The influence of transformed Reynolds number suppression on gas transfer parameterizations and global DMS and CO2 fluxes

Eddy covariance measurements show gas transfer velocity suppression at medium to high wind speed. A wind-wave interaction described by the transformed Reynolds number is used to characterize environmental conditions favoring this suppression. We take the transformed Reynolds number parameterization to review the two most cited wind speed gas transfer velocity parameterizations: Nightingale et al. (2000) and Wanninkhof (1992, 2014). We propose an algorithm to adjust k values for the effect of gas transfer suppression and validate it with two directly measured dimethyl sulfide (DMS) gas transfer velocity data sets that experienced gas transfer suppression. We also show that the data set used in the Nightingale 2000 parameterization experienced gas transfer suppression. A compensation of the suppression effect leads to an average increase of 22% in the k vs. u relationship. Performing the same correction for Wanninkhof 2014 leads to an increase of 9.85 %. Additionally, we applied our gas transfer suppression algorithm to global air-sea flux climatologies of CO2 and DMS. The global application of gas transfer suppression leads to a decrease of 11% in DMS outgassing. We expect the magnitude of Reynolds suppression on any global air-sea gas exchange to be about 10

RV SONNE SO243 Cruise Report / Fahrtbericht Guayaquil, Ecuador: 05. October 2015 Antofagasta, Chile: 22. October 2015 SO243 ASTRA-OMZ: AIR SEA INTERACTION OF TRACE ELEMENTS IN OXYGEN MINIMUM ZONES

The ASTRA-OMZ SO243 cruise on board the R/V Sonne took place between the 5th and 22nd October 2015 from Guayaquil, Ecuador to Antofagasta, Chile. Scientists from Germany, the U.S.A, and Norway participated, spanning chemical, biological, and physical oceanography, as well as atmospheric science. The main goal of the cruise was to determine the impact of low oxygen conditions on trace element cycling and distributions, as well as to determine how air-sea exchange of trace elements is influenced by high productivity conditions. The subsequent impact of trace element ocean-atmosphere exchange on atmospheric chemistry and climate will be determined. A summary of the main preliminary results is below: - a strong source of nitrous oxide (N2O) and carbon dioxide (CO2) was detected from surface waters in the Peruvian upwelling, particularly in the near-coastal area between 9°S and 18°S - generally, surface N2O during the SO-243 cruise was lower than previously observed, probably due to the reduced extent of upwelling events because of El Niño conditions - less dimethyl sulphide (DMS) (< 2nmol L-1) and isoprene (at 20-30 pmol L-1) than on board previous cruises in the coastal upwelling region (8°-12°S) were detected, likely due to suppressed upwelling off of Peru because of the El Niño conditions - a strong source for atmospheric carbonyl sulphide (OCS) was observed, as well as a strong correlation with oxygen. OCS decreased below the detection limit in oxygen depleted zones. - a strong contrast between normal and El Niño conditions were detected for the halocarbon compounds. Both surface and deeper water was characterized by much larger concentrations of bromocarbons than of iodocarbons during ASTRA-OMZ, which stands in contrast to the previous M91 cruise during neutral conditions. - it appears that the direct flux eddy covariance method was successful for sea-to-air flux measurements of N2O (for the first time) - a pronounced atmospheric inversion layer at approximately 1 km altitude was striking, which was accompanied by an accumulation of high relative humidity and moderate to fresh southerly winds below this inversion. Convective activity was limited and very few precipitation events were detected. Tropospheric ozone levels reveal distinct fluctuations within 9.5°S and 16.5°S latitude. - the oxygen distribution measured at about 9°S showed that the upwelling in October 2015 was very weak. Low oxygen water with less than 5 μmol kg-1 was located only below 250 m in October 2015 - higher oxygen distribution in 2015, as well as the changes in water temperature, salinity and density indicate the influence of El Niño. We have already published our first paper related to El Niño during SO243 (Stramma et al. 2016)

A chemical ionization mass spectrometer for continuous underway shipboard analysis of dimethylsulfide in near-surface seawater

A compact, low-cost atmospheric pressure, chemical ionization mass spectrometer ("mini-CIMS") has been developed for continuous underway shipboard measurements of dimethylsulfide (DMS) in seawater. The instrument was used to analyze DMS in air equilibrated with flowing seawater across a porous Teflon membrane equilibrator. The equilibrated gas stream was diluted with air containing an isotopically-labeled internal standard. DMS is ionized at atmospheric pressure via proton transfer from water vapor, then declustered, mass filtered via quadrupole mass spectrometry, and detected with an electron multiplier. The instrument described here is based on a low-cost residual gas analyzer (Stanford Research Systems), which has been modified for use as a chemical ionization mass spectrometer. The mini-CIMS has a gas phase detection limit of 220 ppt DMS for a 1 min averaging time, which is roughly equivalent to a seawater DMS concentration of 0.1 nM DMS at 20°C. The mini-CIMS has the sensitivity, selectivity, and time response required for underway measurements of surface ocean DMS over the full range of oceanographic conditions. The simple, robust design and relatively low cost of the instrument are intended to facilitate use in process studies and surveys, with potential for long-term deployment on research vessels, ships of opportunity, and large buoys

Monthly resolved modelled oceanic emissions of carbonyl sulfide and carbon disulfide for the period 2000–2019

Carbonyl sulfide (OCS) is the most abundant, long-lived sulphur gas in the atmosphere and a major supplier of sulfur to the stratospheric sulfate aerosol layer. The short-lived gas carbon disulfide (CS2) is oxidized to OCS and constitutes a major indirect source to the atmospheric OCS budget. The atmospheric budget of OCS is not well constrained due to a large missing source needed to compensate for substantial evidence that was provided for significantly higher sinks. Oceanic emissions are associated with major uncertainties. Here we provide a first, monthly resolved ocean emission inventory of both gases for the period 2000–2019 (available at https://doi.org/10.5281/zenodo.4297010) (Lennartz et al., 2020a). Emissions are calculated with a numerical box model (resolution 2.8° × 2.8° at equator, T42 grid) for the surface mixed layer. We find that interannual variability in OCS emissions is smaller than seasonal variability, and is mainly driven by variations in chromophoric dissolved organic matter (CDOM), which influences both photochemical and light-independent production. A comparison with a global database of more than 2500 measurements reveals overall good agreement. Emissions of CS2 constitute a larger sulfur source to the atmosphere than OCS, and equally show interannual variability connected to variability of CDOM. The emission estimate of CS2 is associated with higher uncertainties, as process understanding of the marine cycling of CS2 is incomplete. We encourage the use of the data provided here as input for atmospheric modelling studies to further assess the atmospheric OCS budget and the role of OCS in climate

Dimethylsulfide Gas Transfer Coefficients from Algal Blooms in the Southern Ocean

Air-sea dimethylsulfide (DMS) fluxes and bulk air-sea gradients were measured over the Southern Ocean in February-March 2012 during the Surface Ocean Aerosol Production (SOAP) study. The cruise encountered three distinct phytoplankton bloom regions, consisting of two blooms with moderate DMS levels, and a high biomass, dinoflagellate-dominated bloom with high seawater DMS levels (\u3e 15 nM). Gas transfer coefficients were considerably scattered at wind speeds above 5 m s(-1). Bin averaging the data resulted in a linear relationship between wind speed and mean gas transfer velocity consistent with that previously observed. However, the wind-speed-binned gas transfer data distribution at all wind speeds is positively skewed. The flux and seawater DMS distributions were also positively skewed, which suggests that eddy covariance-derived gas transfer velocities are consistently influenced by additional, log-normal noise. A flux footprint analysis was conducted during a transect into the prevailing wind and through elevated DMS levels in the dinoflagellate bloom. Accounting for the temporal/spatial separation between flux and seawater concentration significantly reduces the scatter in computed transfer velocity. The SOAP gas transfer velocity data show no obvious modification of the gas transfer-wind speed relationship by biological activity or waves. This study highlights the challenges associated with eddy covariance gas transfer measurements in biologically active and heterogeneous bloom environments

Marine isoprene production and consumption in the mixed layer of the surface ocean – A field study over 2 oceanic regions.

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

DMS sea-to-air fluxes and their influence on sulfate aerosols over the Southern Ocean, south-east Indian Ocean and north-west Pacific Ocean

Environmental context The ocean-produced dimethyl sulfide (DMS) molecule is thought to affect cloud formation and the solar radiation budget at the Earth's surface, hence playing an important role in regulating climate. In this study, we calculated the DMS sea-to-air flux across the Southern Ocean, south-east Indian Ocean and north-west Pacific Ocean, and analysed the influence of DMS fluxes on sulfate aerosols. These results improved our understanding of the effects of DMS emissions on sulfate compounds in the atmosphere over the global ocean. Oceanic dimethyl sulfide (DMS) is the most abundant biogenic sulfur compound emitted into the atmosphere and could indirectly regulate the global climate by impacting end product sulfate aerosols. DMS emissions and their influence on sulfate aerosols, i.e. methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO42-), were investigated over the Atlantic Ocean and Indian Ocean sectors of the Southern Ocean (SO), the south-east Indian Ocean, and the north-west Pacific Ocean from February to April 2014 during the 30th Chinese National Antarctic Research Expedition. We found a strong large-scale DMS source in the marginal sea ice zone from 34 degrees W to 14 degrees E of the SO (south of 60 degrees S), in which the mean flux was 49.0 +/- 65.6 mu mol m(-2) d(-1) (0.6-308.3 mu mol m(-2) d(-1), n = 424). We also found a second large-scale DMS source in the South Subtropical Front (similar to 40 degrees S, up to 50.8 mu mol m(-2) d(-1)). An inconsistency between concentrations of atmospheric sulfate compounds and DMS emissions along the cruise track was observed. The horizontal advection of air masses was likely the main reason for this discrepancy. Finally, the biological exposure calculation results also indicated that it is very difficult to observe a straightforward relationship between oceanic biomass and atmospheric MSA

The links between marine plastic litter and the air-sea flux of greenhouse gases

Climate change and plastic pollution are two of the most pressing environmental challenges caused by human activity, and they are directly and indirectly linked. We focus on the relationship between marine plastic litter and the air-sea flux of greenhouse gases (GHGs). Marine plastic litter has the potential to both enhance and reduce oceanic GHG fluxes, but this depends on many factors that are not well understood. Different kinds of plastic behave quite differently in the sea, affecting air-sea gas exchange in different, largely unknown, ways. The mechanisms of air-sea exchange of GHGs have been extensively studied and if air-sea gas transfer coefficients and concentrations of the gas in water and air are known, calculating the resulting GHG fluxes is reasonably straightforward. However, relatively little is known about the consequences of marine plastic litter for gas transfer coefficients, concentrations, and fluxes. Here we evaluate the most important aspects controlling the exchange of GHGs between the sea and the atmosphere and how marine plastic litter could change these. The aim is to move towards improving air-sea GHG flux calculations in the presence of plastic litter and we have largely limited ourselves to identifying processes, rather than estimating relative importance

Oxygenated volatile organic carbon in the western Pacific convective center : ocean cycling, air–sea gas exchange and atmospheric transport

© 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.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.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