Significance

Exchange of chemical species and matter at ocean boundaries influences the composition of seawater and is an important process affecting biogeochemical element cycling involving interactions between the atmosphere, hydrosphere, geosphere, and biosphere. However, systematic quantification on the processes and budgets remains scarce. Here, through field, laboratory analysis and modeling, we show that the adsorption–desorption exchange of lead (Pb) between the particulate and dissolved pools at ocean boundaries accounts for about 30 to 40% of Pb input into the ocean before the Anthropocene, which finally resolves the paradox of imbalanced natural sources and sinks of Pb in the ocean. With Pb as an example, our study adds a crucial piece of evidence to the importance of boundary exchange in marine element cycling.

Abstract

Material fluxes at the land–ocean interface impact seawater composition and global cycling of elements. However, most attention has been focused on the fluvial dissolved fluxes. For elements like lead (Pb), whose fluvial particulate flux into the ocean is two orders of magnitude higher than the dissolved counterpart, the role of particulates in elemental cycling is potentially important but currently less appreciated. Using both chemical analyses on samples collected from around equatorial Southeast Asia and model simulations, we show that particulate-dissolved exchange is an important mechanism controlling the concentration and isotopic composition of dissolved Pb in the ocean. Our model indicates that Pb contributed from particulate-dissolved exchange at ocean boundaries is larger than, or at least comparable to, other major Pb sources to the seawater before the Anthropocene, when the anthropogenic Pb was absent. Our work highlights the importance of boundary exchange in understanding marine element cycling and weathering-climate feedback.

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Data, Materials, and Software Availability

All data in this study is included as SI Appendix.

Acknowledgments

This research was funded by the Singapore National Research Foundation (NRF) through the Singapore-MIT Alliance for Research and Technology CENSAM to M.C., G.C., and E.A.B.; NRF Intra-CREATE Seed Collaboration grant NRF2021-ITS007-0003 to M.C.; NRF Marine Environmental Sensing Network to J.T.; Singapore Ministry of Education AcRF Tier1 grant RT 06/19 to M.C. and X.W.; and the Overseas Talent Recruitment Program of China to N.Z. X.W. acknowledges the support of MOE2019-T2-1-174 (S) and NRF2017NRF-NSFC001-047 grants for the geochemistry laboratory. This is Earth Observatory of Singapore (EOS) contribution number 496. We thank Patrick Martin, Jiawei Feng, Caroline Chia, and the crew of S/Y Indigo V for field assistance. We thank Lu Xu for scientific illustration. Permits: We thank the National Park Board Singapore for allowing this research (NP/RP16-156-2a). We are grateful for the permissions to sample in Malaysian water [Johor: P.T.N.J 3/8/6; Marine Park: JTLM 630-7 Jld. 4(17); Port Dickson: Prk. ML.S.04/32-2 Jld. 7(9)].

Author contributions

M.C., G.C., N.Z., and E.A.B. designed research; M.C., G.C., J.N.L., and K.V.A. performed research; M.C., G.C., X.W., J.T.I.T, S.C.P., F.M.L., and D.D. contributed new reagents/analytic tools; M.C. and N.Z. analyzed data; M.C., G.C., and X.W. provided resources for part of the project; J.N.L., K.V.A., S.C.P., A.D.Z., and D.D. provided sampling permits and conducted fieldwork; J.T.I.T. contributed sampling permits, provided resources for part of the project; F.M.L. provided resources for part of the fieldwork; E.A.B. provide supervision and resources for part of the project; and M.C., N.Z., and A.D.Z. wrote the paper.

Competing interests

The authors declare no competing interest.

Supporting Information

Appendix 01 (PDF)
Dataset S01 (XLSX)
Dataset S02 (XLSX)

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Information & Authors

Information

Published in

Go to Proceedings of the National Academy of Sciences
Go to Proceedings of the National Academy of Sciences
Proceedings of the National Academy of Sciences
Vol. 120 | No. 6
February 7, 2023
PubMed: 36716377

Classifications

Data, Materials, and Software Availability

All data in this study is included as SI Appendix.

Submission history

Received: August 10, 2022
Accepted: January 5, 2023
Published online: January 30, 2023
Published in issue: February 7, 2023

Keywords

  1. marine elemental cycling
  2. isotope
  3. Southeast Asia
  4. boundary exchange
  5. Pb

Acknowledgments

This research was funded by the Singapore National Research Foundation (NRF) through the Singapore-MIT Alliance for Research and Technology CENSAM to M.C., G.C., and E.A.B.; NRF Intra-CREATE Seed Collaboration grant NRF2021-ITS007-0003 to M.C.; NRF Marine Environmental Sensing Network to J.T.; Singapore Ministry of Education AcRF Tier1 grant RT 06/19 to M.C. and X.W.; and the Overseas Talent Recruitment Program of China to N.Z. X.W. acknowledges the support of MOE2019-T2-1-174 (S) and NRF2017NRF-NSFC001-047 grants for the geochemistry laboratory. This is Earth Observatory of Singapore (EOS) contribution number 496. We thank Patrick Martin, Jiawei Feng, Caroline Chia, and the crew of S/Y Indigo V for field assistance. We thank Lu Xu for scientific illustration. Permits: We thank the National Park Board Singapore for allowing this research (NP/RP16-156-2a). We are grateful for the permissions to sample in Malaysian water [Johor: P.T.N.J 3/8/6; Marine Park: JTLM 630-7 Jld. 4(17); Port Dickson: Prk. ML.S.04/32-2 Jld. 7(9)].
Author Contributions
M.C., G.C., N.Z., and E.A.B. designed research; M.C., G.C., J.N.L., and K.V.A. performed research; M.C., G.C., X.W., J.T.I.T, S.C.P., F.M.L., and D.D. contributed new reagents/analytic tools; M.C. and N.Z. analyzed data; M.C., G.C., and X.W. provided resources for part of the project; J.N.L., K.V.A., S.C.P., A.D.Z., and D.D. provided sampling permits and conducted fieldwork; J.T.I.T. contributed sampling permits, provided resources for part of the project; F.M.L. provided resources for part of the fieldwork; E.A.B. provide supervision and resources for part of the project; and M.C., N.Z., and A.D.Z. wrote the paper.
Competing Interests
The authors declare no competing interest.

Notes

This article is a PNAS Direct Submission.

Authors

Affiliations

Tropical Marine Science Institute, National University of Singapore 119227, Singapore
Gonzalo Carrasco
Earth Observatory of Singapore, Nanyang Technological University, Singapore 639798, Singapore
State Key Laboratory of Estuarine and Coastal Research and Institute of Eco-Chongming, East China Normal University, Shanghai 200241, China
Xianfeng Wang
Earth Observatory of Singapore, Nanyang Technological University, Singapore 639798, Singapore
Asian School of the Environment, Nanyang Technological University, Singapore 639798, Singapore
Faculty of Science and Marine Environment, Universiti Malaysia Terengganu, Kuala Nerus 210030, Malaysia
Jani T. I. Tanzil
Tropical Marine Science Institute, National University of Singapore 119227, Singapore
Centre of Environmental Sustainability and Water Security, Research Institute for Sustainable Environment, Universiti Teknologi Malaysia, 81310 Johor Bahru, Malaysia
Faculty of Science and Marine Environment, Universiti Malaysia Terengganu, Kuala Nerus 210030, Malaysia
Asian School of the Environment, Nanyang Technological University, Singapore 639798, Singapore
Singapore Centre for Environmental Life Sciences Engineering, Nanyang Technological University, Singapore 637551, Singapore
Faculty of Fisheries Technology and Aquatic Resources, Maejo University, Chiang Mai 50290, Thailand
Decha Duangnamon
Andaman Coastal Research Center for Development, Faculty of Fisheries, Kasetsart University, Ranong 85120, Thailand
Department of Earth, Atmospheric, and Planetary Sciences, Massachusetts Institute of Technology, Cambridge, MA 02139

Notes

1
To whom correspondence may be addressed. Email: [email protected] or [email protected].

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    Boundary exchange completes the marine Pb cycle jigsaw
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