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Science Highlights

Low iron sulfide precipitation rate in hydrothermal fluids during the early stage of mixing

Waeles and co-authors (2017, see reference below) report for the first time on the dissolved-particulate partition of iron (Fe) after in situ filtration at the early stage of mixing of hydrothermal fluids with seawater. This study was performed at three hydrothermal fields on the Mid-Atlantic Ridge (Lucky Strike, TAG and Snakepit). For the different vents examined, Fe predominantly occurred (>90%) in the dissolved fraction and dissolved Fe showed a strictly conservative behavior, arguing for low iron-bearing sulfide precipitation in basalt-hosted systems with low Fe:H2S ratios. The small part of Fe being precipitated as sulfides in the mixing gradient (<10%) is restricted to the inclusion of Fe in minerals of high copper (Cu) and zinc (Zn) content because the kinetic of pyrite formation is slow compared to the time scale of mixing processes. Their works also show that secondary venting, i.e. lower temperature clear smokers and diffusive venting, is a source of Fe-depleted hydrothermal fluids and provide new constrains on Fe fluxes from hydrothermal venting one of the main present issue of the GEOTRACES programme.

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Figure:
 Dissolved Fe (dFe), particulate Fe (pFe) and other chemical species concentrations measured at Aisics, a black smoker vent on the Lucky Strike vent field. Concentrations are given as a function of temperature and dissolved Mn (dMn) which is used as the conservative tracer. a) Dissolved Fe occurs essentially as Fe(II) species and coexists with sulfide until the coldest part of the mixing gradient due to the kinetically limited formation of pyrite particles. b) As opposed to Fe, Zn and Cu precipitate quantitatively before venting and/or during the very early stage of mixing (T > 150°C); Zn and Cu were mainly found as particulate rather than as dissolved species over the studied gradients. c) The data also showed that secondary venting, i.e. lower temperature auxiliary smokers and diffusive venting, is a source of Fe-depleted fluids. Click here to view the figure larger.

Reference:

Waeles, M., L. Cotte, B. Pernet‐Coudrier, V. Chavagnac, C. Cathalot, T. Leleu, A. Laës‐Huon, A. Perhirin, R. Riso, and P. Sarradin (2017), On the early fate of hydrothermal iron at deep‐sea vents: a reassessment after in‐situ filtration, Geophysical Research Letters. DOI: 10.1002/2017GL073315.

 

Complex cobalt story in the Mediterranean Sea

Dulaquais and co-authors (2017, see reference below) propose the first comprehensive study of cobalt behaviour in the Mediterranean Sea, work conducted in the framework of MedBlack GEOTRACES cruise (GA04N). They measured the following cobalt (Co) fractions: soluble (sCo<0.02 μm), dissolved (DCo<0.2 μm), colloidal (cCo, as DCo minus sCo), and particulate (pCo>0.2 μm).

While soluble Co is the predominant form (90%) of the dissolved Co in the Mediterranean Sea, colloidal Co and particulate Co show a close distribution, yielding the authors to suspect a biogeochemical link between these two fractions.

More striking is the scavenged-like profile observed everywhere, with up to 350 nM dissolved Co concentrations in the surface waters dropping to 45 nM at depth. Such behaviour results from several mechanisms. High-surface Co inputs at Gibraltar Strait are horizontally transported by the Mediterranean circulation, surface dissolved Co is stabilized in a soluble form and biogenic particulate Co is very rapidly regenerated: all these processes concur to the accumulation of dissolved Co in the surface layers. Conversely, low particulate Co export, low remineralization of biogenic particulate Co at depth, and removal of dissolved Co by scavenging prevented its accumulation in the intermediate and deep sea.

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Figure: Distribution and partitioning of dissolved cobalt (DCo) in the Mediterranean Sea. We measured DCo along the GA04N section (a) and observed a scavenged like profile in all the different sub-basins of the Mediterranean Sea (b). In the Med, DCo was almost entirely composed of soluble cobalt (sCo) and colloids represented only 10% of the DCo pool (c). Resulting from high recycling rate and its stabilization under a soluble form, surface DCo concentrations increased eastward with ageing of surface waters (d). Differently accumulation of DCo by remineralization in the intermediate water was not discernable (d) and surprisingly the zonal distribution of DCo in the deep sea showed homogenous concentrations (d). We related these features to scavenging rates depth dependents and of different magnitude in the two Mediterranean basins as well as to the fast Mediterranean circulation that homogenize concentrations in the deep sea. Click here to view the figure larger.

Reference:

Dulaquais, G., Planquette, H., L’Helguen, S., Rijkenberg, M. J. A., & Boye, M. (2017). The biogeochemistry of cobalt in the Mediterranean Sea. Global Biogeochemical Cycles, 31(2), 377–399. DOI: 10.1002/2016GB005478

 

 

GEOTRACES intercalibration of the stable silicon isotope composition of dissolved silicic acid in seawater

Dissolved silicon (Si) is a major oceanic nutrient and variations of its stable isotope values are reflecting the intensity of surface primary production. As for other isotopes, agreement between the different laboratories is crucial. Here, the first intercalibration study of the stable silicon (Si) isotopes in seawater (δ30Si(OH)4) is presented as a contribution to the international GEOTRACES programme. 

Eleven laboratories from seven countries participated in the study. Si isotope measurements were performed on three different mass spectrometer types Neptune MC-ICP-MS, Nu Plasma MC-ICP-MS and a MAT 252 IRMS.

Two seawater samples from the North Pacific subtropical gyre (Station ALOHA) collected at 300 m (9 μmol Si L-1; ALOHA300) and at 1000 m (113 μmol Si L -1; ALOHA1000) water depth were analyzed.

Agreement among laboratories is considered very good with mean values for δ30Si(OH)4:

  • ALOHA300 = +1.68 ± 0.35 (2 s.d.; Median: +1.66 ± 0.13)
  • ALOHA1000 = +1.24 ± 0.20 (2 s.d.; Median: +1.25 ± 0.06)

For future studies analyzing δ30Si(OH)4 in seawater it is recommended to analyze ALOHA300 and ALOHA1000 and report these results to facilitate and evaluate comparability of data between laboratories.

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Figure: δ30Si(OH)4 results from all groups for ALOHA300 (red circles) and ALOHA1000 (blue circles). The vertical lines indicates the mean value of all measurements for ALOHA1000 (blue) and for ALOHA300 (red). The data points represent the individual δ30Si(OH)4 values for Si isotopes measurements. Short vertical solid lines are the means obtained by individual laboratories for the two samples. Uncertainty in the mean for all measurements (2 s.d.) is indicated by the horizontal bars at the top of the figure (Modified from Grasse et al. 2017, JAAS). Click here to view the figure larger.

Reference:

Grasse, P., Brzezinski, M. A., Cardinal, D., de Souza, G. F., Andersson, P., Closset, I., et al. (2017). GEOTRACES inter-calibration of the stable silicon isotope composition of dissolved silicic acid in seawater. Journal of Analytical Atomic Spectrometry, 32, 562–578. DOI: 10.1039/C6JA00302H

A new method for simultaneous analysis of nickel, copper and zinc isotopes in seawater

Takano and co-workers (2017, see reference below) have developed a new method to determine nickel (Ni), copper (Cu) and zinc (Zn) isotopes in seawater. This method is very simple and rapid only using single chelating extraction and single anion exchange. First, target metals are extracted from seawater by NOBIAS Chelate PA-1 resin. Then, target metals are purified by anion exchange. Finally, isotope ratios are measured by MC-ICPMS. The analyses of GEOTRACES reference samples showed this method is precise and accurate. Vertical profiles of δ60Ni, δ65Cu, and δ66Zn in the South Pacific Ocean were revealed using this method.

This method is expected to accelerate isotopic research and contribute to our understanding of biogeochemical cycling in the ocean.

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Figure: A schematic diagram of the procedure for isotopic analysis of dissolved Ni, Cu, and Zn in seawater (upper panel). Depth profiles of dissolved δ60Ni, δ65Cu, and δ66Zn at GR15 station (30.00°S, 170.00°W) in the subtropical South Pacific Ocean. The error bars represent 2 standard errors for the MC-ICPMS measurement (lower panel). Click here to view the figure larger.

Reference:

Takano, S., Tanimizu, M., Hirata, T., Shin, K.-C., Fukami, Y., Suzuki, K., & Sohrin, Y. (2017). A simple and rapid method for isotopic analysis of nickel, copper, and zinc in seawater using chelating extraction and anion exchange. Analytica Chimica Acta, 967, 1–11. DOI: 10.1016/j.aca.2017.03.010

 

Important external dissolved iron inputs, HNLC water formation and strong biological seasonality explained in the North Pacific Ocean

Subarctic Pacific is known as High Nutrient, Low Chlorophyll (HNLC) area, where phytoplankton growth is limited by dissolved iron (DFe) availability. The biological activity in the surface waters is also characterized by a marked seasonality. Nishioka and Obata (2017, see reference below) propose a detailed DFe zonal section across the North Pacific (~47°N), realized in the framework of Japan-GEOTRACES programme. Their data reveal important external Fe sources at mid-depth from the Sea of Okhotsk, and the continental margin followed by long range transport in the formation of Fe-rich intermediate water, although these enriched waters do not reach the Alaskan Gyre. This work also enlights why surface macronutrient consumption differ between the western and eastern gyre. Both HNLC water formation in the subarctic Pacific and high amplitude of seasonal variation in biogeochemical parameters in the western subarctic gyre are explained.

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Figure: Dissolved Fe-rich intermediate water is transported laterally and distributed across the western subarctic gyre, over 2000 km (upper panel). The spatial pattern of Fe to nutrient stoichiometry supplied from the intermediate water to the surface (lower panel). Line P data is cited by Martin et al. 1989 and Nishioka et al. 2001. (OKTZ: Oyasio-Kuroshio transition zone, WSG: western subarctic gyre, CNP: central North Pacific, AG: Alaskan Gyre, AS: Alaskan stream). Click here to view the figure larger.

References:

Nishioka, J. and H. Obata, 2017, Dissolved iron distribution in the western and central subarctic Pacific: HNLC water formation and biogeochemical processes, Limnology and Oceanography, doi: 10.1002/lno.10548

Nishioka, J., S. Takeda, C. S. Wong, and W. K. Johnson. 2001. Size-fractionated iron concentrations in the northeast Pacific Ocean: distribution of soluble and small colloidal iron. Mar. Chem. 74: 157-179. doi:10.1016/S0304-4203(01)00013-5

Martin, J. H., R. M. Gordon, S. Fitzwater, and W.W. Broenkow. 1989. VERTEX: Phytoplankton/iron studies in the Gulf of Alaska. Deep Sea Res. Part I Oceanogr. Res. Pap. 36(5): 649–680. doi:10.1016/0198-0149(89)90144-1

 

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