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  • 1
    Publication Date: 2019-09-23
    Description: Halocarbons are produced naturally in the oceans by biological and chemical processes. They are emitted from surface seawater into the atmosphere, where they take part in numerous chemical processes such as ozone destruction and the oxidation of mercury and dimethyl sulfide. Here we present oceanic and atmospheric halocarbon data for the Peruvian upwelling zone obtained during the M91 cruise onboard the research vessel METEOR in December 2012. Surface waters during the cruise were characterized by moderate concentrations of bromoform (CHBr3) and dibromomethane (CH2Br2) correlating with diatom biomass derived from marker pigment concentrations, which suggests this phytoplankton group is a likely source. Concentrations measured for the iodinated compounds methyl iodide (CH3I) of up to 35.4 pmol L−1, chloroiodomethane (CH2ClI) of up to 58.1 pmol L−1 and diiodomethane (CH2I2) of up to 32.4 pmol L−1 in water samples were much higher than previously reported for the tropical Atlantic upwelling systems. Iodocarbons also correlated with the diatom biomass and even more significantly with dissolved organic matter (DOM) components measured in the surface water. Our results suggest a biological source of these compounds as a significant driving factor for the observed large iodocarbon concentrations. Elevated atmospheric mixing ratios of CH3I (up to 3.2 ppt), CH2ClI (up to 2.5 ppt) and CH2I2 (3.3 ppt) above the upwelling were correlated with seawater concentrations and high sea-to-air fluxes. During the first part of the cruise, the enhanced iodocarbon production in the Peruvian upwelling contributed significantly to tropospheric iodine levels, while this contribution was considerably smaller during the second part.
    Type: Article , PeerReviewed
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  • 2
    Publication Date: 2019-07-18
    Description: We use isoprene and related field measurements from three different ocean data sets together with remotely sensed satellite data to model global marine isoprene emissions. We show that using monthly mean satellite-derived chl a concentrations to parameterize isoprene with a constant chl a normalized isoprene production rate underpredicts the measured oceanic isoprene concentration by a mean factor of 19 ± 12. Improving the model by using phytoplankton functional type dependent production values and by decreasing the bacterial degradation rate of isoprene in the water column results in only a slight underestimation (factor 1.7 ± 1.2). We calculate global isoprene emissions of 0.21 Tg C for 2014 using this improved model, which is twice the value calculated using the original model. Nonetheless, the sea-to-air fluxes have to be at least 1 order of magnitude higher to account for measured atmospheric isoprene mixing ratios. These findings suggest that there is at least one missing oceanic source of isoprene and, possibly, other unknown factors in the ocean or atmosphere influencing the atmospheric values. The discrepancy between calculated fluxes and atmospheric observations must be reconciled in order to fully understand the importance of marine-derived isoprene as a precursor to remote marine boundary layer particle formation.
    Type: Article , PeerReviewed
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  • 3
    Publication Date: 2020-02-06
    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.
    Type: Article , PeerReviewed
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  • 4
    Publication Date: 2023-10-20
    Description: Parameterizations of surface ocean isoprene concentrations are numerous, despite the lack of source/sink process understanding. Here we present isoprene and related field measurements in the mixed layer from the Indian Ocean and the eastern Pacific Ocean to investigate the production and consumption rates in two contrasting regions, namely oligotrophic open ocean and the coastal upwelling region. Our data show that the ability of different phytoplankton functional types (PFTs) to produce isoprene seems to be mainly influenced by light, ocean temperature, and salinity. Our field measurements also demonstrate that nutrient availability seems to have a direct influence on the isoprene production. With the help of pigment data, we calculate in-field isoprene production rates for different PFTs under varying biogeochemical and physical conditions. Using these new calculated production rates, we demonstrate that an additional significant and variable loss, besides a known chemical loss and a loss due to air–sea gas exchange, is needed to explain the measured isoprene concentration. We hypothesize that this loss, with a lifetime for isoprene between 10 and 100 days depending on the ocean region, is potentially due to degradation or consumption by bacteria.
    Type: Article , PeerReviewed
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  • 5
    Publication Date: 2022-04-06
    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.
    Type: Article , PeerReviewed , info:eu-repo/semantics/article
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  • 6
    Publication Date: 2022-04-06
    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.
    Type: Article , PeerReviewed
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  • 7
    Publication Date: 2024-02-07
    Description: Our understanding of the biogeochemical cycling of the climate-relevant trace gas dimethyl sulfide (DMS) in the Peruvian upwelling system is still limited. Here we present oceanic and atmospheric DMS measurements which were made during two shipborne cruises in December 2012 (M91) and October 2015 (SO243) in the Peruvian upwelling region. Dimethylsulfoniopropionate (DMSP) and dimethyl sulfoxide (DMSO) were also measured during M91. DMS concentrations were 1.9 ± 0.9 and 2.5 ± 1.9 nmol L−1 in surface waters in October 2015 and December 2012, respectively. Nutrient availability appeared to be the main driver of the observed variability in the surface DMS distributions in the coastal areas. DMS, DMSP, and DMSO showed maxima in the surface layer, and no elevated concentrations associated with the oxygen minimum zone off Peru were measured. The possible role of DMS, DMSP, and DMSO as radical scavengers (stimulated by nitrogen limitation) is supported by their negative correlations with N:P (sum of nitrate and nitrite : dissolved phosphate) ratios. Large variations in atmospheric DMS mole fractions were measured during M91 (144.6 ± 95.0 ppt) and SO243 (91.4 ± 55.8 ppt); however, the atmospheric mole fractions were generally low, and the sea-to-air flux was primarily driven by seawater DMS. The Peruvian upwelling region was identified as a source of atmospheric DMS in December 2012 and October 2015. However, in comparison to the previous measurements in the adjacent regions, the Peru upwelling was a moderate source of DMS emissions at either time (M91: 5.9 ± 5.3 µmol m−2 d−1; SO243: 3.8 ± 2.7 µmol m−2 d−1).
    Type: Article , PeerReviewed
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