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1 SUPPLEMENTARY INFORMATION doi: /ngeo1114 Strong elemental fractionation of Zr-Hf and Nb-Ta across the Pacific Ocean M. Lutfi Firdaus, Tomoharu Minami, Kazuhiro Norisuye and Yoshiki Sohrin Institute for Chemical Research, Kyoto University, Uji, Kyoto , Japan 1. Analytical Methods Seawater samples were collected during two cruises of KH-04-5 (December 2004 March 2005; stations SX) and KH-05-2 (August September 2005; stations ST) of R/V Hakuho Maru (Supplementary Fig. S1). The details of sampling, pretreatment and analysis were published elsewhere 1. Clean technique was adopted throughout the procedure. A CTD Carousel equipped with 12 liter Niskin-X samplers was submerged using a titanium armed cable to collect seawater samples. Seawater was transferred from the sampler to low-density polyethylene bottles (Nalge Nunc) on deck using a silicon tube and filling bell to avoid contamination by airborne particles. Samples were immediately brought into a clean room laboratory (class 100) on the vessel, passed through a 0.2 m Nuclepore filter (Costar) using a closed filtration system, and acidified to ph 2.2 with HCl and HF. These samples were stored at ambient temperature until analysis. Zr, Hf, Nb and Ta were preconcentrated in 1 M HNO 3 with a concentration factor of 50, through solid-phase preconcentration using chelating resin immobilized-8-hydroxyquinoline and evaporation. The four elements were quantitatively recovered; the recovery of spiked metals was 100±4%. Concentrations of Zr, Hf, Nb and Ta in the final solution were determined by HR-ICP-MS (Element II, Thermo Fischer). Measured isotopes were 90 Zr, 91 Zr, 177 Hf, 178 Hf, 93 Nb and 181 Ta. Standard solutions were used for calibration. Detection limit was 0.084, 0.006, and pmol/kg for Zr, Hf, Nb and Ta, respectively. Procedure blank was 0.25, 0.008, and pmol/kg, respectively. The precision was about 5% for each element. The seawater samples for dissolved Mn and Fe were obtained from the same samplers, filtered as described above, and acidified to ph 2.2 with HCl. Mn and Fe were preconcentrated using a column of Nobias Chelate-PA1 resin (Hitachi High-Technologies) and determined by a calibration curve method using an ELAN DRC II ICP-mass spectrometer (Perkin Elmer) 2. Present address: Department of Chemistry, Bengkulu University, Jl. Raya Kandang Limun, Bengkulu 38371, Indonesia. ml.firdaus@gmail.com nature geoscience 1

2 2. Calculation of the Oceanic Residence Time The residence time ( ) of HFSEs in the ocean can be calculated from: C sw M sw F total C sw M sw F riverine F atmospheric F hydrothermal where C sw is the concentration of the element in seawater, M sw is the total mass of seawater ( kg), and F total, F riverine, F atmospheric and F hydrothermal are total, riverine, atmospheric and hydrothermal flux of the element, respectively 3. The results are given in Supplementary Table S2. C sw of HFSEs used here is the average concentration of 163 deep water samples (>1,000 m) on the Pacific section. F riverine can be calculated from: F riverine C water river F river f where C river is the concentration of the element in river water, water F river is the total river discharge ( kg/year), and f is the fraction of riverine element that is not removed from the water column within estuaries and is added to the deep ocean basins. C river is taken from Gaillardet et al 4 for Zr and Nb. C river of Hf and Ta is the concentration determined by ourselves in a river water reference material SLRS-3 (Ottawa River, Canada) 5. These concentrations are 15% and 23% of the proposed world average 4. The concentrations of Zr and Hf in the Hudson River reported recently 6 are comparable with the adopted C river. In the Hudson River estuary, there was ~50% removal of Zr and Hf. It is, however, assumed that f = 1, because we do not know enough details of estuarine removal for each element. F atmospheric consists of wet and dry deposition. The wet deposition flux is obtained by multiplying the concentration in rain water (C rain ) and the rain water flux ( water F rain = kg/year). Because of scarcity of data, the concentration in rain water collected in Japan 5 is used for C rain. Since there is high dust supply from the Asian Continent to Japan, it is possible that the used C rain is higher than the global average, resulting in overestimation of the flux. On the other hand, the dry deposition flux is not considered here, because there are not enough data. F hydrothermal is assumed to be negligible on the basis of our observation. The resulting of HFSEs is comparable with or slightly longer than the oceanic mixing time of 500 1,000 years, and shorter than of silicate 3. The that has been estimated from scavenging models is 800 5,600 years for Zr and 650 1,300 years for Hf 7. The that has been estimated from riverine input is 5,000 years for Zr and 1,500 years for Hf 8. On the data from the Hudson River estuary, of Hf is estimated between 1,500 and 7,500 years 6. Using a weighted average river concentration of 33 pmol/l and variable f, it was argued that of Hf is in a range of 435 1,500 years 9. On the other hand, it has been proposed that of Hf 2

is only a few hundred years, because Hf does not increase along the deep ocean conveyer 10. Thus, our estimates of for Zr and Hf seem to be acceptable. No other data of for Nb and Ta are available.

3 is only a few hundred years, because Hf does not increase along the deep ocean conveyer 10. Thus, our estimates of for Zr and Hf seem to be acceptable. No other data of for Nb and Ta are available. Supplementary Figure S1. Location of sampling stations. Locations of stations SA-12 and N, E, where the vertical profiles of REEs were observed 11,12, are also shown. The map was made using ODV ( 3

4 Supplementary Figure S2. Plot of silicate vs. HFSEs for all data on the Pacific section. Supplementary Figure S3. Vertical profiles of the mole ratio of dissolved metals. (a) Zr/Hf at SX20 (30 S, 170 W) and ST09 (30 N, 160 W), (b) La/Lu at SA-12 (27 S, 175 E) 12 and N, E 11. 4

5 Supplementary Figure S4. Sectional distribution of dissolved Nb/Ta mole ratio in the Pacific Ocean along 170 W and 160 W. Water masses indicated are Western South Pacific Central Water (WSPCW) and Eastern North Pacific Central Water (ENPCW). References used in Supplementary Information: 1 Firdaus, M. L. et al., Preconcentration of Zr, Hf, Nb, Ta and W in seawater using solidphase extraction on TSK-8-hydroxyquinoline resin and determination by inductively coupled plasma-mass spectrometry. Anal. Chim. Acta 583, (2007). 2 Sohrin, Y. et al., Multielemental Determination of GEOTRACES Key Trace Metals in Seawater by ICP-MS after Preconcentration Using an Ethylenediaminetriacetic Acid Chelating Resin. Anal. Chem. 80, (2008). 3 Sarmiento, J. L. & Gruber, N., Ocean Biogeochemical Dynamics. (Princeton University Press, Princeton, 2006). 4 Gaillardet, J., Viers, J. & Dupré, B., in Surface and Ground Water, Weathering, and Soils, edited by Henry Elderfield (Elsevier-Pergamon, Oxford, 2003), pp Firdaus, M. L. et al., Dissolved and labile particulate Zr, Hf, Nb, Ta, Mo and W in the western North Pacific Ocean. J. Oceanogr. 64, (2008). 6 Godfrey, L. V., Field, M. P. & Sherrell, R. M., Estuarine distributions of Zr, Hf, and Ag in the Hudson River and the implications for their continental and anthropogenic sources to seawater. Geochem. Geophys. Geosyst. 9, Q12007 (2008). 7 Orians, K. J. & Merrin, C. L., in Encyclopedia of Ocean Sciences, edited by John H. Steele, Steve A. Thorpe, and Karl K. Turekian (Academic Press, San Diego, 2001), Vol. 4, pp Godfrey, L. V., White, W. M. & Salters, V. J. M., Dissolved Zirconium and Hafnium Distributions across a Shelf Break in the Northeastern Atlantic Ocean. Geochim. Cosmochim. Acta 60, (1996). 9 Zimmermann, B. et al., The hafnium isotope composition of Pacific Ocean water. Geochim. Cosmochim. Acta 73, (2009). 10 Rickli, J., Frank, M. & Halliday, A. N., The hafnium-neodymium isotopic composition of Atlantic seawater. Earth Planet. Sci. Lett. 280, (2009). 11 Alibo, D. S. & Nozaki, Y., Rare earth elements in seawater: particle association, shalenormalization, and Ce oxidation. Geochim. Cosmochim. Acta 63, (1999). 12 Zhang, J. & Nozaki, Y., Rare earth elements and yttrium in seawater: ICP-MS determinations in the East Caroline, Coral Sea, and South Fiji basins of the western South Pacific Ocean. Geochim. Cosmochim. Acta 60, (1996). 5

6 Supplementary Table S1. Trace elements, nutrients and physical properties Cruise Station Longitude Latitude Depth (m) Temp (C) Salinity O2 (ml/l) Phosphate (umol/l) Silicate (umol/l) Chl a (ug/l) Zr (pmol/kg ) Hf (pmol/kg ) Nb (pmol/kg ) Ta (pmol/kg ) KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX

7 KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX

8 KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX

9 KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX N.D KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX

10 KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX N.D KH-04-5 SX N.D KH-04-5 SX N.D KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX

11 KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX No Data KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX

12 KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX ? KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX ? KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX

13 KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX

14 KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX

15 KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX ? KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX ? KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX ? KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX KH-04-5 SX ? KH-04-5 SX KH-04-5 SX ? KH-04-5 SX

16 KH-04-5 SX KH-04-5 SX KH-05-2 ST < KH-05-2 ST < KH-05-2 ST < KH-05-2 ST < KH-05-2 ST < KH-05-2 ST < KH-05-2 ST < KH-05-2 ST < KH-05-2 ST < KH-05-2 ST < KH-05-2 ST KH-05-2 ST ND KH-05-2 ST ND KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST

17 KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST

18 KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST KH-05-2 ST

Temperature, salinity, density, and the oceanic pressure field

Chapter 2 Temperature, salinity, density, and the oceanic pressure field The ratios of the many components which make up the salt in the ocean are remarkably constant, and salinity, the total salt content