Observations of I2 at a remote marine site

Inorganic iodine plays a significant role in the photochemistry of the marine boundary layer, but the sources and cycling of iodine are not well understood. We report the first I2 observations in marine air that is not impacted by coastal macroalgal emissions or sea ice chemistry. The data clearly demonstrate that the very high I2 levels previously reported for coastal air are not representative of open ocean conditions. In this study, gas phase I2 was measured at the Cape Verde Atmospheric Observatory, a semi-remote site in the eastern tropical Atlantic, using atmospheric pressure chemical ionization tandem mass spectrometry. Atmospheric I2 levels typically increased beginning at sunset, leveled off after midnight, and then rapidly decreased at sunrise. There was also a smaller midday maximum in I 2 that was probably caused by a measurement artifact. Ambient I 2 mixing ratios ranged from <0.02-0.6 pmol mol-1 in May 2007 and <0.03-1.67 pmol mol-1 in May 2009. The sea-air flux implied by the nighttime buildup of I2 is too small to explain the observed daytime IO levels at this site. Iodocarbon measurements made in this region previously are also insufficient to explain the observed 1-2 pmol mol-1 of daytime IO. The observations imply the existence of an unknown daytime source of gas phase inorganic iodine. Carpenter et al. (2013) recently proposed that sea surface emissions of HOI are several times larger than the flux of I2. Such a flux could account for both the nighttime I2 and the daytime IO observations

Gradient flux measurements of sea–air DMS transfer during the Surface Ocean Aerosol Production (SOAP) experiment

Direct measurements of marine dimethylsulfide (DMS) fluxes are sparse, particularly in the Southern Ocean. The Surface Ocean Aerosol Production (SOAP) voyage in February–March 2012 examined the distribution and flux of DMS in a biologically active frontal system in the southwest Pacific Ocean. Three distinct phytoplankton blooms were studied with oceanic DMS concentrations as high as 25 nmol L−1. Measurements of DMS fluxes were made using two independent methods: the eddy covariance (EC) technique using atmospheric pressure chemical ionization–mass spectrometry (API-CIMS) and the gradient flux (GF) technique from an autonomous catamaran platform. Catamaran flux measurements are relatively unaffected by airflow distortion and are made close to the water surface, where gas gradients are largest. Flux measurements were complemented by near-surface hydrographic measurements to elucidate physical factors influencing DMS emission. Individual DMS fluxes derived by EC showed significant scatter and, at times, consistent departures from the Coupled Ocean–Atmosphere Response Experiment gas transfer algorithm (COAREG). A direct comparison between the two flux methods was carried out to separate instrumental effects from environmental effects and showed good agreement with a regression slope of 0.96 (r2 = 0.89). A period of abnormal downward atmospheric heat flux enhanced near-surface ocean stratification and reduced turbulent exchange, during which GF and EC transfer velocities showed good agreement but modelled COAREG values were significantly higher. The transfer velocity derived from near-surface ocean turbulence measurements on a spar buoy compared well with the COAREG model in general but showed less variation. This first direct comparison between EC and GF fluxes of DMS provides confidence in compilation of flux estimates from both techniques, as well as in the stable periods when the observations are not well predicted by the COAREG model

Using eddy covariance to measure the dependence of air–sea CO2 exchange rate on friction velocity

Parameterisation of the air–sea gas transfer velocity of CO2 and other trace gases under open-ocean conditions has been a focus of air–sea interaction research and is required for accurately determining ocean carbon uptake. Ships are the most widely used platform for air–sea flux measurements but the quality of the data can be compromised by airflow distortion and sensor cross-sensitivity effects. Recent improvements in the understanding of these effects have led to enhanced corrections to the shipboard eddy covariance (EC) measurements. Here, we present a revised analysis of eddy covariance measurements of air–sea CO2 and momentum fluxes from the Southern Ocean Surface Ocean Aerosol Production (SOAP) study. We show that it is possible to significantly reduce the scatter in the EC data and achieve consistency between measurements taken on station and with the ship underway. The gas transfer velocities from the EC measurements correlate better with the EC friction velocity (u*) than with mean wind speeds derived from shipboard measurements corrected with an airflow distortion model. For the observed range of wind speeds (u10 N = 3–23 m s−1), the transfer velocities can be parameterised with a linear fit to u*. The SOAP data are compared to previous gas transfer parameterisations using u10 N computed from the EC friction velocity with the drag coefficient from the Coupled Ocean–Atmosphere Response Experiment (COARE) model version 3.5. The SOAP results are consistent with previous gas transfer studies, but at high wind speeds they do not support the sharp increase in gas transfer associated with bubble-mediated transfer predicted by physically based models

Air/sea DMS gas transfer in the North Atlantic: evidence for limited interfacial gas exchange at high wind speed

Shipboard measurements of eddy covariance dimethylsulfide (DMS) air–sea fluxes and seawater concentration were carried out in the North Atlantic bloom region in June/July 2011. Gas transfer coefficients (k660) show a linear dependence on mean horizontal wind speed at wind speeds up to 11 m s−1. At higher wind speeds the relationship between k660 and wind speed weakens. At high winds, measured DMS fluxes were lower than predicted based on the linear relationship between wind speed and interfacial stress extrapolated from low to intermediate wind speeds. In contrast, the transfer coefficient for sensible heat did not exhibit this effect. The apparent suppression of air–sea gas flux at higher wind speeds appears to be related to sea state, as determined from shipboard wave measurements. These observations are consistent with the idea that long waves suppress near-surface water-side turbulence, and decrease interfacial gas transfer. This effect may be more easily observed for DMS than for less soluble gases, such as CO2, because the air–sea exchange of DMS is controlled by interfacial rather than bubble-mediated gas transfer under high wind speed conditions

Methanethiol, dimethyl sulfide and acetone over biologically productive waters in the southwest Pacific Ocean

Atmospheric methanethiol (MeSHa), dimethyl sulfide (DMSa) and acetone (acetonea) were measured over biologically productive frontal waters in the remote southwest Pacific Ocean in summertime 2012 during the Surface Ocean Aerosol Production (SOAP) voyage. MeSHa mixing ratios varied from below the detection limit (<10ppt) up to 65ppt and were 3%–36% of parallel DMSa mixing ratios. MeSHa and DMSa were correlated over the voyage(R2=0.3,slope=0.07)with a stronger correlation over a coccolithophore-dominated phytoplankton bloom (R2= 0.5, slope 0.13). The diurnal cycle for MeSHa shows similar behaviour to DMSa with mixing ratios varying by a factor of ∼2 according to time of day with the minimum levels of both MeSHa and DMSa occurring at around 16:00LT (local time, all times in this paper are in local time). A positive flux of MeSH out of the ocean was calculated for three different nights and ranged from 3.5 to 5.8µmolm−2 d−1, corresponding to 14%–24% of the DMS flux (MeSH/(MeSH+DMS)). Spearman rank correlations with ocean biogeochemical parameters showed a moderate to-strong positive, highly significant relationship between both MeSHa and DMSa with seawater DMS (DMSsw) and a moderate correlation with total dimethylsulfoniopropionate (total DMSP). A positive correlation of acetonea with water temperature and negative correlation with nutrient concentrations are consistent with reports of acetone production in warmer subtropical waters. Positive correlations of acetonea with cryptophyte and eukaryotic phytoplankton numbers, and high-molecular-weight sugars and chromophoric dissolved organic matter (CDOM), suggest an organic source. This work points to a significant ocean source of MeSH, highlighting the need for further studies into the distribution and fate of MeSH, and it suggests links between atmospheric acetone levels and biogeochemistry over the midlatitude ocean. In addition, an intercalibration of DMSa at ambient levels using three independently calibrated instruments showed ∼15%–25% higher mixing ratios from an atmospheric pressure ionisation chemical ionisation mass spectrometer (mesoCIMS) compared to a gas chromatograph with a sulfurchemiluminescencedetector(GC-SCD)and proton transfer reaction mass spectrometer (PTR-MS). Some differences were attributed to the DMSa gradient above the sea surface and differing approaches of integrated versus discrete measurements. Remaining discrepancies were likely due to different calibrationscales,suggesting that further investigation of the stability and/or absolute calibration of DMSstandards used at sea is warranted

Predictability of Seawater DMS During the North Atlantic Aerosol and Marine Ecosystem Study (NAAMES)

This work presents an overview of a unique set of surface ocean dimethylsulfide (DMS) measurements from four shipboard field campaigns conducted during the North Atlantic Aerosol and Marine Ecosystem Study (NAAMES) project. Variations in surface seawater DMS are discussed in relation to biological and physical observations. Results are considered at a range of timescales (seasons to days) and spatial scales (regional to sub-mesoscale). Elevated DMS concentrations are generally associated with greater biological productivity, although chlorophyll a (Chl) only explains a small fraction of the DMS variability (15%). Physical factors that determine the location of oceanic temperature fronts and depth of vertical mixing have an important influence on seawater DMS concentrations during all seasons. The interplay of biomass and physics influences DMS concentrations at regional/seasonal scales and at smaller spatial and shorter temporal scales. Seawater DMS measurements are compared with the global seawater DMS climatology and predictions made using a recently published algorithm and by a neural network model. The climatology is successful at capturing the seasonal progression in average seawater DMS, but does not reproduce the shorter spatial/temporal scale variability. The input terms common to the algorithm and neural network approaches are biological (Chl) and physical (mixed layer depth, photosynthetically active radiation, seawater temperature). Both models predict the seasonal North Atlantic average seawater DMS trends better than the climatology. However, DMS concentrations tend to be under-predicted and the episodic occurrence of higher DMS concentrations is poorly predicted. The choice of climatological seawater DMS product makes a substantial impact on the estimated DMS flux into the North Atlantic atmosphere. These results suggest that additional input terms are needed to improve the predictive capability of current state-of-the-art approaches to estimating seawater DMS

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 (> 15 nM). Gas transfer coefficients were considerably scattered at wind speeds above 5 m/s. 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

Assessing the potential for dimethylsulfide enrichment at the sea surface and its influence on air–sea flux

The flux of dimethylsulfide (DMS) to the atmosphere is generally inferred using water sampled at or below 2 m depth, thereby excluding any concentration anomalies at the air–sea interface. Two independent techniques were used to assess the potential for near-surface DMS enrichment to influence DMS emissions and also identify the factors influencing enrichment. DMS measurements in productive frontal waters over the Chatham Rise, east of New Zealand, did not identify any significant gradients between 0.01 and 6 m in sub-surface seawater, whereas DMS enrichment in the sea-surface microlayer was variable, with a mean enrichment factor (EF; the concentration ratio between DMS in the sea-surface microlayer and in sub-surface water) of 1.7. Physical and biological factors influenced sea-surface microlayer DMS concentration, with high enrichment (EF > 1.3) only recorded in a dinoflagellate-dominated bloom, and associated with low to medium wind speeds and near-surface temperature gradients. On occasion, high DMS enrichment preceded periods when the air–sea DMS flux, measured by eddy covariance, exceeded the flux calculated using National Oceanic and Atmospheric Administration (NOAA) Coupled-Ocean Atmospheric Response Experiment (COARE) parameterized gas transfer velocities and measured sub-surface seawater DMS concentrations. The results of these two independent approaches suggest that air–sea emissions may be influenced by near-surface DMS production under certain conditions, and highlight the need for further study to constrain the magnitude and mechanisms of DMS production in the sea-surface microlayer

The relationship between ocean surface turbulence and air-sea gas transfer velocity: An in-situ evaluation

Although the air-sea gas transfer velocity k is usually parameterized with wind speed, the so-called small-eddy model suggests a relationship between k and ocean surface dissipation of turbulent kinetic energy . Laboratory and field measurements of k and have shown that this model holds in various ecosystems. Here, field observations are presented supporting the theoretical model in the open ocean. These observations are based on measurements from the Air-Sea Interaction Profiler and eddy covariance CO2 and DMS air-sea flux data collected during the Knorr11 cruise. We show that the model results can be improved when applying a variable Schmidt number exponent compared to a commonly used constant value of 1/2. Scaling to the viscous sublayer allows us to investigate the model at different depths and to expand its applicability for more extensive data sets