science.sciencemag.org/cgi/content/full/science.aax5345/DC1

Supplementary Materials for

Mineralogical control on the fate of continentally derived organic

matter in the ocean

T. M. Blattmann*, Z. Liu*, Y. Zhang, Y. Zhao, N. Haghipour, D. B. Montluçon,

M. Plötze, T. I. Eglinton

*Corresponding author. Email: thomas.blattmann@erdw.ethz.ch (T.M.B.); lzhifei@tongji.edu.cn (Z.L.)

Published 3 October 2019 on Science First Release

DOI: 10.1126/science.aax5345

This PDF file includes:

Materials and Methods

Supplementary Text

Figs. S1 to S7

Captions for Data S1 and S2

References

Other Supplementary Material for this manuscript includes the following:

(available at science.sciencemag.org/cgi/content/full/science.aax5345/DC1)

Data S1 and S2 (.xlsx)

2

Materials and Methods Study area and samples

In the SCS, settling particles were intercepted using bottom-tethered sediment traps deployed on three moorings in a setup described elsewhere (16, 36, 37). The array of moorings is illustrated in Fig. S1. In brief, settling particles were collected between May 2014 to May 2016 in 18-day time intervals at water depths of 1960 m, 2045 m, 3795 m, and 2055 m for traps TJ-A-DOWN, TJ-C-MID, TJ-C-DOWN, and TJ-G-DOWN, respectively. Sedimenting particulate matter recovered from the trap cups were split, sieved to < 1mm, rinsed on 47 mm diameter 0.2 µm pore size polycarbonate filters, and oven dried. Methods and results for stable and radiocarbon isotopic analysis of bulk OC are reported in (16), with results for the 2015-2016 deployment reported in Data S2. In preparation for MSA and CEC measurement and mineral phase quantification, OM was removed using the sodium bicarbonate-buffered sodium persulfate wet chemical oxidation method (38, 39) followed by two overnight exchanges with calcium chloride and subsequent washing by centrifugation and oven drying at 65 °C.

Mineral surface properties MSA was measured on a Quantachrome NOVA 4000e instrument using nitrogen gas

isotherms following the BET theory (40) with 5-point adsorption isotherms in the p/p0 range 0.05-0.3 using a nitrogen cross-sectional area of 16.2 Å2. These MSA measurements were preceded by degassing using a Quantachrome FLOVAC degasser at 150 °C under vacuum overnight. MSA were normalized to degassed sediment masses. Measured MSA was within error of consensus values of standards 2007 (Alumina) and 2009 (82% aluminum oxide, 18% silicon oxide) supplied by Quantachrome. CEC was measured photometrically using copper triethylenetetramine following methods described elsewhere (41). The CEC method was modified to suit small sample sizes by scaling the volume of the copper exchange solution down to one-fifth of the original method description. CEC quantities were routinely monitored using in-house bentonite standard (Montigel; 73.0±2.2 meq/100g n=16).

Mineralogy Quantitative mineralogical content was assessed based on X-ray diffraction and Rietveld

refinement using BGMN® Autoquan (42, 43). Samples were prepared as described elsewhere (26,44). In brief, samples were sequentially milled in ethanol using a McCrone mill until all sample material was < 20 µm. Randomly oriented powdered samples were measured on a Bruker AXS D8 Theta-Theta X-ray diffractometer using Co-Kα radiation. Samples were spiked with corundum as internal standard to quantify x-ray amorphous content. Representative X-ray diffraction patterns measured for the different sediment traps are reported in Fig. S2-S6. Data S1 contains X-ray amorphous content, carbonate content (sum of aragonite, calcite, and dolomite), accessory mineral content (sum of magnetite and rutile), total silicate content (sum of clinoptilolite, hornblende, laumontite, plagioclase, quartz, and the phyllosilicates), and separately, the absolute abundances of the individual phyllosilicates (chlorite, kaolinite, mica, and smectite). In this work, mica includes the dioctahedral forms binning together muscovite and illite.

3

Supplementary Text Discrimination and quantification of OC type

OC of sinking particles in the study area are characterized by a coherent linear relationship between Fm and δ13C (see inset in Fig. 2a; R2=0.91), reflecting the binary mixing of marine biospheric and continentally-derived OC characterized by stable carbon isotopic end-member signatures of -22.0 and -25.4 ‰ (16) - assignments in agreement with other regional studies of suspended, sinking, and deposited marine sediments (20, 45, 46) - and radiocarbon isotopic end-member signatures of 1.04 and 0 Fm (i.e., radiocarbon dead), respectively (16). The absence of a modern component in continentally-derived OC, as seen in integrated river sediments (47, 48),reveals the overwhelming contribution of petrogenic OC. Sinking particle fluxes of continentally-derived OC (i.e., petrogenic OC from Taiwan) are consistent with the geospatial deployment of the sediment traps (i.e., as a function of distance from land and depth) and marine background sedimentation converges with predominant marine OC composition (16,46). Based on radiocarbon isotopic composition, the abundances of marine and petrogenic OC are quantified using a bilinear mixing model (16). The contents for marine biospheric and petrogenic OC lie between 0.2-5.9 wt.% and 0.05-0.5 wt.%, respectively.

4

Fig. S1. Study site showing the locations of the deployed moorings. Figure from (16).

5

Fig. S2. Representative X-ray diffraction pattern from trap TJ-C-MID (TJ-C-MID 10). Measured pattern shown as dotted blue line with modeled patterns superimposed. The difference between modeled and measured patterns is shown in the lower panel.

CalciteChlorite IIb-2modHornblende, Iron MagnesiumKaolinite C1, an, BISHMagnetiteMicrocline, maximumMuscovite_2M1Plagioclase AlbiteQuartzSmectitedi2wfix

2 Theta / °8070605040302010

I / c

ps

0

2 Theta / °8075706560555045403530252015105

I / c

ps

600

400

200

0

-200

-400

-600

6

Fig. S3. Representative X-ray diffraction pattern from trap TJ-C-DOWN (TJ-C-DOWN 3). Measured pattern shown as dotted blue line with modeled patterns superimposed. The difference between modeled and measured patterns is shown in the lower panel.

CalciteChlorite IIb-2modKaolsimpleKGa2Muscovite_2M1Plagioclase AlbiteQuartzSmectitedi2wfix

2 Theta / °8070605040302010

I / c

ps

0

2 Theta / °8075706560555045403530252015105

I / c

ps

800

600

400

200

0

-200

-400

-600

-800

7

Fig. S4. Representative X-ray diffraction pattern from trap TJ-G-DOWN (TJ-G-DOWN 17). Measured pattern shown as dotted blue line with modeled patterns superimposed. The difference between modeled and measured patterns is shown in the lower panel.

CalciteChlorite IIb-2modDolomiteKaolinite C1, ideal, BISHMuscovite_2M1Muscovite_2M1_smallPlagioclase AlbiteQuartzRutileSmectitedi2wfix

2 Theta / °8070605040302010

I / c

ps

5'000

0

2 Theta / °8075706560555045403530252015105

I / c

ps

2'000

1'500

1'000

500

0

-500

-1'000

-1'500

-2'000

8

Fig. S5. Representative X-ray diffraction pattern from trap TJ-A-DOWN (TJ-A-DOWN 15). Measured pattern shown as dotted blue line with modeled patterns superimposed. The difference between modeled and measured patterns is shown in the lower panel.

AragoniteCalciteChlorite IIb-2modKaolsimpleKGa2Muscovite_2M1Plagioclase AlbiteQuartzSmectitedi2wfix

2 Theta / °8070605040302010

I / c

ps

0

2 Theta / °8075706560555045403530252015105

I / c

ps

800

600

400

200

0

-200

-400

-600

-800

9

Fig. S6. Representative X-ray diffraction pattern spiked with corundum for quantifying X-ray amorphous content from trap TJ-A-DOWN. (TJ-A-DOWN 15). Measured pattern shown as dotted blue line with modeled patterns superimposed. The difference between modeled and measured patterns is shown in the lower panel.

AragoniteCalciteChlorite IIb-2modCorundumDolomiteKaolinite C1, ideal, BISHMuscovite_2M1Muscovite_2M1_smallPlagioclase AlbiteQuartzRutileSmectitedi2wfix

2 Theta / °8070605040302010

I / c

ps

0

2 Theta / °8075706560555045403530252015105

I / c

ps

800

600

400

200

0

-200

-400

-600

-800

10

Fig. S7. (A) Mineral surface area versus smectite content and (B) cation exchange capacity versus smectite content for SCS sediments. Measurement error bars (±1σ) are shown. Abs. wt. %, absolute weight %.

11

Data S1. (separate file) Quantitative mineral content and mineral surface properties.

Data S2. (separate file) Carbon isotopic compositions of sediment trap organic carbon May 2015-2016.

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