The Physical and Chemical Characteristics of Marine Primary Open Access Organic Aerosol: a Review Biogeosciences Biogeosciences Discussions B
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EGU Journal Logos (RGB) Open Access Open Access Open Access Advances in Annales Nonlinear Processes Geosciences Geophysicae in Geophysics Open Access Open Access Natural Hazards Natural Hazards and Earth System and Earth System Sciences Sciences Discussions Open Access Open Access Atmos. Chem. Phys., 13, 3979–3996, 2013 Atmospheric Atmospheric www.atmos-chem-phys.net/13/3979/2013/ doi:10.5194/acp-13-3979-2013 Chemistry Chemistry © Author(s) 2013. CC Attribution 3.0 License. and Physics and Physics Discussions Open Access Open Access Atmospheric Atmospheric Measurement Measurement Techniques Techniques Discussions Open Access The physical and chemical characteristics of marine primary Open Access organic aerosol: a review Biogeosciences Biogeosciences Discussions B. Gantt and N. Meskhidze Department of Marine, Earth, and Atmospheric Sciences, North Carolina State University, Raleigh, North Carolina, USA Open Access Open Access Correspondence to: N. Meskhidze ([email protected]) Climate Climate Received: 19 July 2012 – Published in Atmos. Chem. Phys. Discuss.: 23 August 2012 of the Past of the Past Revised: 5 March 2013 – Accepted: 24 March 2013 – Published: 18 April 2013 Discussions Open Access Open Access Abstract. Knowledge of the physical characteristics and 1 Introduction Earth System chemical composition of marine organic aerosols is needed Earth System for the quantification of their effects on solar radiation trans- Dynamics Dynamics fer and cloud processes. This review examines research per- One of the largest uncertainties of the aerosol-cloud sys- Discussions tinent to the chemical composition, size distribution, mixing tem is the background concentration of natural aerosols, es- state, emission mechanism, photochemical oxidation and cli- pecially over clean marine regions where cloud condensa- Open Access Open Access matic impact of marine primary organic aerosol (POA) asso- tion nuclei (CCN) concentrationGeoscientific ranges from less than 100 Geoscientific −3 ciated with sea-spray. Numerous measurements have shown to ∼500 cm (AndreaeInstrumentation and Rosenfeld, 2008). As estimates Instrumentation that both the ambient mass concentration of marine POA and of anthropogenic forcing areMethods based on a pre-industrialand atmo- sphere composed mainly of natural aerosols, the representa- Methods and size-resolved organic mass fraction of sea-spray aerosol are Data Systems related to surface ocean biological activity. Recent studies tion of marine aerosols in climate models strongly influences Data Systems have also indicated that fine mode (smaller than 200 nm in the predictions of current and future climate effects of an- Discussions Open Access Open Access diameter) marine POA can have a size distribution indepen- thropogenic aerosols. The lower bounds of aerosol number −3 Geoscientific dent from sea-salt, while coarse mode aerosols (larger than concentration over the oceansGeoscientific (from 0 to 40 cm ) often pre- scribed in global climate models can vary the simulated in- Model Development 1000 nm in diameter) are more likely to be internally mixed Model Development with sea-salt. Modelling studies have estimated global sub- direct effect of anthropogenic aerosols by as much as 80 % Discussions micron marine POA emission rates of ∼10 ± 5 Tg yr−1, with (Hoose et al., 2009). Marine aerosols can be derived from both primary and sec- Open Access a considerable fraction of these emissions occurring over Open Access regions most susceptible to aerosol perturbations. Climate ondary processes. Sea-saltHydrology aerosols, with and estimated global Hydrology and emissions of 2000–10 000 Tg yr−1 (when limited to diame- studies have found that marine POA can cause large local Earth System Earth System increases in the cloud condensation nuclei concentration and ters less than 20 µm), were proposed to be a major compo- have a non-negligible influence on model assessments of the nent of primary marine aerosol massSciences over the regions where Sciences anthropogenic aerosol forcing of climate. Despite these signs wind speeds are high and/or other aerosol sources are weak Discussions Open Access of climate-relevance, the source strength, chemical composi- (O’Dowd et al., 1997; Murphy et al., 1998; BatesOpen Access et al., 2005; tion, mixing state, hygroscopicity, cloud droplet activation de Leeuw et al., 2011). Dimethyl sulfide (DMS)-derived sulfate was thought to be the key precursor to secondary Ocean Science potential, atmospheric aging and removal of marine POA Ocean Science remain poorly quantified. Additional laboratory, field, and marine aerosol mass over biologically-productive regions Discussions modelling studies focused on the chemistry, size distribution (Shaw, 1983; Charlson et al., 1987). Several recent reviews and mixing state of marine POA are needed to better under- addressing marine aerosols focused on their production and Open Access stand and quantify their importance. physicochemical characteristics (Lewis and Schwartz,Open Access 2004; O’Dowd and de Leeuw, 2007; de Leeuw et al., 2011), contri- Solid Earth bution to marine boundary layerSolid (MBL) Earth CCN budget (Quinn and Bates, 2011), role for cloud-precipitation interactions Discussions (Andreae and Rosenfeld, 2008), and feedbacks within the Open Access Open Access Published by Copernicus Publications on behalf of the European Geosciences Union. The Cryosphere The Cryosphere Discussions 3980 B. Gantt and N. Meskhidze: Physical and chemical characteristics of marine POA Earth system (Carslaw et al., 2010). Overall, these studies restrial and/or secondary organic aerosols as these were not suggest that ocean-derived aerosols in general and sea-spray explicitly separated in the original studies. aerosols (SSA) in particular can influence the radiation bal- ance of the atmosphere, modify cloud microphysical prop- erties and participate in chemical transformations in remote 2 Chemistry marine and coastal regions. Despite many open questions re- lated to the production mechanism, most studies agree that 2.1 Bulk aerosol concentrations a large number of SSA particles are produced through burst- ing bubbles and involve both jet and film drops. Recent stud- The first detectors of organic matter in SSA used surface ac- ies also suggested that the definition of SSA be expanded to tive nature of organics to separate them from sea-salt (Blan- include both sea-salt and primary organic matter of marine chard, 1964). Barger and Garrett (1970) collected SSA from origin. the Hawaiian coast on glass fiber filters and determined the It has been known for quite some time that large amounts concentration of chloroform extractable surface-active or- of organic matter can be incorporated in submicron SSA ganic matter to be 0.7 to 7.9 µg m−3, contributing 5 to 15 % (Blanchard, 1964). However, the mixing state of sea-salt of airborne particulate mass. Ship-borne measurements by and organics, chemical fractionation of the organic matter, Barger and Garrett (1976) in the Pacific Ocean near Galapa- and the production mechanism leading to enrichment (rel- gos Islands using the similar analytical technique were con- ative to seawater) of organics in SSA is not well charac- siderably lower, from 0.08 to 4.02 µg m−3 with the majority terised. There have been numerous measurements of the of samples having concentrations much less than 1 µg m−3 organic aerosol concentration in the clean marine areas, (the highest value of 4.02 µg m−3 was measured off the Pa- with a reported average surface concentration of ∼0.5 and cific coast of Panama). Hoffman and Duce (1974) used the ∼0.2 µg C m−3 in the Northern and Southern Hemisphere, hot persulfate-induced organic matter oxidation method of respectively (Duce, 1978; Penner, 1995). As these concen- Menzel and Vaccaro (1964) to measure an organic aerosol trations are well below that of rural continental and urban concentration in Bermuda ranging from 0.15 to 0.47 µg m−3. regions, relatively little attention has been devoted to the for- This was the first of many measurements (summarised in mation processes, chemical composition and physical prop- Fig. 1 and Supplement Table S1) of organic aerosol con- erties of marine organic aerosols. There are two well es- centrations in “clean marine” conditions having black carbon tablished production mechanisms for ocean-derived organic (BC) concentrations < 0.05 µg m−3 (Clarke, 1989). Shank et aerosol: (1) bubbles produced by breaking waves that scav- al. (2012) recently suggested that the 0.05 µg m−3 BC con- enge surface-active organic matter and other materials (e.g., centration threshold for clean marine conditions may be too bacteria, viruses and detritus) during their ascent and inject high over specific oceanic regions, as MBL organic aerosol it into the atmosphere as marine primary organic aerosols and BC concentrations were positively correlated even at (POA) upon bursting (Blanchard and Woodcock, 1957; Blan- very low (0.02 µg m−3) BC levels. This increases the uncer- chard, 1964; Barger and Garrett, 1970), and (2) oxidation of tainty associated with older measurements, as the detection phytoplankton-emitted volatile organic compounds (VOCs) limit (if measured) of BC concentrations was likely higher such as DMS, aliphatic amines, isoprene, and monoterpenes than this value. At Mace Head, Ireland, the criteria for clean which can form secondary organic aerosols (SOA) (Charl- marine conditions include onshore wind direction, BC con- son et al., 1987; Bates et al., 1992; Bonsang et al., 1992; centration <