www.sciencemag.org/cgi/content/full/339/6126/1419/DC1

Supplementary Materials for

Two Modes of Change in Southern Ocean Productivity

Over the Past Million Years

S. L. Jaccard,* C. T. Hayes, A. Martínez-García,

D. A. Hodell, R. F. Anderson, D. M. Sigman, G. H. Haug

*Corresponding author. E-mail: samuel.jaccard@erdw.ethz.ch

Published 22 March 2013, Science 339, 1419 (2013)

DOI: 10.1126/science.1227545

This PDF file includes:

Materials and Methods

Figs. S1 to S3

References

Supporting Online Material for

“Two modes of change in Southern Ocean ocean productivity over the past million years”

Jaccard, S.L., Hayes, C.T., Martinez-Garcia, A., Hodell, D.A., Anderson, R.F., Sigman, D.M., Haug, G.H.

1. Material and Methods

ODP Site 1094 is located in the Atlantic sector of the Southern Ocean (53.2°S S, 05.1°E;

water depth 2850 m), south of the present-day position of the Polar Frontal Zone and about 2°

north of the average limit of winter sea-ice (Fig. 1). The core contains undisturbed diatomaceous

ooze sequences with discontinuous carbonate-bearing intervals and occasional ice-rafted debris

(IRD) layers. The stratigraphy is based on planktonic foraminifera δ18O (S1, S2) correlation to the

EDC ice core age scale (S3) assuming an in-phase relationship (Fig. S1). Sedimentation rates are

high, typically ranging between < 10 - 50 cm*kyr-1, for glacial and peak interglacial intervals,

respectively.

Relative sedimentary elemental concentrations (Ca, Fe, Ba) were measured with an

Aavatech profiling X-ray Fluorescence (XRF) core scanner at Bremen University at a 1-2 cm (i.e.

submillennial) resolution. Absolute elemental concentrations of major elements (Fe, Ca) were

measured by ICP-OES (Varian Vista Pro) while minor elements (Ba) were measured by ICP-MS

(Perkin-Elmer ELAN 9000) by ALS Chemex Ltd, North Vancouver, Canada. Accuracy was better

than 5% and 2%, respectively, for replicate measurements. The biogenic fraction of Ba (bioBa)

was determined by normalization by Fe; bioBa = Batot – (Fe * (Ba/Fe)lithogenic), with (Ba/Fe)lithogenic

= 0.0157 (S4). Comparison between discrete ICP-MS and relative Ba/Fe and Ca/Fe

measurements shows a significant statistical correlation (Fig. S2A & B). Similarly, discrete

coulometric CaCO3 quantifications show a high degree of fidelity when compared to core-

scanning XRF Ca/Fe determinations (Fig. S2C). For the analysis of phytoplankton pigment

transformation products (chlorins) sediment samples were freeze-dried and solvent extracted

using an Accelerated Solvent Extractor (ASE). The absorbance of the organic extracts at the

characteristic wavelength of the chlorins was measured with a Photodiode Array Detector (PDA)

coupled to an HPLC system following the methods described in detail by (S5). 230Th-normalized

fluxes (S6) were evaluated as described in Chase et al. (2003). Concentrations of U and Th

isotopes were determined by isotope dilution ICP mass spectrometry (S7). The authigenic U

content of each sample was evaluated using the measured 232Th and 238U concentrations.

Measured 230Th concentrations were corrected for the detrital contribution using 232Th and for

ingrowth produced by authigenic U, and then decay corrected to the time of deposition to derive

230Th -normalized fluxes. Concentrations of biogenic opal were measured by alkaline extraction

and molybdate-blue spectrophotometry (S8). All variables were determined on aliquots of the

same homogenized sample.

2. Figures

Fig. S1 Final solution of the age model reappraisal resulting from fine-tuning the ODP 1094 planktonic δ18O composite record (purple) (S1, S2) to EDC δD (grey) (S3). The correlation factor exceeds 0.90. The fine bars represent the tie-points defined to tune both records.

-460

-440

-420

-400

-380

-360

EDC

!D

(‰

)

2.5

3.0

3.5

4.0

4.5

5.0

2.0

OD

P 1094 - !18O

plank (‰)

0 100 200 300 400 500 600 700 800 900 1000

Age (kyr)

Fig. S2 Comparison between XRF-scanning elemental- and log ratios (S9) and discrete ICP-MS and CaCO3 measurements.

R2 = 0.94, n = 87

-1.0 0 1.0 2.0 3.0 4.0ln (Ca/Fe) - ICP-MS

-3.0

-2.0

-1.0

0

1.0

2.0

3.0

ln (C

a/Fe

) - X

RF

R2 = 0.86, n = 87

0 10 20 300

2.0

4.0

6.0

8.0

10.0

12.0

Ca/Fe - ICP-Ms

Ca/F

e - X

RF

-4.0

-3.0

-2.0

-1.0

0

ln (Ba/Fe) - ICP-MS

ln (B

a/Fe

) - X

RF

R2 = 0.89, n = 87

0 0.2 0.4 0.60

0.2

0.4

0.6

0.8

1.0

Ba/Fe - ICP-Ms

R2 = 0.75, n = 87

Ba/F

e - X

RF

-3.0 -2.0 -1.0 0-4.0

R2 = 0.76, n = 84

A

B

0

2.0

4.0

6.0

8.0

10.0

12.0

Ca/F

e - X

RF

0 5 10 15 20CaCO3 (wt%)

C

Fig. S3 Compilation of available bioBa flux and MAR record from the Atlantic sector of the Southern Ocean. Core locations are shown on sea-surface temperature field, dissolved nitrate and silic acid climatologies, respectively. Each record is on its own, independent age model. (A) ODP 1094/TN57-13PC (53.2°S S, 05.1°E; water depth 2850 m; this study); (B) PS1768 (53°36.4’S, 4°28’E, 3270m) (S10); (C) PS1722 (55°27.5’S, 1°09.8’E, 4135m) (S10); (D) PS1575 (62°50.097’S, 43°20.013’W, 3461m) (S11); (E) PS1821 (67°03.092’S, 37°28083’E, 4027m) (S11); (F) PS1648 (69°44.040’S, 06°31.048’W, 2529m) (S11). All records show consistently high export during early interglacials and low values during ice ages.

PS1821

0 50 100 150 200 250 300 3500

2

4

6

8

10

12

bioB

a M

AR (m

g*cm

-2*k

yr--1

)

0

5

10

15

20 bioBa MAR (m

g*cm-2*kyr --1)

cm-2*kyr --1)

Age (kyr)

0 50 100 150

0

2

4

6

8

10

12

ODP 1094/TN57-13PC

cm-2

*kyr

--1)

PS1648

PS1768

PS1772

0

1

2

3

4

5

6

7

PS1575

0

2

4

6

8

10

12

0

2

4

6

8

Age (kyr)

80!S70!S60!S50!S40!S

30!S

90!W

60!W

30!W0!

30!E

w

0

5

10

15

20

25

30

35

ODP 1094

PS1768

PS1772

PS1575

PS1821

PS1648

80!S70!S60!S50!S40!S

30!S

60!W

30!W0!

30!E

60!E

Ocean

Data

Vie

w

80!S70!S60!S50!S40!S

30!S

90!W

60!W

30!W0!

30!E

60!E

w

0

5

10

15

20

25

ODP 1094

PS1768

PS1772

PS1575

PS1821

PS1648

80!S70!S60!S50!S40!S

30!S

90!W

60!W

30!W0!

30!E

60!E

Ocean

Data

Vie

w

80!S70!S60!S50!S40!S

30!S90!W

60!W

30!W0!

30!E

60!E

Ocean

Data

Vie

w

0

20

40

60

80

100

ODP 1094

PS1768

PS1772

PS1575

PS1821

PS1648

80!S70!S60!S50!S40!S

30!S90!W

60!W

30!W0!

30!E

60!E

Ocean

Data

Vie

w

SST (ºC) WO

A09

Nitrate (µ

mol l -1) W

OA

09Silicate (µ

mol l -1) W

OA

09

A

B

C

D

E

F

3. References

S1. D. A. Hodell et al., in Proceedings of the Ocean Driling Program, Scientific

Results, R. Gersonde, D. A. Hodell, P. Blum, Eds. (Ocean Drilling Program, College Station, TX, 2003), vol. 177, pp. 1-26.

S2. H. F. Kleiven, E. Jansen, in Proceedings of the Ocean Drilling Program, Scientific Results, R. Gersonde, D. A. Hodell, P. Blum, Eds. (Ocean Drilling Program, College station, TX, 2003), vol. 177, pp. 1-20.

S3. J. Jouzel et al., Orbital and Millenial Antarctic Climate Variability over the Past 800,000 Years. Science 317, 793 (2007).

S4. S. R. Taylor, S. M. McLennan, The geochemical evolution of the continental crust. Reviews of Geophysics 33, 241 (1995).

S5. S. Fietz et al., Crenarchea and phytoplankton coupling in sedimentary archives: Common trigger or metabolic dependence. Limnology and Oceanography 56, 1907 (2011).

S6. R. François, M. Frank, M. Rutgers van der Loeff, M. P. Bacon, 230Th normalization: An essential tool for interpreting sedimentary fluxes during the late Quaternary. Paleoceanography 19, PA1018 (2004).

S7. M. Q. Fleisher, R. F. Anderson, Assessing the collection efficiency of Ross Sea sediment traps using 230Th and 231Pa. Deep-Sea Research II 50, 693 (2003).

S8. R. A. Mortlock, P. N. Froelich, A simple method for the rapid determination of biogenic opal in pelagic marine sediments. Deep-Sea Research I 36, 1415 (1989).

S9. G. J. Weltje, R. Tjallingii, Calibration of XRF core scanners for quantitative geochemical logging of sediment cores: Theory and application. Earth and Planetary Science Letters 274, 423 (2008).

S10. M. Frank et al., Similar glacial and interglacial export bioproductivity in the Atlantic sector of the Southern Ocean: Multiproxy evidence and implications for glacial atmospheric CO2. Paleoceanography 15, 642 (2000).

S11. W. J. Bonn, F. X. Gingele, H. Grobe, A. Mackensen, D. K. Fütterer, Paleoproductivity at the Antarctic continental margin: opal and barium records for the last 400 ka. Paleogeography, Paleclimatology, Paleoecology 139, 195 (1998).