Benzene, toluene, ethylbenzene and xylenes can contribute to hydroxyl reactivity and secondary aerosol formation in the atmosphere. These aromatic hydrocarbons are typically classified as anthropogenic air pollutants, but there is growing evidence of biogenic sources, such as emissions from plants and phytoplankton. Here we use a series of shipborne measurements of the remote marine atmosphere, seawater mesocosm incubation experiments and phytoplankton laboratory cultures to investigate potential marine biogenic sources of these compounds in the oceanic atmosphere. Laboratory culture experiments confirmed marine phytoplankton are a source of benzene, toluene, ethylbenzene, xylenes and in mesocosm experiments their sea-air fluxes varied between seawater samples containing differing phytoplankton communities. These fluxes were of a similar magnitude or greater than the fluxes of dimethyl sulfide, which is considered to be the key reactive organic species in the marine atmosphere. Benzene, toluene, ethylbenzene, xylenes fluxes were observed to increase under elevated headspace ozone concentration in the mesocosm incubation experiments, indicating that phytoplankton produce these compounds in response to oxidative stress. Our findings suggest that biogenic sources of these gases may be sufficiently strong to influence atmospheric chemistry in some remote ocean regions.

One pathway by which the oceans influence climate is via the emission of sea spray that may subsequently influence cloud properties. Sea spray emissions are known to be dependent on atmospheric and oceanic physicochemical parameters, but the potential role of ocean biology on sea spray fluxes remains poorly characterized. Here we show a consistent significant relationship between seawater nanophytoplankton cell abundances and sea-spray derived Cloud Condensation Nuclei (CCN) number fluxes, generated using water from three different oceanic regions. This sensitivity of CCN number fluxes to ocean biology is currently unaccounted for in climate models yet our measurements indicate that it influences fluxes by more than one order of magnitude over the range of phytoplankton investigated.

Due to its remote location and extreme weather conditions, atmospheric in situ measurements are rare in the Southern Ocean. As a result, aerosol–cloud interactions in this region are poorly understood and remain a major source of uncertainty in climate models. This, in turn, contributes substantially to persistent biases in climate model simulations such as the well-known positive shortwave radiation bias at the surface, as well as biases in numerical weather prediction models and reanalyses. It has been shown in previous studies that in situ and ground-based remote sensing measurements across the Southern Ocean are critical for complementing satellite data sets due to the importance of boundary layer and low-level cloud processes. These processes are poorly sampled by satellite-based measurements and are often obscured by multiple overlying cloud layers. Satellite measurements also do not constrain the aerosol–cloud processes very well with imprecise estimation of cloud condensation nuclei. In this work, we present a comprehensive set of ship-based aerosol and meteorological observations collected on the 6-week Southern Ocean Ross Sea Marine Ecosystem and Environment voyage (TAN1802) voyage of RV Tangaroa across the Southern Ocean, from Wellington, New Zealand, to the Ross Sea, Antarctica. The voyage was carried out from 8 February to 21 March 2018. Many distinct, but contemporaneous, data sets were collected throughout the voyage. The compiled data sets include measurements from a range of instruments, such as (i) meteorological conditions at the sea surface and profile measurements; (ii) the size and concentration of particles; (iii) trace gases dissolved in the ocean surface such as dimethyl sulfide and carbonyl sulfide; (iv) and remotely sensed observations of low clouds. Here, we describe the voyage, the instruments, and data processing, and provide a brief overview of some of the data products available. We encourage the scientific community to use these measurements for further analysis and model evaluation studies, in particular, for studies of Southern Ocean clouds, aerosol, and their interaction. The data sets presented in this study are publicly available at https://doi.org/10.5281/zenodo.4060237 (Kremser et al., 2020).

Elevated dimethyl sulfide (DMS) concentrations in the sea surface microlayer (SML) have been previously related to DMS air–sea flux anomalies in the southwestern Pacific. To further address this, DMS, its precursor dimethylsulfoniopropionate (DMSP), and ancillary variables were sampled in the SML and also subsurface water at 0.5 m depth (SSW) in different water masses east of New Zealand. Despite high phytoplankton biomass at some stations, the SML chlorophyll a enrichment factor (EF) was low (< 1.06), and DMSP was enriched at one station with DMSP EF ranging from 0.81 to 1.25. DMS in the SML was determined using a novel gas-permeable tube technique which measured consistently higher concentrations than with the traditional glass plate technique; however, significant DMS enrichment was present at only one station, with the EF ranging from 0.40 to 1.22. SML DMSP and DMS were influenced by phytoplankton community composition, with correlations with dinoflagellate and Gymnodinium biomass, respectively. DMSP and DMS concentrations were also correlated between the SML and SSW, with the difference in ratio attributable to greater DMS loss to the atmosphere from the SML. In the absence of significant enrichment, DMS in the SML did not influence DMS emissions, with the calculated air–sea DMS flux of 2.28 to 11.0 µmol m⁻² d⁻¹ consistent with climatological estimates for the region. These results confirm previous regional observations that DMS is associated with dinoflagellate abundance but indicate that additional factors are required to support significant enrichment in the SML.

The cycling of the trace gas dimethyl sulfide (DMS) and its precursor dimethylsulfoniopropionate (DMSP) may be affected by future ocean acidification and warming. DMSP and DMS concentrations were monitored over 20-days in four mesocosm experiments in which the temperature and pH of coastal water were manipulated to projected values for the year 2100 and 2150. This had no effect on DMSP in the two-initial nutrient-depleted experiments; however, in the two nutrient-amended experiments, warmer temperature combined with lower pH had a more significant effect on DMSP & DMS concentrations than lower pH alone. Overall, this indicates that future warming may have greater influence on DMS production than ocean acidification. The observed reduction in DMSP at warmer temperatures was associated with changes in phytoplankton community and in particular with small flagellate biomass. A small decrease in DMS concentration was measured in the treatments relative to other studies, from −2% in the nutrient-amended low pH treatment to −16% in the year 2150 pH and temperature conditions. Temporal variation was also observed with DMS concentration increasing earlier in the higher temperature treatment. Nutrient availability and community composition should be considered in models of future DMS.

Dimethyl sulphide (DMS) and methanethiol (MeSH) emissions from South Pacific surface seawater were determined in deck board Air‐Sea Interface Tanks during the Sea2Cloud voyage in March 2020. The measured fluxes from water to headspace (F) varied with water mass type, with lowest fluxes observed with Subtropical and Subantarctic waters and highest fluxes from Frontal waters. Measured DMS fluxes were consistent with fluxes calculated using a two‐layer model and seawater DMS concentrations. The MeSH:DMS flux ratio was 11%–18% across the three water mass types, confirming that MeSH may represent a significant unaccounted contribution to the atmospheric sulfur budget, with potentially important implications for marine aerosol formation and growth in models. Combining data from the ASITs and ambient surface seawater identified significant Spearman rank correlations for both dissolved DMS and MeSH with nanophytoplankton cell abundance (p_value < 0.012), suggesting an important role for this phytoplankton size class in determining regional DMS and MeSH emissions. Applying a nanophytoplankton‐based parameterization to estimate DMS_w provided good agreement with a recent DMS climatology. Consequently, the observed relationship between DMS_w, MeSH_w and nanophytoplankton cell abundances may be applicable for modeling atmospheric fluxes.