CDOM Sources and Photobleaching Control Quantum Yields for Oceanic DMS Photolysis

Martí Galí; David J. Kieber; Cristina Romera-Castillo; Joanna D. Kinsey; Emmanuel Devred; Gonzalo L. Pérez; George R. Westby; Cèlia Marrasé; Marcel Babin; Maurice Levasseur; Carlos M. Duarte; Susana Agusti; Rafel Simó

doi:10.1021/acs.est.6b04278

CDOM Sources and Photobleaching Control Quantum Yields for Oceanic DMS Photolysis

Martí Galí, David J. Kieber, Cristina Romera-Castillo, Joanna D. Kinsey, Emmanuel Devred, Gonzalo L. Pérez, George R. Westby, Cèlia Marrasé, Marcel Babin, Maurice Levasseur, Carlos M. Duarte, Susana Agusti, Rafel Simó

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Abstract

Photolysis is a major removal pathway for the biogenic gas dimethylsulfide (DMS) in the surface ocean. Here we tested the hypothesis that apparent quantum yields (AQY) for DMS photolysis varied according to the quantity and quality of its photosensitizers, chiefly chromophoric dissolved organic matter (CDOM) and nitrate. AQY compiled from the literature and unpublished studies ranged across 3 orders of magnitude at the 330 nm reference wavelength. The smallest AQY(330) were observed in coastal waters receiving major riverine inputs of terrestrial CDOM (0.06-0.5 m3 (mol quanta)-1). In open-ocean waters, AQY(330) generally ranged between 1 and 10 m3 (mol quanta)-1. The largest AQY(330), up to 34 m3 (mol quanta)-1), were seen in the Southern Ocean potentially associated with upwelling. Despite the large AQY variability, daily photolysis rate constants at the sea surface spanned a smaller range (0.04-3.7 d-1), mainly because of the inverse relationship between CDOM absorption and AQY. Comparison of AQY(330) with CDOM spectral signatures suggests there is an interplay between CDOM origin (terrestrial versus marine) and photobleaching that controls variations in AQYs, with a secondary role for nitrate. Our results can be used for regional or large-scale assessment of DMS photolysis rates in future studies.

Original language	English (US)
Pages (from-to)	13361-13370
Number of pages	10
Journal	Environmental Science & Technology
Volume	50
Issue number	24
DOIs	https://doi.org/10.1021/acs.est.6b04278
State	Published - Dec 2 2016

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: We thank the NASA Ocean Biology Distributed Active Archive Center (OB.DAAC) for access to SeaWiFS datasets, Maxime Benoît-Gagné for assistance with radiative transfer computations, and three anonymous reviewers for their constructive comments that helped improve the manuscript. Funding was provided by the (former) Spanish Ministry of Science and Innovation through projects ATOS (POL2006-00550/CTM), SUMMER (CTM2008-03309/MAR) and Malaspina (CSD2008-00077) to RS, and through the National Science Foundation to DJK (ANT-0944686, OCE-0961831). MG acknowledges the receipt of a Beatriu de Pinós postdoctoral fellowship funded by the Generalitat de Catalunya. This is a contribution of the CERC in Remote Sensing of Canada’s New Arctic Frontier and Takuvik Joint International Laboratory.

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Galí, M., Kieber, D. J., Romera-Castillo, C., Kinsey, J. D., Devred, E., Pérez, G. L., Westby, G. R., Marrasé, C., Babin, M., Levasseur, M., Duarte, C. M., Agusti, S., & Simó, R. (2016). CDOM Sources and Photobleaching Control Quantum Yields for Oceanic DMS Photolysis. Environmental Science & Technology, 50(24), 13361-13370. https://doi.org/10.1021/acs.est.6b04278

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title = "CDOM Sources and Photobleaching Control Quantum Yields for Oceanic DMS Photolysis",

abstract = "Photolysis is a major removal pathway for the biogenic gas dimethylsulfide (DMS) in the surface ocean. Here we tested the hypothesis that apparent quantum yields (AQY) for DMS photolysis varied according to the quantity and quality of its photosensitizers, chiefly chromophoric dissolved organic matter (CDOM) and nitrate. AQY compiled from the literature and unpublished studies ranged across 3 orders of magnitude at the 330 nm reference wavelength. The smallest AQY(330) were observed in coastal waters receiving major riverine inputs of terrestrial CDOM (0.06-0.5 m3 (mol quanta)-1). In open-ocean waters, AQY(330) generally ranged between 1 and 10 m3 (mol quanta)-1. The largest AQY(330), up to 34 m3 (mol quanta)-1), were seen in the Southern Ocean potentially associated with upwelling. Despite the large AQY variability, daily photolysis rate constants at the sea surface spanned a smaller range (0.04-3.7 d-1), mainly because of the inverse relationship between CDOM absorption and AQY. Comparison of AQY(330) with CDOM spectral signatures suggests there is an interplay between CDOM origin (terrestrial versus marine) and photobleaching that controls variations in AQYs, with a secondary role for nitrate. Our results can be used for regional or large-scale assessment of DMS photolysis rates in future studies.",

author = "Mart{\'i} Gal{\'i} and Kieber, {David J.} and Cristina Romera-Castillo and Kinsey, {Joanna D.} and Emmanuel Devred and P{\'e}rez, {Gonzalo L.} and Westby, {George R.} and C{\`e}lia Marras{\'e} and Marcel Babin and Maurice Levasseur and Duarte, {Carlos M.} and Susana Agusti and Rafel Sim{\'o}",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: We thank the NASA Ocean Biology Distributed Active Archive Center (OB.DAAC) for access to SeaWiFS datasets, Maxime Beno{\^i}t-Gagn{\'e} for assistance with radiative transfer computations, and three anonymous reviewers for their constructive comments that helped improve the manuscript. Funding was provided by the (former) Spanish Ministry of Science and Innovation through projects ATOS (POL2006-00550/CTM), SUMMER (CTM2008-03309/MAR) and Malaspina (CSD2008-00077) to RS, and through the National Science Foundation to DJK (ANT-0944686, OCE-0961831). MG acknowledges the receipt of a Beatriu de Pin{\'o}s postdoctoral fellowship funded by the Generalitat de Catalunya. This is a contribution of the CERC in Remote Sensing of Canada{\textquoteright}s New Arctic Frontier and Takuvik Joint International Laboratory.",

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doi = "10.1021/acs.est.6b04278",

language = "English (US)",

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T1 - CDOM Sources and Photobleaching Control Quantum Yields for Oceanic DMS Photolysis

AU - Galí, Martí

AU - Kieber, David J.

AU - Romera-Castillo, Cristina

AU - Kinsey, Joanna D.

AU - Devred, Emmanuel

AU - Pérez, Gonzalo L.

AU - Westby, George R.

AU - Marrasé, Cèlia

AU - Babin, Marcel

AU - Levasseur, Maurice

AU - Duarte, Carlos M.

AU - Agusti, Susana

AU - Simó, Rafel

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: We thank the NASA Ocean Biology Distributed Active Archive Center (OB.DAAC) for access to SeaWiFS datasets, Maxime Benoît-Gagné for assistance with radiative transfer computations, and three anonymous reviewers for their constructive comments that helped improve the manuscript. Funding was provided by the (former) Spanish Ministry of Science and Innovation through projects ATOS (POL2006-00550/CTM), SUMMER (CTM2008-03309/MAR) and Malaspina (CSD2008-00077) to RS, and through the National Science Foundation to DJK (ANT-0944686, OCE-0961831). MG acknowledges the receipt of a Beatriu de Pinós postdoctoral fellowship funded by the Generalitat de Catalunya. This is a contribution of the CERC in Remote Sensing of Canada’s New Arctic Frontier and Takuvik Joint International Laboratory.

PY - 2016/12/2

Y1 - 2016/12/2

N2 - Photolysis is a major removal pathway for the biogenic gas dimethylsulfide (DMS) in the surface ocean. Here we tested the hypothesis that apparent quantum yields (AQY) for DMS photolysis varied according to the quantity and quality of its photosensitizers, chiefly chromophoric dissolved organic matter (CDOM) and nitrate. AQY compiled from the literature and unpublished studies ranged across 3 orders of magnitude at the 330 nm reference wavelength. The smallest AQY(330) were observed in coastal waters receiving major riverine inputs of terrestrial CDOM (0.06-0.5 m3 (mol quanta)-1). In open-ocean waters, AQY(330) generally ranged between 1 and 10 m3 (mol quanta)-1. The largest AQY(330), up to 34 m3 (mol quanta)-1), were seen in the Southern Ocean potentially associated with upwelling. Despite the large AQY variability, daily photolysis rate constants at the sea surface spanned a smaller range (0.04-3.7 d-1), mainly because of the inverse relationship between CDOM absorption and AQY. Comparison of AQY(330) with CDOM spectral signatures suggests there is an interplay between CDOM origin (terrestrial versus marine) and photobleaching that controls variations in AQYs, with a secondary role for nitrate. Our results can be used for regional or large-scale assessment of DMS photolysis rates in future studies.

AB - Photolysis is a major removal pathway for the biogenic gas dimethylsulfide (DMS) in the surface ocean. Here we tested the hypothesis that apparent quantum yields (AQY) for DMS photolysis varied according to the quantity and quality of its photosensitizers, chiefly chromophoric dissolved organic matter (CDOM) and nitrate. AQY compiled from the literature and unpublished studies ranged across 3 orders of magnitude at the 330 nm reference wavelength. The smallest AQY(330) were observed in coastal waters receiving major riverine inputs of terrestrial CDOM (0.06-0.5 m3 (mol quanta)-1). In open-ocean waters, AQY(330) generally ranged between 1 and 10 m3 (mol quanta)-1. The largest AQY(330), up to 34 m3 (mol quanta)-1), were seen in the Southern Ocean potentially associated with upwelling. Despite the large AQY variability, daily photolysis rate constants at the sea surface spanned a smaller range (0.04-3.7 d-1), mainly because of the inverse relationship between CDOM absorption and AQY. Comparison of AQY(330) with CDOM spectral signatures suggests there is an interplay between CDOM origin (terrestrial versus marine) and photobleaching that controls variations in AQYs, with a secondary role for nitrate. Our results can be used for regional or large-scale assessment of DMS photolysis rates in future studies.

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DO - 10.1021/acs.est.6b04278

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VL - 50

SP - 13361

EP - 13370

JO - Environmental Science & Technology

JF - Environmental Science & Technology

IS - 24

ER -

CDOM Sources and Photobleaching Control Quantum Yields for Oceanic DMS Photolysis

Abstract

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