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Dissolved Iron in the Tropical North Atlantic Ocean

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Dissolved Iron in the Tropical North Atlantic Ocean Marine Chemistry 154 (2013) 87–99 Contents lists available at SciVerse ScienceDirect Marine Chemistry journal homepage: www.elsevier.com/locate/marchem Dissolved iron in the tropical North Atlantic Ocean Jessica N. Fitzsimmons a,⁎, Ruifeng Zhang b,1, Edward A. Boyle c,2 a MIT/WHOI Joint Program in Chemical Oceanography, MIT E25-615, 45 Carleton St, Cambridge, MA 02142, USA b State Key Laboratory for Estuarine & Coastal Research, East China Normal University, 3663 North Zhongshan Road, Shanghai 200062, China c Massachusetts Institute of Technology, MIT E25-619, 45 Carleton St, Cambridge, MA 02142, USA article info abstract Article history: Seawater from 27 stations was sampled in a zig-zag transect across the tropical North Atlantic from Barbados to the Received 26 December 2012 Cape Verde Islands, 7–20°N and 21–58°W. Under the Northwest African dust plume, surface dissolved Fe (dFe) was Received in revised form 6 May 2013 elevated, averaging 0.55 ± 0.29 nmol/kg (1SD), but showed a wide range from 0.12 to 1.31 nmol/kg with no clear Accepted 6 May 2013 longitudinal or latitudinal gradients. A subsurface dFe maximum in excess of 1 nmol/kg was evident coincident Available online 23 May 2013 with the oxygen minimum zone. Our goal was to determine whether this maximum occurred as a result of remineralization of high Fe:C organic material formed in the dust-laden (Fe-rich) surface ocean or as a result of lat- Keywords: Dissolved iron eral mixing of a coastal Fe signal from the African margin. We found that dFe is directly related to apparent oxygen Oxygen minimum zone utilization (AOU) with the same slope across all depths sampled, which implies a remineralization source through- Trace metals out the water column. A continental margin dFe supply was discounted because a modeled margin Fe source should Tropical North Atlantic cause curvature in the Fe–AOU relationship that was not observed. We also did not see a significant dissolved man- Biogeochemistry ganese (dMn) plume emanating from the margin. Regenerated Fe:C ratios calculated from the dFe:AOU relation- GEOTRACES ships ranged from 9.6 to 12.4 μmol Fe/mol C, which is much higher than ratios found in HNLC and dust-poor regions. Deep waters measured at one station in the eastern tropical North Atlantic reflected typical NADW concen- trations until 4000 m, where the dFe increased to 0.82 nmol/kg in four discrete samples down to 5000 m. We propose that this increase in dFe may reflect dFe inputs to deep waters as they traverse the Mid-Atlantic Ridge and enter the eastern basin. © 2013 Elsevier B.V. All rights reserved. 1. Introduction by circulation is minimized because this region lies in an under-ventilated “shadow zone” (Luyten et al., 1983). While these suboxic oxygen concen- Dissolved iron (dFe) is a marine micronutrient essential for pro- trations are not low enough to favor the stability of soluble Fe(II), this re- teins in the photosynthetic apparatus as well as pathways responsible gion is still an important OMZ in which to juxtapose Fe cycling with OMZs for the conversion between fixed nitrogen species (Morel et al., that do favor Fe(II) formation such as the subtropical Southeastern Pacific 2003). Models of nutrient limitation for photosynthesis and nitrogen OMZ (Blain et al., 2008), the Peru upwelling region (Bruland et al., 2005), fixation suggest that more than 40% of surface ocean primary produc- and the Arabian Sea OMZ (Moffettetal.,2007). The tropical North Atlantic tion is limited by Fe (Moore and Braucher, 2008; Moore et al., 2002). has also been shown to be the OMZ that has expanded and intensified the The accuracy of these models, however, is limited by how well marine most in the last fifty years (Stramma et al., 2008b), with a measured de- nutrient distributions are known, and measurements of micronutri- oxygenation rate of 0.5 μmol/kg/year (Stramma et al., 2009), providing ent dFe are still relatively scarce in many regions of the ocean. cause for a thorough investigation of Fe distributions in order to predict The tropical North Atlantic Ocean is an especially important area to how further intensification of the OMZ might change future Fe and carbon study the distribution and cycling of dFe for several reasons. First, an ex- cycling there. Finally, and arguably most importantly, the tropical North tensive oxygen minimum zone (OMZ) extends westward from the north- Atlantic receives some of the highest rates of dust deposition in the ernAfricancoastwithoxygenconcentrationsaslowas40–60 μmol/kg. world, as the trade winds blow dust from northwest Africa over the trop- This OMZ forms because coastal upwelling promotes oxygen consump- ical North Atlantic (Gao et al., 2001). Since ~3.5% of African dust is com- tion via respiration in the thermocline (Karstensen et al., 2008), while at posed of Fe (Zhu et al., 1997), dissolved Fe (dFe) concentrations in the the same time, physical replenishment of the biologically utilized oxygen tropical North Atlantic are likely to be higher than other oceanic regions (Jickells et al., 2005). Thus, the tropical North Atlantic is an ideal location in which to investigate how atmospherically derived Fe is translated into ⁎ Corresponding author. Tel.: +1 617 324 0283. oceanic dFe. E-mail addresses: jessfi[email protected] (J.N. Fitzsimmons), [email protected] Only three studies have reported dFe profiles in the tropical North (R. Zhang), [email protected] (E.A. Boyle). 1 Tel.: +86 21 62233890. Atlantic Ocean. Rijkenberg et al. (2012) recently investigated dFe 2 Tel.: +1 617 253 3388. concentrations near the Cape Verde Islands, and Bergquist and Boyle 0304-4203/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.marchem.2013.05.009 88 J.N. Fitzsimmons et al. / Marine Chemistry 154 (2013) 87–99 (2006a) reported in the western tropical North Atlantic a dFe maximum A rosette of 24 × 8 L Niskin bottles with a Seabird CTD were used to of 1.2 nmol/kg at 500 m, coincident with the oxygen minimum, at make the hydrographic measurements on the cruise. At each depth, 10°N, 45°W. Similarly, a north–south transect of dFe along 20–29°W three unfiltered seawater samples were collected for nutrient analysis was reported by Measures et al. (2008) who observed a dFe maximum in 30 mL vials after three rinses each. An unfiltered seawater sample for from 4 to 19°N in excess of 1.5 nM, again coincident with the oxygen min- dissolved oxygen analysis was also collected in a 125 mL Erlenmeyer imum. Although it is expected that dFe should be elevated in surface wa- flask through a tube that filled the flask from the bottom until it ters underlying the North African dust plume and that this signal would overflowed at least twice its volume, at which point the tube was re- be transferred to the OMZ via particle sinking and remineralization, moved and the fl ask was immediately stoppered to minimize bubbles; these high dFe concentrations imply Fe:C ratios three times what is con- alleffortsweremadetoreducebubblesinthetubeandinthesampledur- sidered typical of oceanic organic matter (Sunda, 1997). These dFe max- ing sample collection. ima in excess of 1 nmol/kg are surprising considering that minimum The uncontaminated seawater samples reported in this study were dissolved oxygen concentrations reach only 50–100 μmol/kg, making collected using the weathervane version of the Moored In situ Trace Ele- it unlikely that Fe(II) contributes significantly to the dFe maximum. ment Serial Samplers (MITESS) (Bell et al., 2002) following the techniques Two possible hypotheses for the enrichment of dFe in this region are: described in Fitzsimmons and Boyle (2012). Each MITESS module, made 1) remineralization in the oxygen minimum zone of high Fe:C entirely of ultrahigh molecular weight polyethylene, opens and closes organic matter formed in the Fe-rich (dust-laden) surface ocean, or 2) an acid-cleaned 1 L HDPE bottle while underwater in order to minimize lateral mixing of a dFe plume released from reducing sediments along contamination by the ship and eliminate sample handling effects on the the African margin. Several recent studies have suggested that ship's deck. Near-surface samples (~7 m) were collected using the continentally-derived Fe fluxes to the open ocean may be as significant “ATE” (Automated Trace Element) sampler, a single MITESS unit deployed as dust fluxes (Elrod et al., 2004), and particulate shelf Fe has been manually off the side of the ship, using a plastic-coated line. All deeper found hundreds of kilometers from shore (Lam et al., 2006). In this samples were collected using MITESS Vanes attached to a metal hydro- paper, we describe the spatial variability of dFe in the tropical North wire; the metal wire does not contaminate the seawater sample because Atlantic from 6 to 20°N and from 52 to 22°W to evaluate which of the plastic vane rotates freely around the hydrowire, orienting the sam- these two aforementioned hypotheses contributes most significantly pling bottle upstream of the metal wire. Samples were 0.5 atm vacuum- to the dFe maximum in this region. filtered through 0.4 μmNuclepore™ filters on a Teflon filter holder directly into acid-cleaned 30 mL HDPE sub-sampling bottles after rinsing once with ~10 mL of filtered sample. All filtrates were acidified on the 2. Methods ship to pH 2. MITESS Vane sample collection has been found to produce dFe concentrations indistinguishable from those collected by the U.S. 2.1. Seawater sampling GEOTRACES GO-FLO carousel system (Fitzsimmons and Boyle, 2012). In August 2008, trace metal clean seawater samples were collected 2.2.
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