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Atmospheric marine particle concentrations impact cloud properties, which strongly impact the amount of solar radiation reflected back into space or absorbed by the ocean surface. While satellites can provide a snapshot of current conditions at the overpass time, models are necessary to simulate temporal variations in both particle and cloud properties. However, poor model accuracy limits the reliability with which these tools can be used to predict future climate. Here, we leverage the comprehensive ocean ecosystem and atmospheric aerosol–cloud dataset obtained during the third deployment of the North Atlantic Aerosols and Marine Ecosystems Study (NAAMES3). Airborne and ship-based measurements were collected in and around a cold-air outbreak during a 3 d (where d stands for day) intensive operations period from 17–19 September 2017. Cold-air outbreaks are of keen interest for model validation because they are challenging to accurately simulate, which is due, in part, to the numerous feedbacks and sub-grid-scale processes that influence aerosol and cloud evolution. The NAAMES observations are particularly valuable because the flight plans were tailored to lie along Lagrangian trajectories, making it possible to spatiotemporally connect upwind and downwind measurements with the state-of-the-art FLEXible PARTicle (FLEXPART) Lagrangian particle dispersion model and then calculate a rate of change in particle properties. Initial aerosol conditions spanning an east–west, closed-cell-to-clear-air transition region of the cold-air outbreak indicate similar particle concentrations and properties. However, despite the similarities in the aerosol fields, the cloud properties downwind of each region evolved quite differently. One trajectory carried particles through a cold-air outbreak, resulting in a decrease in accumulation mode particle concentration (−42 %) and cloud droplet concentrations, while the other remained outside of the cold-air outbreak and experienced an increase in accumulation mode particle concentrations (+62 %). The variable meteorological conditions between these two adjacent trajectories result from differences in the local sea surface temperature in the Labrador Current and surrounding waters, altering the stability of the marine atmospheric boundary layer. Further comparisons of historical satellite observations indicate that the observed pattern occurs annually in the region, making it an ideal location for future airborne Lagrangian studies tracking the evolution of aerosols and clouds over time under cold-air outbreak conditions.

Marine biogenic particle contributions to atmospheric aerosol concentrations are not well understood though they are important for determining cloud optical and cloud-nucleating properties. Here we examine the relationship between marine aerosol measurements (with satellites and model fields of ocean biology) and meteorological variables during the North Atlantic Aerosols and Marine Ecosystems Study (NAAMES). NAAMES consisted of four field campaigns between November 2015 and April 2018 that aligned with the four major phases of the annual phytoplankton bloom cycle. The FLEXible PARTicle (FLEXPART) Lagrangian particle dispersion model is used to spatiotemporally connect these variables to ship-based aerosol and dimethyl sulfide (DMS) observations. We find that correlations between some aerosol measurements with satellite-measured and modeled variables increase with increasing trajectory length, indicating that biological and meteorological processes over the air mass history are influential for measured particle properties and that using only spatially coincident data would miss correlative connections that are lagged in time. In particular, the marine non-refractory organic aerosol mass correlates with modeled marine net primary production when weighted by 5 d air mass trajectory residence time (r=0.62). This result indicates that non-refractory organic aerosol mass is influenced by biogenic volatile organic compound (VOC) emissions that are typically produced through bacterial degradation of dissolved organic matter, zooplankton grazing on marine phytoplankton, and as a by-product of photosynthesis by phytoplankton stocks during advection into the region. This is further supported by the correlation of non-refractory organic mass with 2 d residence-time-weighted chlorophyll a (r=0.39), a proxy for phytoplankton abundance, and 5 d residence-time-weighted downward shortwave forcing (r=0.58), a requirement for photosynthesis. In contrast, DMS (formed through biological processes in the seawater) and primary marine aerosol (PMA) concentrations showed better correlations with explanatory biological and meteorological variables weighted with shorter air mass residence times, which reflects their localized origin as primary emissions. Aerosol submicron number and mass negatively correlate with sea surface wind speed. The negative correlation is attributed to enhanced PMA concentrations under higher wind speed conditions. We hypothesized that the elevated total particle surface area associated with high PMA concentrations leads to enhanced rates of condensation of VOC oxidation products onto PMA. Given the high deposition velocity of PMA relative to submicron aerosol, PMA can limit the accumulation of secondary aerosol mass. This study provides observational evidence for connections between marine aerosols and underlying ocean biology through complex secondary formation processes, emphasizing the need to consider air mass history in future analyses.

The composition of organic compounds in marine aerosols and the relative contributions of primary and secondary organic compounds remain uncertain. We report results from a novel approach to characterize and quantify organic components of the marine aerosol. Size-segregated discrete aerosol filter samples were collected at sea in the North Atlantic from both ambient aerosol and artificially generated primary sea spray over four cruises timed to capture the seasonal phytoplankton bloom dynamics. Samples were analyzed by Fourier transform infrared spectroscopy (FTIR), extracted into water, and analyzed by offline thermal desorption chemical ionization mass spectrometry (TDCIMS) and ion chromatography (IC). A positive matrix factorization (PMF) analysis identified several characteristic aerosol components in the TDCIMS mass spectra. Among these is a polysaccharide factor representing about 10 %–30 % of the submicron organic aerosol mass. Aerosol polysaccharide : sodium mass ratios were consistently higher in ambient air than in the artificially generated sea spray, and we hypothesize that this results from more rapid wet deposition of sodium-rich aerosol. An unquantified recalcitrant factor of highly thermally stable organics showed significant correlation with FTIR-measured alcohol groups, consistently the main organic functional group associated with sea spray aerosol. We hypothesize that this factor represents recalcitrant dissolved organic matter (DOM) in seawater and that by extension alcohol functional groups identified in marine aerosol may more typically represent recalcitrant DOM rather than biogenic saccharide-like material, contrary to inferences made in previous studies. The recalcitrant factor showed little seasonal variability in its contribution to primary marine aerosol. The relative contribution of polysaccharides was highest in late spring and summer in the smallest particle size fraction characterized ( nm).

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 (< 10 ppt) up to 65 ppt 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 16:00 LT (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 5.8 µmol m−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 mid-latitude 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 sulfur chemiluminescence detector (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 calibration scales, suggesting that further investigation of the stability and/or absolute calibration of DMS standards used at sea is warranted.

Deposition to the sea surface is a major atmospheric loss pathway for many important trace gases, such as sulfur dioxide (SO2). The air–sea transfer of SO2 is controlled entirely on the atmospheric side of the air–sea interface due to high effective solubility and other physical–chemical properties. There have been few direct field measurements of such fluxes due to the challenges associated with making fast-response measurements of highly soluble trace gases at very low ambient levels. In this study, we report direct eddy covariance air–sea flux measurements of SO2, sensible heat, water vapor, and momentum. The measurements were made over shallow coastal waters from the Scripps Pier, La Jolla, CA, using negative ion chemical ionization mass spectrometry as the SO2 sensor. The observed transfer velocities for SO2, sensible heat, water vapor, and momentum and their wind speed dependences indicate that SO2 fluxes can be reliably measured using this approach. As expected, the transfer velocities for SO2, sensible heat, and water vapor are lower than that for momentum, demonstrating the contribution of molecular diffusion to the overall air-side resistance to gas transfer. Furthermore, transfer velocities of SO2 were lower than those of sensible heat and water vapor when observed simultaneously. This result is attributed to diffusive resistance in the interfacial layer of the air–sea interface.

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.

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.

Establishing the relationship between marine boundary layer (MBL) aerosols and surface water biogeochemistry is required to understand aerosol and cloud production processes over the remote ocean and represent them more accurately in earth system models and global climate projections. This was addressed by the SOAP (Surface Ocean Aerosol Production) campaign, which examined air–sea interaction over biologically productive frontal waters east of New Zealand. This overview details the objectives, regional context, sampling strategy and provisional findings of a pilot study, PreSOAP, in austral summer 2011 and the following SOAP voyage in late austral summer 2012. Both voyages characterized surface water and MBL composition in three phytoplankton blooms of differing species composition and biogeochemistry, with significant regional correlation observed between chlorophyll a and DMSsw. Surface seawater dimethylsulfide (DMSsw) and associated air–sea DMS flux showed spatial variation during the SOAP voyage, with maxima of 25 nmol L−1 and 100 µmol m−2 d−1, respectively, recorded in a dinoflagellate bloom. Inclusion of SOAP data in a regional DMSsw compilation indicates that the current climatological mean is an underestimate for this region of the southwest Pacific. Estimation of the DMS gas transfer velocity (kDMS) by independent techniques of eddy covariance and gradient flux showed good agreement, although both exhibited periodic deviations from model estimates. Flux anomalies were related to surface warming and sea surface microlayer enrichment and also reflected the heterogeneous distribution of DMSsw and the associated flux footprint. Other aerosol precursors measured included the halides and various volatile organic carbon compounds, with first measurements of the short-lived gases glyoxal and methylglyoxal in pristine Southern Ocean marine air indicating an unidentified local source. The application of a real-time clean sector, contaminant markers and a common aerosol inlet facilitated multi-sensor measurement of uncontaminated air. Aerosol characterization identified variable Aitken mode and consistent submicron-sized accumulation and coarse modes. Submicron aerosol mass was dominated by secondary particles containing ammonium sulfate/bisulfate under light winds, with an increase in sea salt under higher wind speeds. MBL measurements and chamber experiments identified a significant organic component in primary and secondary aerosols. Comparison of SOAP aerosol number and size distributions reveals an underprediction in GLOMAP (GLObal Model of Aerosol Processes)-mode aerosol number in clean marine air masses, suggesting a missing marine aerosol source in the model. The SOAP data will be further examined for evidence of nucleation events and also to identify relationships between MBL composition and surface ocean biogeochemistry that may provide potential proxies for aerosol precursors and production.

Simultaneous air–sea fluxes and concentration differences of dimethylsulfide (DMS) and carbon dioxide (CO2) were measured during a summertime North Atlantic cruise in 2011. This data set reveals significant differences between the gas transfer velocities of these two gases (Δkw) over a range of wind speeds up to 21 m s−1. These differences occur at and above the approximate wind speed threshold when waves begin breaking. Whitecap fraction (a proxy for bubbles) was also measured and has a positive relationship with Δkw, consistent with enhanced bubble-mediated transfer of the less soluble CO2 relative to that of the more soluble DMS. However, the correlation of Δkw with whitecap fraction is no stronger than with wind speed. Models used to estimate bubble-mediated transfer from in situ whitecap fraction underpredict the observations, particularly at intermediate wind speeds. Examining the differences between gas transfer velocities of gases with different solubilities is a useful way to detect the impact of bubble-mediated exchange. More simultaneous gas transfer measurements of different solubility gases across a wide range of oceanic conditions are needed to understand the factors controlling the magnitude and scaling of bubble-mediated gas exchange.

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.

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−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.

The 17O excess (Δ17O = δ17O−0.52 × δ18O) of sulfate and nitrate reflects the relative importance of their different production pathways in the atmosphere. A new record of sulfate and nitrate Δ17O spanning the last 2400 years from the West Antarctic Ice Sheet Divide ice core project shows significant changes in both sulfate and nitrate Δ17O in the most recent 200 years, indicating changes in their formation pathways. The sulfate Δ17O record exhibits a 1.1 ‰ increase in the early 19th century from (2.4 ± 0.2) ‰ to (3.5 ± 0.2) ‰, which suggests that an additional 12–18% of sulfate formation occurs via aqueous-phase production by O3, relative to that in the gas phase. Nitrate Δ17O gradually decreases over the whole record, with a more rapid decrease between the mid-19th century and the present day of 5.6 ‰, indicating an increasing importance of RO2 in NOx cycling between the mid-19th century and the present day in the mid- to high-latitude Southern Hemisphere. The former has implications for the climate impacts of sulfate aerosol, while the latter has implications for the tropospheric O3 production rate in remote low-NOx environments. Using other ice core observations, we rule out drivers for these changes other than variability in extratropical oxidant (OH, O3, RO2, H2O2, and reactive halogens) concentrations. However, assuming OH, H2O2, and O3 are the main oxidants contributing to sulfate formation, Monte Carlo box model simulations require a large (≥ 260%) increase in the O3 / OH mole fraction ratio over the Southern Ocean in the early 19th century to match the sulfate Δ17O record. This unlikely scenario points to a~deficiency in our understanding of sulfur chemistry and suggests other oxidants may play an important role in sulfate formation in the mid- to high-latitude marine boundary layer. The observed decrease in nitrate Δ17O since the mid-19th century is most likely due to an increased importance of RO2 over O3 in NOx cycling and can be explained by a 60–90% decrease in the O3 / RO2 mole fraction ratio in the extratropical Southern Hemisphere NOx-source regions.

Eddy covariance measurements of air–sea CO2 fluxes can be affected by cross-sensitivities of the CO2 measurement to water vapour, resulting in order-of-magnitude biases. Well-established causes for these biases are (i) cross-sensitivity of the broadband non-dispersive infrared sensors due to band-broadening and spectral overlap (commercial sensors typically correct for this) and (ii) the effect of air density fluctuations (removed by determining the dry air CO2 mixing ratio). Another bias related to water vapour fluctuations has recently been observed with open-path sensors, attributed to sea salt build-up and water films on sensor optics. Two very different approaches have been used to deal with these water vapour-related biases. Miller et al. (2010) employed a membrane drier to physically eliminate 97% of the water vapour fluctuations in the sample air before it entered a closed-path gas analyser. Prytherch et al. (2010a) employed the empirical (Peter K. Taylor, PKT) post-processing correction to correct open-path sensor data. In this paper, we test these methods side by side using data from the Surface Ocean Aerosol Production (SOAP) experiment in the Southern Ocean. The air–sea CO2 flux was directly measured with four closed-path analysers, two of which were positioned down-stream of a membrane dryer. The CO2 fluxes from the two dried gas analysers matched each other and were in general agreement with common parameterisations. The flux estimates from the un-dried sensors agreed with the dried sensors only during periods with low latent heat flux (&leq;7 W m−2). When latent heat flux was higher, CO2 flux estimates from the un-dried sensors exhibited large scatter and an order-of-magnitude bias. Applying the PKT correction to the flux data from the un-dried analysers did not remove the bias when compared to the data from the dried gas analyser. The results of this study demonstrate the validity of measuring CO2 fluxes using a pre-dried air stream and show that the PKT correction is not valid for the correction of CO2 fluxes.

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 I2 that was probably caused by a measurement artifact. Ambient I2 mixing ratios ranged from −1 in May 2007 and −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.

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.

Cl atoms in the marine atmosphere may significantly impact the lifetimes of methane and other hydrocarbons. However, the existing estimates of Cl atom levels in marine air are based on indirect evidence. Here we present measurements of the Cl precursors HOCl and Cl2 in the marine boundary layer during June of 2009 at the Cape Verde Atmospheric Observatory in the eastern tropical Atlantic. These are the first measurements of tropospheric HOCl. HOCl and Cl2 levels were low in air with open ocean back trajectories, with maximum levels always below 60 and 10 ppt (pmol/mol), respectively. In air with trajectories originating over Europe, HOCl and Cl2 levels were higher, with HOCl maxima exceeding 100 ppt each day and Cl2 reaching up to 35 ppt. The increased Cl cycling associated with long distance pollutant transport over the oceans likely impacts a wide geographic area and represents a mechanism by which human activities have increased the reactivity of the marine atmosphere. Data-constrained model simulations indicate that Cl atoms account for approximately 15 % of methane destruction on days when aged polluted air arrives at the site. A photochemical model does not adequately simulate the observed abundances of HOCl and Cl2, raising the possibility of an unknown HOCl source.

In this study, we report measurements of CFC-12 (CCl2F2) in firn air and in air extracted from shallow ice cores from three Antarctic sites. The firn air data are consistent with the known atmospheric history of CFC-12. In contrast, some of the ice core samples collected near the firn-ice transition exhibit anomalously high CFC-12 levels. Together, the ice core and firn air data provide evidence for the presence of modern air entrapped in the shallow ice core samples that likely contained open pores at the time of collection. We propose that this is due to closure of the open pores after drilling, entrapping modern air and resulting in elevated CFC-12 mixing ratios. Our results reveal that open porosity can exist below the maximum depth at which firn air samples can be collected, particularly at sites with lower accumulation rates. CFC-12 measurements demonstrate that post-drilling closure of open pores can lead to a change in the composition of bubble air in shallow ice cores through purely physical processes. The results have implications for investigations involving trace gas composition of bubbles in shallow ice cores collected near the firn-ice transition.

The NERC UK SOLAS-funded Reactive Halogens in the Marine Boundary Layer (RHaMBLe) programme comprised three field experiments. This manuscript presents an overview of the measurements made within the two simultaneous remote experiments conducted in the tropical North Atlantic in May and June 2007. Measurements were made from two mobile and one ground-based platforms. The heavily instrumented cruise D319 on the RRS Discovery from Lisbon, Portugal to São Vicente, Cape Verde and back to Falmouth, UK was used to characterise the spatial distribution of boundary layer components likely to play a role in reactive halogen chemistry. Measurements onboard the ARSF Dornier aircraft were used to allow the observations to be interpreted in the context of their vertical distribution and to confirm the interpretation of atmospheric structure in the vicinity of the Cape Verde islands. Long-term ground-based measurements at the Cape Verde Atmospheric Observatory (CVAO) on São Vicente were supplemented by long-term measurements of reactive halogen species and characterisation of additional trace gas and aerosol species during the intensive experimental period. This paper presents a summary of the measurements made within the RHaMBLe remote experiments and discusses them in their meteorological and chemical context as determined from these three platforms and from additional meteorological analyses. Air always arrived at the CVAO from the North East with a range of air mass origins (European, Atlantic and North American continental). Trace gases were present at stable and fairly low concentrations with the exception of a slight increase in some anthropogenic components in air of North American origin, though NOx mixing ratios during this period remained below 20 pptv (note the non-IUPAC adoption in this manuscript of pptv and ppbv, equivalent to pmol mol−1 and nmol mol−1 to reflect common practice). Consistency with these air mass classifications is observed in the time series of soluble gas and aerosol composition measurements, with additional identification of periods of slightly elevated dust concentrations consistent with the trajectories passing over the African continent. The CVAO is shown to be broadly representative of the wider North Atlantic marine boundary layer; measurements of NO, O3 and black carbon from the ship are consistent with a clean Northern Hemisphere marine background. Aerosol composition measurements do not indicate elevated organic material associated with clean marine air. Closer to the African coast, black carbon and NO levels start to increase, indicating greater anthropogenic influence. Lower ozone in this region is possibly associated with the increased levels of measured halocarbons, associated with the nutrient rich waters of the Mauritanian upwelling. Bromide and chloride deficits in coarse mode aerosol at both the CVAO and on D319 and the continuous abundance of inorganic gaseous halogen species at CVAO indicate significant reactive cycling of halogens. Aircraft measurements of O3 and CO show that surface measurements are representative of the entire boundary layer in the vicinity both in diurnal variability and absolute levels. Above the inversion layer similar diurnal behaviour in O3 and CO is observed at lower mixing ratios in the air that had originated from south of Cape Verde, possibly from within the ITCZ. ECMWF calculations on two days indicate very different boundary layer depths and aircraft flights over the ship replicate this, giving confidence in the calculated boundary layer depth.

Fluorescence Assay by Gas Expansion (FAGE) has been used to detect ambient levels of OH and HO2 radicals at the Cape Verde Atmospheric Observatory, located in the tropical Atlantic marine boundary layer, during May and June 2007. Midday radical concentrations were high, with maximum concentrations of 9 ×106 molecule cm−3 and 6×108 molecule cm−3 observed for OH and HO2, respectively. A box model incorporating the detailed Master Chemical Mechanism, extended to include halogen chemistry, heterogeneous loss processes and constrained by all available measurements including halogen and nitrogen oxides, has been used to assess the chemical and physical parameters controlling the radical chemistry. The model was able to reproduce the daytime radical concentrations to within the 1 σ measurement uncertainty of 20% during the latter half of the measurement period but significantly under-predicted [HO2] by 39% during the first half of the project. Sensitivity analyses demonstrate that elevated [HCHO] (~2 ppbv) on specific days during the early part of the project, which were much greater than the mean [HCHO] (328 pptv) used to constrain the model, could account for a large portion of the discrepancy between modelled and measured [HO2] at this time. IO and BrO, although present only at a few pptv, constituted ~19% of the instantaneous sinks for HO2, whilst aerosol uptake and surface deposition to the ocean accounted for a further 23% of the HO2 loss at noon. Photolysis of HOI and HOBr accounted for ~13% of the instantaneous OH formation. Taking into account that halogen oxides increase the oxidation of NOx (NO → NO2), and in turn reduce the rate of formation of OH from the reaction of HO2 with NO, OH concentrations were estimated to be 9% higher overall due to the presence of halogens. The increase in modelled OH from halogen chemistry gives an estimated 9% shorter lifetime for methane in this region, and the inclusion of halogen chemistry is necessary to model the observed daily cycle of O3 destruction that is observed at the surface. Due to surface losses, we hypothesise that HO2 concentrations increase with height and therefore contribute a larger fraction of the O3 destruction than at the surface.

The atmospheric methyl bromide (CH3Br) burden has declined in recent years, in response to the phaseout of agricultural and structural fumigation consumption under the amendments to the Montreal Protocol. The timing and magnitude of this decrease represents an opportunity to examine our current understanding of atmospheric CH3Br and its budget, response to the phaseout, and response to interannual variability in biomass burning and global OH. In this study, simulations obtained from a time-dependent global model of atmospheric CH3Br emissions and uptake are compared to observations from the NOAA flask network. The model includes a detailed gridded ocean model coupled to a time-dependant atmospheric 2-box model. The phaseout of CH3Br production for agricultural uses began in 1998, concurrent with the pulse in biomass burning associated with the 1998 El Niño. The combined effects of three factors (biomass burning, global OH, and anthropogenic phaseout) appear to explain most of the observed atmospheric methyl bromide variability over the 1997–2008 period. The global budget remains imbalanced, with a large missing source indicated. The missing source does not exhibit a systematic decline during the phaseout period, and therefore, is not the result of significantly underestimating non-QPS agricultural CH3Br emissions. The model results suggest that the oceans should be less undersaturated than before the phaseout began.

Air/sea fluxes of dimethylsulfide (DMS) were measured by eddy correlation over the Eastern South Pacific Ocean during January 2006. The cruise track extended from Manzanillo, Mexico, along 110° W, to Punta Arenas, Chile. Bulk air and surface ocean DMS levels were also measured and gas transfer coefficients (kDMS) were computed. Air and seawater DMS measurements were made using chemical ionization mass spectrometry (API-CIMS) and a gas/liquid membrane equilibrator. Mean surface seawater DMS concentrations were 3.8±2.2 nM and atmospheric mixing ratios were 340±370 ppt. The air/sea flux of DMS was uniformly out of the ocean, with an average value of 12±15 μmol m−2 d−1. Sea surface concentration and flux were highest around 15° S, in a region influenced by shelf waters and lowest around 25° S, in low chlorophyll gyre waters. The DMS gas transfer coefficient exhibited a linear wind speed-dependence over the wind speed range of 1 to 9 m s−1. This relationship is compared with previously measured estimates of k from DMS, CO2, and dual tracer data from the Atlantic and Pacific Ocean, and with the NOAA/COARE gas transfer model. The model generated slope of k vs. wind speed is at the low end of those observed in previous DMS field studies.

In this study, we present carbonyl sulfide (COS) measurements from an ice core drilled near South Pole, East Antarctica (SPRESSO). The samples are from 135–291 m, with estimated mean COS ages ranging from 278 to 2155 years before present (defined as 2000 C.E.). When combined with the previous records of COS from Antarctic ice cores and firn air, the current data provide a continuous record of COS extending beyond the last two millennia. The general agreement between ice cores, firn air, and modern air measurements supports the idea that polar ice is a valid archive for paleoatmospheric COS. The average COS mixing ratio of the SPRESSO data set is (331±18) ppt (parts per trillion in mol/mol, ±1σ, n=100), excluding 6 outliers. These data confirm earlier firn air and ice core measurements indicating that the late 20th century COS levels of 500 ppt are greatly increased over preindustrial levels and represent the highest atmospheric levels over the past 2000 years. The data also provide evidence of climate-related variability on centennial time-scales, with relative maxima at the peaks of Medieval Climate Anomaly and Little Ice Age. There is evidence for a long-term increasing trend in COS of 1.8 ppt per 100 years. Further ice core studies will be needed to determine whether this trend reflects secular variability in atmospheric COS, or a slow post-depositional chemical loss of COS in the ice core.