Description: The climate active trace-gas carbonyl sulfide (OCS) is the most abundant sulfur gas in the atmosphere. A missing source in its atmospheric budget is currently suggested, resulting from an upward revision of the vegetation sink. Tropical oceanic emissions have been proposed to close the resulting gap in the atmospheric budget. We present a bottom-up approach including (i) new observations of OCS in surface waters of the tropical Atlantic, Pacific and Indian oceans and (ii) a further improved global box model to show that direct OCS emissions are unlikely to account for the missing source. The box model suggests an undersaturation of the surface water with respect to OCS integrated over the entire tropical ocean area and, further, global annual direct emissions of OCS well below that suggested by top-down estimates. In addition, we discuss the potential of indirect emission from CS2 and dimethylsulfide (DMS) to account for the gap in the atmospheric budget. This bottom-up estimate of oceanic emissions has implications for using OCS as a proxy for global terrestrial CO2 uptake, which is currently impeded by the inadequate quantification of atmospheric OCS sources and sinks.

Description: Halocarbons from oceanic sources contribute to halogens in the troposphere, and can be transported into the stratosphere where they take part in ozone depletion. This paper presents distribution and sources in the equatorial Atlantic from June and July 2011 of the four compounds bromoform (CHBr3), dibromomethane (CH2Br2), methyl iodide (CH3I) and diiodomethane (CH2I2). Enhanced biological production during the Atlantic Cold Tongue (ACT) season, indicated by phytoplankton pigment concentrations, led to elevated concentrations of CHBr3 of up to 44.7 and up to 9.2 pmol L−1 for CH2Br2 in surface water, which is comparable to other tropical upwelling systems. While both compounds correlated very well with each other in the surface water, CH2Br2 was often more elevated in greater depth than CHBr3, which showed maxima in the vicinity of the deep chlorophyll maximum. The deeper maximum of CH2Br2 indicates an additional source in comparison to CHBr3 or a slower degradation of CH2Br2. Concentrations of CH3I of up to 12.8 pmol L−1 in the surface water were measured. In contrary to expectations of a predominantly photochemical source in the tropical ocean, its distribution was mostly in agreement with biological parameters, indicating a biological source. CH2I2 was very low in the near surface water with maximum concentrations of only 3.7 pmol L−1. CH2I2 showed distinct maxima in deeper waters similar to CH2Br2. For the first time, diapycnal fluxes of the four halocarbons from the upper thermocline into and out of the mixed layer were determined. These fluxes were low in comparison to the halocarbon sea-to-air fluxes. This indicates that despite the observed maximum concentrations at depth, production in the surface mixed layer is the main oceanic source for all four compounds and one of the main driving factors of their emissions into the atmosphere in the ACT-region. The calculated production rates of the compounds in the mixed layer are 34 ± 65 pmol m−3 h−1 for CHBr3, 10 ± 12 pmol m−3 h−1 for CH2Br2, 21 ± 24 pmol m−3 h−1 for CH3I and 384 ± 318 pmol m−3 h−1 for CH2I2 determined from 13 depth profiles.

Description: © The Author(s), 2017. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Atmospheric Chemistry and Physics 17 (2017): 10837–10854, doi:10.5194/acp-17-10837-2017.

Description: A suite of oxygenated volatile organic compounds (OVOCs – acetaldehyde, acetone, propanal, butanal and butanone) were measured concurrently in the surface water and atmosphere of the South China Sea and Sulu Sea in November 2011. A strong correlation was observed between all OVOC concentrations in the surface seawater along the entire cruise track, except for acetaldehyde, suggesting similar sources and sinks in the surface ocean. Additionally, several phytoplankton groups, such as haptophytes or pelagophytes, were also correlated to all OVOCs, indicating that phytoplankton may be an important source of marine OVOCs in the South China and Sulu seas. Humic- and protein-like fluorescent dissolved organic matter (FDOM) components seemed to be additional precursors for butanone and acetaldehyde. The measurement-inferred OVOC fluxes generally showed an uptake of atmospheric OVOCs by the ocean for all gases, except for butanal. A few important exceptions were found along the Borneo coast, where OVOC fluxes from the ocean to the atmosphere were inferred. The atmospheric OVOC mixing ratios over the northern coast of Borneo were relatively high compared with literature values, suggesting that this coastal region is a local hotspot for atmospheric OVOCs. The calculated amount of OVOCs entrained into the ocean seemed to be an important source of OVOCs to the surface ocean. When the fluxes were out of the ocean, marine OVOCs were found to be enough to control the locally measured OVOC distribution in the atmosphere. Based on our model calculations, at least 0.4 ppb of marine-derived acetone and butanone can reach the upper troposphere, where they may have an important influence on hydrogen oxide radical formation over the western Pacific Ocean.

Description: This work was supported by the EU project SHIVA under grant agreement no. FP7-ENV- 2007-1-226224 and by the BMBF grants SHIVA-Sonne (FKZ: 03G0218A). Astrid Bracher and Wee Cheah were funded via the HGF Young Investigator Group PHYTOOPTICS (VH-NG-300) from the Helmholtz Association through the President. Astrid Bracher’s contribution was also partly funded by ESRIN/ESA within the SEOM (Scientific Exploration of operational missions) – Sentinel for Science Synergy (SY-4Sci Synergy) program via the project SynSenPFT. Additional funding for Cathleen Schlundt, Christa A. Marandino and Sinikka T. Lennartz came from the Helmholtz Young Investigator Group of Christa A. Marandino, TRASE-EC (VH-NG-819), from the Helmholtz Association through the President’s Initiative and Networking Fund and the GEOMAR Helmholtz-Zentrum für Ozeanforschung Kiel.

Description: Oceanic emissions of the climate-relevant trace gases carbonyl sulfide (OCS) and carbon disulfide (CS2) are a major source to their atmospheric budget. Their current and future emission estimates are still uncertain due to incomplete process understanding and therefore inexact quantification across different biogeochemical regimes. Here we present the first concurrent measurements of both gases together with related fractions of the dissolved organic matter (DOM) pool, i.e., solid-phase extractable dissolved organic sulfur (DOSSPE, n=24, 0.16±0.04 µmol L−1), chromophoric (CDOM, n=76, 0.152±0.03), and fluorescent dissolved organic matter (FDOM, n=35), from the Peruvian upwelling region (Guayaquil, Ecuador to Antofagasta, Chile, October 2015). OCS was measured continuously with an equilibrator connected to an off-axis integrated cavity output spectrometer at the surface (29.8±19.8 pmol L−1) and at four profiles ranging down to 136 m. CS2 was measured at the surface (n=143, 17.8±9.0 pmol L−1) and below, ranging down to 1000 m (24 profiles). These observations were used to estimate in situ production rates and identify their drivers. We find different limiting factors of marine photoproduction: while OCS production is limited by the humic-like DOM fraction that can act as a photosensitizer, high CS2 production coincides with high DOSSPE concentration. Quantifying OCS photoproduction using a specific humic-like FDOM component as proxy, together with an updated parameterization for dark production, improves agreement with observations in a 1-D biogeochemical model. Our results will help to better predict oceanic concentrations and emissions of both gases on regional and, potentially, global scales