ALBERT

Description: 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.

Description: 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.

Description: Wildfires and their emissions have significant impacts on ecosystems, climate, atmospheric chemistry, and carbon cycling. Well-dated proxy records are needed to study the long-term climatic controls on biomass burning and the associated climate feedbacks. There is a particular lack of information about long-term biomass burning variations in Siberia, the largest forested area in the Northern Hemisphere. In this study we report analyses of aromatic acids (vanillic and para-hydroxybenzoic acids) over the past 2600 years in the Eurasian Arctic Akademii Nauk ice core. These compounds are aerosol-borne, semi-volatile organic compounds derived from lignin combustion. The analyses were made using ion chromatography with electrospray mass spectrometric detection. The levels of these aromatic acids ranged from below the detection limit (0.01 to 0.05 ppb; 1 ppb  =  1000 ng L−1) to about 1 ppb, with roughly 30 % of the samples above the detection limit. In the preindustrial late Holocene, highly elevated aromatic acid levels are observed during three distinct periods (650–300 BCE, 340–660 CE, and 1460–1660 CE). The timing of the two most recent periods coincides with the episodic pulsing of ice-rafted debris in the North Atlantic known as Bond events and a weakened Asian monsoon, suggesting a link between fires and large-scale climate variability on millennial timescales. Aromatic acid levels also are elevated during the onset of the industrial period from 1780 to 1860 CE, but with a different ratio of vanillic and para-hydroxybenzoic acid than is observed during the preindustrial period. This study provides the first millennial-scale record of aromatic acids. This study clearly demonstrates that coherent aromatic acid signals are recorded in polar ice cores that can be used as proxies for past trends in biomass burning.

Description: 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.

Description: 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.

Description: 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.

Description: For the past decade, observations of carbonyl sulfide (OCS or COS) have been investigated as a proxy for carbon uptake by plants. OCS is destroyed by enzymes that interact with CO2 during photosynthesis, namely carbonic anhydrase (CA) and RuBisCO, where CA is the more important. The majority of sources of OCS to the atmosphere are geographically separated from this large plant sink, whereas the sources and sinks of CO2 are co-located in ecosystems. The drawdown of OCS can therefore be related to the uptake of CO2 without the added complication of co-located emissions comparable in magnitude. Here we review the state of our understanding of the global OCS cycle and its applications to ecosystem carbon cycle science. OCS uptake is correlated well to plant carbon uptake, especially at the regional scale. OCS can be used in conjunction with other independent measures of ecosystem function, like solar-induced fluorescence and carbon and water isotope studies. More work needs to be done to generate global coverage for OCS observations and to link this powerful atmospheric tracer to systems where fundamental questions concerning the carbon and water cycle remain.

Description: This study presents vanillic acid and para-hydroxybenzoic acid levels in an Arctic ice core from Lomonosovfonna, Svalbard covering the past 800 years. These methoxy aromatic acids are likely derived from lignin combustion in wildfires and long-range aerosol transport. Vanillic and para-hydroxybenzoic acid are present throughout the ice core, confirming that these compounds are preserved on millennial time scales. Vanillic and para-hydroxybenzoic acid concentrations in the Lomonosovfonna ice core ranged from below the limits of detection to 0.2 and 0.07 ppb, respectively (1 ppb = 1000 ng/l). Vanillic acid levels are high (below the limit of detection to 0.1 ppb) from 1200–1400 CE, then gradually decline into the 20th century. The largest peak in the vanillic acid in the record occurs from 2000–2008 CE. In the para-hydrobenzoic acid record, there are three centennial-scale peaks around 1300, 1550, and 1650 CE superimposed on a long-term decline in the baseline levels throughout the record. Air mass back trajectory analysis indicates that Siberia and Europe are the primary source regions for wildfire emissions reaching the Lomonosovfonna site. The Lomonosovfonna data are similar to those from the Eurasian Arctic Akademii Nauk ice core during the early part of the record (1220–1400 CE), but the two ice cores diverge markedly after 1400 CE. This coincides with a shift in North Atlantic climate marked by a change of the North Atlantic Oscillation from a positive to a more negative state.

Description: For the past decade, observations of carbonyl sulfide (OCS or COS) have been investigated as a proxy for carbon uptake by plants. OCS is destroyed by enzymes that interact with CO2 during photosynthesis, namely carbonic anhydrase (CA) and RuBisCO, where CA is the more important one. The majority of sources of OCS to the atmosphere are geographically separated from this large plant sink, whereas the sources and sinks of CO2 are co-located in ecosystems. The drawdown of OCS can therefore be related to the uptake of CO2 without the added complication of co-located emissions comparable in magnitude. Here we review the state of our understanding of the global OCS cycle and its applications to ecosystem carbon cycle science. OCS uptake is correlated well to plant carbon uptake, especially at the regional scale. OCS can be used in conjunction with other independent measures of ecosystem function, like solar-induced fluorescence and carbon and water isotope studies. More work needs to be done to generate global coverage for OCS observations and to link this powerful atmospheric tracer to systems where fundamental questions concerning the carbon and water cycle remain.

Description: 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.