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Trace element and isotope proxies in paleoceanography:

Starting a new synergic effort around marine

geochemical proxies

Tachikawa Kazuyo, Anderson Robert, Vidal Laurence, Jeandel Catherine

To cite this version:

Tachikawa Kazuyo, Anderson Robert, Vidal Laurence, Jeandel Catherine.

Trace element and

isotope proxies in paleoceanography: Starting a new synergic effort around marine geochemical

proxies.

Past Global Changes Magazine, Past Global Changes (PAGES) project, 2019, 27 (1),

�10.22498/pages.27.1.35�. �hal-03008314�

(2)

PAGES MAGAZINE ∙ VOLUME 27 ∙ NO 1 ∙ MAy 2019

CC-BY

41

WORKSHOP REPORT

Reconstruction of past ocean states relies on the use of “proxies” (indicators or tracers), since it is impossible to directly measure variables such as water temperature, biological production and ocean circulation. In order to clarify the ocean’s response to natural and anthropogenic forcings, it is essential to improve our knowledge of proxy behavior and the associated uncertainty. This task will be most efficiently achieved by the synergy between marine geochemists and paleoceanographers, as well as proxy and climate modelers. The first joint workshop of GEOTRACES-PAGES (geotracespages.sciencesconf.org) was such an occasion to identify open questions and scientific gaps of proxies used in paleoceanography. We focused mainly on trace elements and their isotopes (Fig. 1) that are targets of GEOTRACES program (geotraces.org). These proxies are preserved in biogenic phases and/or bulk sediments and can be used to compare with simulated distribution to quantify physical and biogeochemical processes (Fig. 1). Sixty-four researchers and students from 11 countries from four continents gathered for this objective. The workshop consisted of a series of keynote talks and discussions around working groups with the following subjects: biological productivity, oceanic circulation, particle flux and sedimentation rate, and physical and/or biogeochemical modeling.

The keynote talks pointed out some recent findings, including the importance of recycled iron for biological productivity on seasonal to ice-age timescales (Rafter et al. 2017), and complex biomineraliza-tion processes of silicifiers and their impact on the silicon isotopic ratio (Hendry et al. 2018). Multi-tracer analysis of the same water sample is one of the strongest strategies of the GEOTRACES program, and multi-proxy reconstruction provides the most reliable re-sults. However, different proxies sometimes tell us distinct stories. Since each proxy has its own advantage and potential bias, decou-pling them can provide additional informa-tion. One of the most interesting examples of this decoupling is deep water circulation in the Atlantic Ocean during the last glacial maximum (LGM, 23-18 kyr BP). Three of the most frequently used geochemical proxies in paleoceanography do not tell a single, simple story: benthic foraminiferal carbon isotopic ratios (13C/12C or δ13C) suggest

weaker and shallower glacial North Atlantic deep water circulation with a dominant contribution of the southern source water (Lynch-Stieglitz et al. 2007), whereas the neo-dymium isotopic composition (143Nd/144Nd

or εNd) recorded in authigenic oxides of

planktonic foraminiferal calcites indicates a significant proportion of northern compo-nent waters in the North Atlantic over the LGM (Howe et al. 2016). The particle-reactive radionuclide ratio 231Pa/230Th suggests

persistent southward transport of 231Pa

during the LGM (Bradtmiller et al. 2014). Reconciliation of these proxy reconstruc-tions will be achieved by improved spatial coverage of tracer data in the modern ocean and proxy-enabled model experiments (Menviel et al. 2017; Muglia et al. 2018) with well-constrained parameters (e.g. particle concentration and partition coefficients ac-cording to the chemical composition of the particle), which can be obtained by process studies of the modern ocean, for example, from GEOTRACES.

The workshop identified the necessity to re-inforce the study of the water-sediment inter-face and early diagenetic processes. Benthic fluxes from the water-sediment interface may affect proxy distribution in the water column, and early diagenesis could modify the signature acquired in the upper-water column. More systematic and coordinated sampling of surface sediments and pore wa-ters with samples collected in the overlying water column would help to scrutinize proxy behavior across this interface and promote core-top calibration.

The workshop was a great occasion to trig-ger coordinated actions that will be further developed in coming years. We identified products such as a compilation database of core-top samples suitable for proxy develop-ment and calibration, sensitivity tests and model-data comparisons, a synthesis paper on trace elements and isotope proxies used in paleoceanography and particle flux, intercalibration of methods used to analyze core-top sediments, and an outreach piece on paleo productivity.

AFFILIATIONS

1Aix Marseille Univ, CNRS, IRD, INRA, Coll France,

CEREGE, Aix-en-Provence, France

2Lamont-Doherty Earth Observatory, Columbia

University, Palisades, Ny, USA

3LEGOS (Université de Toulouse/CNRS/CNES/IRD/

UPS), Observatoire Midi-Pyrénées, Toulouse, France

CONTACT

Kazuyo Tachikawa: kazuyo@cerege.fr

REFERENCES

Bradtmiller LI et al. (2014) Nat Commun 5: 5817 Hendry KR et al. (2018) Front Mar Sci 5: 22

Howe JNW et al. (2016) Nat Commun 7: 11765 and related Supplementary Material

Lynch-Stieglitz J et al. (2007) Science 316: 66-69 Menviel L et al. (2017) Paleoceanography 32: 2-17 Muglia J et al. (2018) Earth Planet Sci Lett 496: 47-56 Rafter PA et al. (2017) Nat Commun 8: 1100

Trace element and isotope proxies in

paleoceanography: Starting a new synergic

effort around marine geochemical proxies

Kazuyo Tachikawa

1

, R. Anderson

2

, L. Vidal

1

and C. Jeandel

3

GEOTRACES-PAGES joint workshop, Aix-Marseille, France, 3-5 December 2018

doi.org/10.22498/pages.27.1.41

Figure 1: A schematic diagram presenting possible areas of interaction between the GEOTRACES and PAGES communities: targeted geochemical proxies, factors affecting their distribution, and paleoceanographic approaches associated with the proxies.

c c c Runoff Sediments Dust Ridge Uptake Regeneration Burial Circulation

Proxy behavior

Proxy reconstruction

Climate modeling

O. Cartapanis et al.: Pacific Oxygen Minimum Zone under interglacial conditions 409

Fig. 3. The XRF intensities for Ca, Ti, Br / Cl, and Si / Ti (spatial

resolution of 200 µm) of a 10 cm long sample of MD02-2508, repre-senting roughly 300 yr of sediment deposition, and the correspond-ing photography of the core with gray scale analyses. Contrast and lightness of the image were slightly enhanced, and gray scale mea-surements were performed using ImageJ software. The position of the sample within the record is indicated with a red tick at the top of Fig. 2. Vertical dashed lines show 1 cm intervals.

winds are enhanced (Fig. 1, Thomas et al., 2001). Despite the influence of local bottom topography and angular orienta-tion of the coastline, upwelling is stronger during early sum-mer at MD08 core (Zaytsev et al., 2003; Cartapanis et al., 2011). Upwelled waters originate from up to 300 m depth along the California coast (van Geen and Husby, 1996), at the mixing zone between SW and NPIW. Thus, NPIW nu-trient inventory related to tidal mixing at high northern lat-itude in the Pacific (Sarmiento et al., 2004), might influ-ence surface productivity. High local productivity is thus as-sociated with warm condition on seasonal timescales when the Intertropical Convergence Zone (ITCZ) is situated on its northern position.

4 Results

Highly resolved XRF Si / Ti (log-scale) is well correlated (R2 = 0.93) to opal content obtained by chemical leaching

of bulk sediments (Fig. 2). Br is contained in marine or-ganic matter, but also in pore water (Ziegler et al., 2008). Since pore water content in opal-rich sediment is strongly affected by opal concentration, we used Br / Cl ratio as indi-cator of marine organic matter to correct pore water contri-bution using Cl (Croudace et al., 2006). Log Br / Cl is well

Table 2. Minimal, maximal, and mean values for Al content

(µg g−1), Cd / Al, Mo / Al, and Ni / Al in MD08 core. Mean val-ues in Upper Continental Crust (McLennan, 2001) and mean en-richment factors ((Mean Element / Al)MD08/(Element / Al)UPC)are displayed at the bottom of the table.

Al (µg g−1) Cd / Al (g g−1) Mo / Al (g g−1) Ni / Al (g g−1) Min 3200 2.77 ⇥ 10−5 1.32 ⇥ 10−4 1.38 ⇥ 10−3 Max 51 813 4.21 ⇥ 10−3 2.00 ⇥ 10−2 8.49 ⇥ 10−3 Mean 32 343 3.97 ⇥ 10−4 1.30 ⇥ 10−3 3.41 ⇥ 10−3 UPC 80 400 1.22 ⇥ 10−6 1.87 ⇥ 10−5 5.47 ⇥ 10−4 Enrichment 326 70 6 Factor

correlated (R2 = 0.68) to TOC content (Fig. 2). The MD08

sediment column is divided in three different units (Fig. 2). The first unit (Unit I) that corresponds to the Holocene con-sists of laminated high TOC (⇡ 13 %), relatively low carbon-ates (⇡ 20 %) and terrigenous compounds (⇡ 45 %) sapro-pelic mud (Fig. 2). The second unit (Unit II) was deposited during MIS2, 3 and 4, and is composed of light homogenous calcareous clay (carbonates ⇡ 35 %, terrigenous ⇡ 60 %, and TOC ⇡ 7 %). Interbeds of dark laminated sapropelic mud similar to Unit I (Fig. 2) were deposited during interstadial events (Cartapanis et al., 2011). Opal content within Units I and II is low (0 to 10 %) but is higher within laminated inter-vals (up to 20 %, Fig. 2). The third unit (Unit III) corresponds to MIS5 and mainly consists of laminated sapropelic diatom ooze (Fig. 3) with some homogenous layers composed of calcareous clays, similar to Unit II non-laminated sediment (Fig. 2). The millimetric to centimetric laminations in the Unit III are composed of light colour biogenic remains, and dark coloured organic matter mixed with terrigenous sedi-ment (Fig. 3). Opal content rises up to 40 % in MIS5 lamina-tions and reaches over 80 % in particular laminalamina-tions (Fig. 2). Micro sedimentologic analyses suggest that high opal con-tent laminae in Unit III were deposited abruptly, and could correspond to algal blooms during upwelling events or in the frontal zone between water masses of different densities (Murdmaa et al., 2010).

Trace element (Cd, Mo, Ni) to Al ratios show extremely high values relative to the so-called UPC values (McLennan, 2001, Table 2): The mean Ni / Al ratio is six times higher than in UPC, seventy times higher for Mo / Al, and more than three hundreds times higher for Cd / Al (Table 2). Even the lowest element to Al ratios, which occur mainly in Unit II, are higher than the corresponding value in UPC. The results indicate that significant parts of these elements are not re-lated to the input of terrigenous minerals, but rather to in-situ biogenic and authigenic enrichments. The highest values for elemental ratios and enrichments in MD08 core occur within laminated intervals, and are even higher within sedimentary Unit III as compared to Unit I (Fig. 2).

www.clim-past.net/10/405/2014/ Clim. Past, 10, 405–418, 2014

diagenesis

Figure

Figure 1: A schematic diagram presenting possible areas of interaction between the GEOTRACES and PAGES  communities: targeted geochemical proxies, factors affecting their distribution, and paleoceanographic  approaches associated with the proxies.

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