal (Si).</p
Uncertainty contributions to the measurement of dissolved Co, Fe, Pb and v in seawater using flow injection with solid phase preconcentration and detection by collision/reaction cell - Quadrupole ICP-MS
No full textA flow injection manifold incorporating a solid phase chelating resin (Toyopearl AF-Chelate-650) is reported for the preconcentration of dissolved metals from seawater, with a focus on investigating the effect of the loading pH, wash solution composition and wash time. Cobalt, iron, lead and vanadium have been used as target analytes with contrasting oceanographic behaviour. Quadrupole ICP-MS has been used for detection to make the approach accessible to most laboratories and a collision/reaction cell has been incorporated to minimise polyatomic interferences. Results for the seawater CRM NASS-6 and two GEOTRACES reference materials were in good agreement with the certified/consensus values, demonstrating the suitability of the approach for the determination of trace metals in seawater. The experimental design used allowed a thorough investigation of the uncertainty contribution from each method parameter to the overall expanded uncertainty of the measurement. The results showed that the parameters making the largest contributions were the precision of the peak area measurement and the uncertainty associated with the slope of the calibration curve. Therefore, these are the critical parameters that should be targeted in order to reduce the overall measurement uncertainty. For iron, the wash blank also gave a measureable contribution.</p
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