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Primary and Secondary Organic Marine Aerosol and Oceanic Biological Activity: Recent Results and New Perspectives for Future Studies

Primary and Secondary Organic Marine Aerosol and Oceanic Biological Activity: Recent Results and... Hindawi Publishing Corporation Advances in Meteorology Volume 2010, Article ID 310682, 10 pages doi:10.1155/2010/310682 Research Article Primary and Secondary Organic Marine Aerosol and Oceanic Biological Activity: Recent Results and New Perspectives for Future Studies 1 1 1 1 1 Matteo Rinaldi, Stefano Decesari, Emanuela Finessi, Lara Giulianelli, Claudio Carbone, 1 2 2 1 Sandro Fuzzi, Colin D. O’Dowd, Darius Ceburnis, and Maria Cristina Facchini Institute of Atmospheric Sciences and Climate, National Research Council, Via P. Gobetti 101, 40129 Bologna, Italy School of Physics and Centre for Climate and Air Pollution Studies, Environmental Change Institute, National University of Ireland, University Road, Galway, Ireland Correspondence should be addressed to Matteo Rinaldi, m.rinaldi@isac.cnr.it Received 15 February 2010; Accepted 6 April 2010 Academic Editor: Markus D. Petters Copyright © 2010 Matteo Rinaldi et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. One of the most important natural aerosol systems at the global level is marine aerosol that comprises both organic and inorganic components of primary and secondary origin. The present paper reviews some new results on primary and secondary organic marine aerosol, achieved during the EU project MAP (Marine Aerosol Production), comparing them with those reported in the recent literature. Marine aerosol samples collected at the coastal site of Mace Head, Ireland, show a chemical composition trend that is influenced by the oceanic biological activity cycle, in agreement with other observations. Laboratory experiments show that sea- spray aerosol from biologically active sea water can be highly enriched in organics, and the authors highlight the need for further studies on the atmospheric fate of such primary organics. With regard to the secondary fraction of organic aerosol, the average chemical composition and molecular tracer (methanesulfonic-acid, amines) distribution could be successfully characterized by adopting a multitechnique analytical approach. 1. Introduction In recent years, particular interest has focused on the marine aerosol organic fraction, its biogenic origin and The literature contains a great deal of evidence that large the possible sources and mechanisms responsible for the sectors of the marine atmosphere are influenced by continen- high concentrations of organics observed in the submicron tal outflows (natural or anthropogenic) and by ship exhaust size fraction [6–8]. Figure 1 summarizes schematically the emissions [1, 2]. However, the ocean is an important source main potential formation pathways of organic aerosol in the of fine particles, and in background marine regions aerosol marine boundary layer (MBL). Marine aerosol can derive populations are dominated by natural marine particles [3, 4]. both from primary or secondary processes. Primary aerosol Given the ocean’s extension, marine aerosol constitutes one production derives from the interaction of wind with the of the most important natural aerosol systems at the global ocean surface and results in the mechanical production level. It contributes significantly to the Earth’s radiative of sea spray aerosol. Traditionally, sea spray has been budget, biogeochemical cycling, with impacts on ecosystems assumed to be composed of sea salt and water, with water and also on regional air quality [5]. The knowledge of reaching the equilibrium with the vapor phase after ejection. particle chemical composition, as a function of size, is Nevertheless, the hypothesis that sea spray may become necessary for understanding and predicting the marine enriched in organic matter (OM) when the sea surface is aerosol properties relevant to climate, for example, their characterized by high concentrations of biogenic OM, dates ability to act as cloud condensation nuclei (CCN) and to influence the cloud droplet number concentration (CDNC) back to the 1960s [9]. The result of the said process is an over background ocean regions. internally mixed primary marine aerosol composed of sea 2 Advances in Meteorology POA oxidation SOA NPF Liquid phase reactions Oxidation POA-containing Condensation onto pre- sea-spray existing particles BVOCs Surface film Degradation of organic surface film DOC, POC Emission of LMW metabolites Figure 1: Diagram summarizing primary and secondary organic aerosol main formation routes in the marine boundary layer. DOC, POC and POA stand for Dissolved Organic Carbon, Particulate Organic Carbon and Primary Organic Aerosol, respectively salt and organics, in which the organic fraction can be a significantly to the submicrometer aerosol mass. Their results major component [10]. are consistent with the evidence that cloud condensation Secondary organic aerosol (SOA) can form in the MBL nuclei (CCN) concentration in remote marine regions through anumberofdifferent processes. Biogenic volatile follows a seasonal trend, with maxima in spring-summer organic compounds (BVOCs), emitted by the sea surface, [18] and with the more recent findings of Sorooshian et al. or their oxidation products, can be involved in new particle [19], who observed increased average CCN activity during formation (NPF) events via nucleation of stable clusters periods of higher chlorophyll-a levels, probably as a result of of 0.5–1 nm in size (such clusters can grow to larger sizes aerosol size distribution and composition changes over the via condensation/coagulation processes). BVOCs and related North Pacific Ocean. oxidation products can also condense on preexisting particles During the EU Project MAP (Marine Aerosol Produc- and droplets, contributing to the particulate mass. SOA can tion; http://macehead.nuigalway.ie/map/) coastal and open also derive from the chemical transformation of primary ocean aerosol measurements, together with field-lab exper- or secondary components present in the condensed phase. iments, were carried out to achieve a better understanding Such transformations may take place at the particle surface of marine organic aerosol sources, chemical properties and [11, 12] or in the aqueous phase [13, 14], and may also effects on the climate system and on atmospheric chemistry. involve a further step through the gas phase, in which In the present paper, some of the main MAP results semivolatile aerosol components can be oxidized to form are discussed, and compared with parallel results recently new condensable products. The best known SOA component published in the literature. In particular, the observed in marine aerosol is methanesulfonic acid (MSA), resulting aerosol chemical composition seasonal trend and a WSOC from the atmospheric oxidation of dimethylsulphide (DMS) chemical composition representative of the HBA period, [15, 16]. Very recently, other formation processes, involving never published before, are presented. different precursors, such as biogenic isoprene [7], have been postulated. In spite of this, the observed high concen- 2. Experimental Approach trations of oxidized OM in marine aerosol largely remain unexplained, suggesting that other formation processes and In the MAP framework, marine aerosol samples were col- alternative SOA components should be considered. lected at Mace Head Atmospheric Research Station. Located To date, the most complete size segregated chemical on the west coast of Ireland, the station is unique in Europe, characterisation of unperturbed marine aerosols is that offering westerly exposure to the North Atlantic Ocean provided by O’Dowd et al. [6] and Cavalli et al. [17], and the opportunity to study atmospheric composition based on measurements performed at Mace Head (Ireland). under Northern Hemispheric background conditions. The They show that marine aerosol chemical composition is site location, at 53 degrees 20 minutes N, 9 degrees 54 influenced by the oceanic yearly biological cycle and that, minutes W, is in the path of the mid-latitude cyclones which during periods of high biological oceanic activity (HBA), frequently traverse the North Atlantic. The main Atlantic the organic fraction (mainly water insoluble) can contribute shipping routes are over 150 km away, while the transatlantic Advances in Meteorology 3 air corridors are over 80 km away. The site characteristics Table 1: Median, minimum and maximum (in brackets) relative contribution of the main marine aerosol components to the are ideal for carrying out marine background aerosol and analyzed total mass, expressed as percentages. Median values are trace gas measurements. The sampling took place through- reported only when greater than zero. “n” indicates the number of out 2006, while, during an intensive observation period, samples. coinciding with peak oceanic biological activity (June-July 2006), measurements were also performed onboard the [%] HBA (n = 5) LBA (n = 7) oceanographic vessel Celtic Explorer sailing off the Irish −2 nssSO 50 (38–57) 22 (5–27) coast. NH 7 (6–9) 1 (0–3) Details on the adopted clean sector aerosol sampling NO (0–1) 1 (1–2) strategy and instrumentation can be found in previously WSOM 23 (11–33) 6 (0–11) published papers [20, 21]. Laboratory experiments for sea salt 20 (6–25) 65 (59–77) the production of artificial sea spray aerosol from highly −3 WIOM 7 (2–10) 6 (2–17) biologically active ([chlorophyll-a] = 1.4 ± 0.8 mg m ), freshly collected, sea water were performed onboard the Celtic Explorer. Full details on the experiment, including the sea water chemical characterization, and the sample analysis Parallel laboratory experiments during the same project are described in [22]. [22] showed that nascent submicron marine organics from A complete suite of chemical characterization techniques bubble bursting mainly comprise (94%) WIOM. Moreover, were applied to both ambient and laboratory aerosol sam- the pattern of WIOM and sea-salt content in the different ples: ion chromatography (IC), for the determination of size intervals observed in the laboratory experiments was inorganic water soluble ions, amines and organic acids, and similar to that measured in atmospheric marine aerosol solid/liquid phase elemental analyses, for the determination samples collected during periods of HBA, thus pointing of water soluble organic carbon (WSOC), water soluble to a WIOM/sea-salt fingerprint associated with submicron organic nitrogen (WSON) and water insoluble organic primary marine aerosol production in biologically rich carbon (WIOC). Full details on sample handling and analysis waters. The indirect consequence of this observation is that can be found in [20, 21]. WSOM observed in HBA will derive mainly from secondary The organic chemical characterization was achieved processes. A secondary formation route for WSOM is also through proton nuclear magnetic resonance ( HNMR) supported by the findings of a recent experiment performed spectroscopy [21–23] and by the anion-exchange high per- at Mace Head [25], in which downward fluxes, characteristic formance liquid chromatography (HPLC-TOC) technique of chemical species forming through secondary processes, −2 described by Mancinelli et al. [24]. Using HPLC-TOC, it is were measured for submicron aerosol nssSO and WSOM. possible to speciate WSOC into four macroclasses: neutral- The seasonal trend of the main component concentra- basic compounds (NB), mono-acids (MA), di-acids (DA) tions in submicron size range exhibits maxima in spring and poly-acids (PA, representative of humic-like substances), and summer (HBA) and minima during winter (LBA), with and to quantify each fraction in terms of organic carbon the exception of sea salt (Figure 2), in good agreement content. with Mace Head aerosol climatology for the 2002–2004 Here, the acronym WSOM (water soluble organic mat- period [26], thus suggesting a dependence of submicron ter) is used to indicate the estimated mass of WSOC, aerosol chemical composition on the seasonal cycle of the obtained multiplying WSOC by a conversion factor of 1.8, North Atlantic biological activity. Similar results showing derived from the functional group composition of WSOC maximum concentration in spring-summer in conjunction [21]. Similarly, WIOM (water insoluble organic matter) was with phytoplankton activity in surface sea water, have obtained by multiplying WIOC by a conversion factor of 1.4, been reported by several investigators for MSA [27, 28] −2 according to the functional group composition observed by and nssSO [29]. The maxima observed in atmospheric 1 −2 + H NMR in sea spray organic aerosols [22]. concentrations for nssSO ,MSA andNH can be attributed 4 4 to the increase in the emission of gaseous precursors, mainly DMS [16, 30]and NH [31], produced by the marine biota during the HBA period, and to the concurrent enhanced 3. Marine Aerosol Chemical Composition photochemical activity of the atmosphere [32]. In analogy, the WSOC spring-summer peak can be attributed to the during the 1-Year Sampling Campaign increased emission of volatile organic compounds (VOCs) at Mace Head by the marine biota and to the concurrently enhanced Figure 2 shows the chemical composition of the submicron photo-oxidative capacity of the atmosphere, generating low aerosol samples collected during 2006 at Mace Head. Table 1 vapor pressure oxidation products which can condense on reports the percentage contribution of each of the main preexisting particles. Another potential path for WSOC submicron aerosol components, in the HBA and LBA (low production could be through the aging process of the biological activity) periods. Marine aerosol mainly com- insoluble primary fraction, obviously more efficient during −2 + prised a mixture of sea salt of primary origin, nssSO ,NH , period of high photochemical activity. 4 4 NO , clearly secondary components, and soluble (WSOM) Submicron aerosol chemical composition is different and insoluble (WIOM) organic compounds. during HBA with respect to the LBA period. During HBA the 4 Advances in Meteorology −3 1.5 comparable (∼0.2 μgm ), suggesting a lower influence of LBA HBA LBA the primary source in MAP samples. Sciare et al. [33] also reported marked seasonal trends for marine aerosol collected at Amsterdam Island (Southern Indian Ocean). WIOC, MSA and nMSA-WSOC (WSOC not deriving from MSA) showed concentration enhancement 0.5 during the austral summer. Moreover, it was found that marine aerosol organics were mainly accounted for by WIOC, in agreement with the previous observation in the North Atlantic [6]. The investigators also pointed out the likely biogenic origin of marine aerosol organics, evidencing its main source in a very productive oceanic area located around 40 S. It must be concluded that submicron marine aerosol chemical composition can be extremely variable over the year and, probably, from year to year, depending Sampling interval Sea salt Ammonium on the predominance of the primary source with respect Nitrate WSOM to secondary ones, ocean dynamic conditions, influence of nss-sulphate WIOM different oceanic source regions and atmospheric photo- chemical activity. These studies demonstrate the importance Figure 2: Seasonal evolution of submicron marine aerosol chemical of biogenic organic aerosols over the ocean, at high latitudes composition observed through the twelve samples collected at ◦ ◦ (<40 Sand >40 N), during periods of high biological Mace Head during MAP. The horizontal axis reports the nominal productivity. sampling time for each sample, that is, the time during which the filter/substrate has been exposed (the actual sampling time In the following paragraphs, the most recent findings depended on the occurrence of the clean sector conditions during on primary and secondary biogenic organics in submicron the exposition time). Samples are grouped in HBA and LBA period marine aerosol are discussed. to evidence the differences between the two periods. 4. Primary Organic Aerosol and Its Evolution in theMarineBoundaryLayer −2 greater part of the mass was accounted for by nssSO and −2 WSOM: nssSO median contribution to the total analyzed Several attempts to quantify and characterize sea spray mass was 50% (ranging from 38 to 57%), that of WSOM organics have recently been carried out. Keene et al. [34] 23% (11%–33%). Conversely, in the LBA period sea salt reported high enrichment factors for water soluble organics, accounts for the greater part of the analyzed submicron mass, in nascent lab-produced sea spray particles, with respect to with a median contribution of 65% (59%–77%), while the sea water. WSOC was highly enriched in all aerosol size −2 contributions of nssSO andWSOMare reducedto22% fractions and the greatest enrichments were associated with (5%–27%) and 6% (0%–11%), respectively. Water insoluble the smallest size fraction (about 80% of aerosol mass was organics contributed almost equally to the analyzed total organic at 0.13 μm). The authors concluded that bursting submicron mass during the HBA and LBA periods. bubbles at the ocean surface produce significant numbers Submicron organics were clearly dominated by WSOM of subμm, hygroscopic, organic-dominated aerosols, thereby during the HBA period, while the contribution of soluble and supporting the hypothesis that this pathway is a potentially insoluble organic compounds was comparable during the important global source of climate relevant particles. LBA period. This picture of marine aerosol is different from Facchini et al. [22] similarly reported a high contribution the one reported by O’Dowd et al. [6], who observed at Mace of organic matter in nascent submicron sea spray particles, Head a submicron aerosol chemical composition dominated up to 77 ± 5% in the 0.125–0.25 μmsizerange (Table 2), by water insoluble organic species during the HBA period. although their analysis discriminated between water soluble Such discrepancy could be due to a different location of and insoluble organic carbon, finding a dominant contribu- highly biologically productive waters with respect to the tion of WIOM (up to 94 ± 4% of OC in the 0.125–0.25 μm Irish coast during MAP [21], or to different meteorological size range). Moreover, Facchini et al. [22] highlighted that conditions encountered in the sampling periods: most of sea spray organics tend to aggregate and form colloids or the samples discussed in the present work were collected in suspended particles, making the definition of water solubility summer, when the photochemical activity is at its maximum, a complex issue. Whether the difference in the results of the while most of the 2002 samples reported in O’Dowd et two experiments is attributable only to the different organic al. [6] were collected during spring and autumn, when sea carbon measurement approach, or also to differences in the spray production is higher. The main difference between the chemical properties of the sea water used for generating two datasets, indeed, regards WIOM absolute concentration aerosol particles by bubble bursting (oligotrophic Sargasso −3 during the HBA period (∼0.6 μgm in 2002 and less than Sea versus North Atlantic Ocean during algal bloom) is still −3 0.1 μgm during MAP, averagely), while WSOM one is an issue of debate. −3 (μgm ) 11–18 Jan 06 18–22 Jan 06 10–20 Feb 06 29 Mar–04 Apr 06 12–26 Apr 06 12–19 Jun 06 19–28 Jun 06 28 Jun–05 Jul 06 03–08 Sep 06 05–11 Oct 06 15–22 Nov 06 04–11 Dec 06 Advances in Meteorology 5 Furthermore, Modini et al. [35] presented the results of between primary and secondary organic aerosol components a similar experiment in which the organic volume contri- were also provided by Jimenez et al. [41], who showed, in bution in lab-produced sea spray particles, indirectly deter- a recent chamber experiment, how aerosolized squalane, a mined by volatility/hygroscopicity tandem measurements proxy for the refractory fraction of primary marine organic (HV-TDMA), was estimated to be (8 ± 6%) in the 71–77 nm aerosol, was subjected to photochemical ageing, showing size range, corresponding to a mass contribution of only 4%. mass spectral features progressively transforming into those Such results may be conditioned by the interpretation of HV- of oxidized organic aerosols, which are ubiquitous in the TDMA measurements to calculate the organic fraction, or atmosphere. by the use of coastal waters (potentially high in terrestrial runoff ) for spray generation. However, they could also be evidence of a high system variability, stressing the necessity 5. Advances in Marine SOA Chemical forfurtherinvestigation. Characterization Several papers have reported the presence of carbo- hydrate-like material in marine particles, attributing this to New results on marine WSOC chemical composition have primary sea spray processes. been obtained over past years, allowing the identification of Bigg and Leck [36] observed the presence of complex typical marine SOA components, other than MSA and DMS structures behaving as lipopolysaccharides in submicron oxidation products. marine aerosol. Facchini et al. [22] evidenced the presence The presence of amines and aminoacids over the oceans of hydroxyl groups, both in water soluble and insoluble sea has been sporadically reported since the 1980s in rain spray OM, using HNMR analyses. These hydroxyl signals samples over the ocean [42–44]. Gibb et al. [45] reported the were always associated in the NMR spectra to important presence of monomethylammonium (MMA ), dimethylam- + + signals due to aliphatic chains with terminal methyls, typical monium (DMA ) and trimethylammonium (TMA ) salts in of lipids. Moreover, the HNMR spectra of oceanic water aerosol particles collected in unpolluted conditions over the closely resembled that of nascent aerosol, and were in agree- Arabian Sea. The authors attributed the presence of aerosol ment with several observations in the literature reporting the phase alkyl ammonium salts to secondary production, due presence in oceanic waters of phytoplankton exudates with a to the condensation of gaseous alkyl amines emitted by the composition dominated by lipopolysaccharides [37, 38]. sea, in analogy with NH . More recently, this hypothesis has Very recently Russell et al. [39]observedanocean- been strengthened by evidence that alkyl amines participate derived component, in marine aerosol, dominated by in SOA formation in many different environments through carbohydrate-like material, based on multi-technique mea- reaction with acids [46–48]. surements of submicron marine aerosol over the North Facchini et al. [20] highlighted the importance of alkyl- Atlantic and Arctic Oceans and on Positive Matrix Factor- ammonium salts as submicron marine aerosol components, ization data elaboration. According to these authors, the and reported dimethyl and diethyl-ammonium salts (DMA primary marine signal in submicron marine aerosol is made and DEA ) concentrations ranging, together between <0.4 −3 on average for 88% of hydroxyl groups. Although the low and 56 ng m over the North Atlantic Ocean during the signal-to-noise ratio of the spectra made difficult a precise HBA period, turning out to be the most abundant organic quantification of the carbohydrate-like material, HNMR species, second only to MSA, in submicron marine particles. analyses exclude a contribution as high as the one observed Alkyl-ammonium salts represented on average 11% of the by Russell et al. [39] for these components in the North marine SOA and a dominant fraction (35% on average) of Atlantic during periods of HBA. aerosol water soluble organic nitrogen (WSON). Such new, often contrasting results on primary organics The above cited paper presents considerable evidence + + in marine aerosol reflect the limits of current knowledge that DMA and DEA are secondary aerosol components, on this topic. Furthermore, the fate of primary organics in originating from biogenic precursors emitted by the ocean. the atmosphere is even more uncertain, and few data are Their size distributions exhibited maxima in the accu- available on sea spray organic oxidation routes, rates and mulation mode, as is also the case of other well known −2 + products. Zhou et al. [40] evidenced that OM in marine secondary components (nssSO ,NH , MSA), supporting 4 4 aerosols plays a dual role, being an important precur- the hypothesis that a gas-to-particle conversion process is sor/source and a dominant sink for the OH radical, leading responsible for the accumulation of alkyl-ammonium salts to the degradation of OM, and the likely production of a in the fine aerosol fraction. The most likely hypothesis is series of low-molecular weight (LMW) organic compounds. that gaseous dimethylamine and diethylamine react with Therefore, primary and secondary organic components must sulphuric acid or acidic sulphates, accumulating within be considered as closely correlated in marine aerosol, as the aerosol particles in close analogy with ammonia. Regarding oxidation products of biogenic primary organics in marine the precursor origin, a main anthropogenic source of gaseous aerosol particles can lead to the production of both oxidized alkyl-amines over the ocean can be excluded, because the + + aerosol components (belonging to the broad category of aerosol DMA and DEA concentrations measured at Mace SOA) and of volatile LMW products, which can partition Head, were always higher in clean marine samples (roughly into the gas phase and influence the multiphase photochem- double) than in polluted air masses, in analogy with MSA. ical evolution of the marine troposphere (including SOA Like other reduced biogenic gases (DMS, CH ) and in formation). Supporting evidence of this gliding boundary analogy with NH ,DMA andDEA couldbethe endproducts 3 6 Advances in Meteorology Table 2: Summary of the sea spray OM contribution measured in the most recent sea spray production laboratory experiments. Max OM mass Particle diameter Sea water sampling site Notes Reference contribution [%] [nm] Only WSOC Sargasso Sea ∼80 130 measured. No Keene et al. [34] (oligotrophic) filtration WSOC and WIOC North Atlantic Ocean 77 ± 5 125–250 measured. Facchini et al. [22] (algal bloom) Filtration. Moreton Bay (Australia) 4 71–77 Coastal water Modini et al. [35] of microbial turnover of marine labile OM [45, 49, 50]. Notwithstanding recent improvements, current knowl- Furthermore, alkyl-ammonium ions in submicron aerosol edge on the chemical composition of marine SOA remains particles showed the typical seasonal variation of biogenic limited, and further research is required to address the many components, with high concentrations measured in the HBA unresolved issues. During MAP a multi-technique approach period, and much lower concentrations in the LBA period was deployed to characterize marine WSOC. Coupling (Table 3). HPLC-TOC and IC, it was possible to achieve an almost- Table 3 summarizes the marine aerosol alkylammonium complete chemical characterization of submicron marine ion concentration data so far available: two very recent WSOC, on a selected subset of samples (5, from both papers confirm the findings of Facchini et al. [20]. Mul ¨ ler Mace Head and Celtic Explorer sampling) representative of + + et al. [51] reported monomethylammonium (MA ), DMA the HBA period (Figure 3). Marine aerosol WSOC can be and DEA at non-negligible concentrations in submicrom- divided into three chemical macroclasses based on acid-base eter particles at Cape Verde, during algal blooms in 2007, properties: neutral-basic compounds (NB), accounting for attributing them to secondary formation processes. More- 32 (±8) % of WSOC, mono-diacids (MDA), contributing over, high levels of amines were observed in coincidence 42 (±9) %, and polyacids (PA), accounting for 4 (±3) %. with high near surface Chlorophyll-a concentrations. Finally, Averagely 22 (±11) % of WSOC escaped this classification, Sorooshian et al. [19] also observed DEA in submicron probably as a result of strong and irreversible binding with particles over the North Pacific Ocean, with concentrations the HPLC column: this fraction is labeled “uncharacterized” rather well correlated to the chlorophyll-a sea surface in the Figure. From the HPLC-TOC macroclasses average concentration. contribution, the average contribution of each compound, Besides alkylammonium salts and MSA, carboxylic and identified by IC, has been subtracted, obtaining the classi- di-carboxylic acids have been identified in marine aerosol fication of Figure 3. Only 30% of WSOC was characterized [52, 53 and references therein], found to account for less at the molecular level by IC, with MSA (11 ± 5%) and than 10% of total particulate organic carbon in remote oxalic acid (3 ± 2%) being the only two MDA components marine environments. The above mentioned papers attribute identified. This leaves more than a half of the dominant class a secondary origin to detected di-carboxylic acids, citing of compounds still uncharacterized, although it is likely that oxalic acid as the most abundant one. However, oxidized other LMW dicarboxylic acids, like malonic and succinic organics, such as C –C carboxylic or di-carboxylic acids, acid, not identified by IC, can account together for another 5 10 can also be produced by the oxidative degradation of primary 1%-2%. As for the NB compounds, 6 ± 7and 10 ± 12% + + particles generated by sea spray and rich in fatty acids [52]. of the WSOC can be ascribed to DMA and DEA , leaving Recent instrumental advances have allowed a deeper about 15% of WSOC as uncharacterized NB compounds. insight into organic marine aerosol chemical composi- In WSOC extracted from marine aerosol collected during tion. Using liquid chromatography/negative ion electrospray MAP, HPLC analysis showed the occurrence of fulvic-like ionization mass spectrometry, Claeys et al. [53]inves- material (polyacids macroclass), in lower concentrations tigated marine organic aerosol chemical composition at than suggested by previous studies, that is, 22% [17]. The Amsterdam Island (Southern Indian Ocean), reporting a finding indicates that primary emissions of fulvic substances WSOC contribution of 32 ± 12% to submicron OC. About from seawater did not make a major contribution to 25% of WSOC was characterized and attributed to MSA marine water-soluble aerosols during MAP. This picture (17%–21%), oxalate (5 ± 2%), malonate (1.8 ± 0.9%) of submicron marine aerosol WSOC is coherent with the and organosulphates (0.8 ± 1.5%). The organosulphates hypothesis of its mainly secondary origin, even though characterized in Claeys et al. [53] can be considered tracers the uncharacterized fraction escaping classification in NB, for an SOA formation process that is specific to the marine MDA and PA may be due to the contribution of primarily environment, that is, oxidation of marine biomass. More emitted, aggregate forming, organic matter, similar to that specifically, the organosulfates correspond to sulfate esters characterized in laboratory experiments on nascent sea spray –C hydroxyl carboxylic acids, which are attributed to of C aerosol by Facchini et al. [22]. 9 13 oxidation of unsaturated fatty acid residues present in algal Information on the chemical composition of the unchar- cell membranes. acterized fractions of NB, MDA and PA has been derived Advances in Meteorology 7 Table 3: Alkylammonium ions aerosol concentration range (in brackets) and median value (when available) reported in the literature for −3 the marine environment. All concentrations are in ng m . All data refer to submicron particles except for Mul ¨ ler et al. [51], whosesizecut was 0.14–0.42 μm, and Gorzelska and Galloway [44], who did not report any particle size information. + −3 + −3 + −3 + −3 + −3 Location MA [ng m ]DMA [ng m ] TMA [ng m ]EA [ng m ]DEA [ng m ] Reference North Atlantic Gorzelska & (<dl–3.9) (<dl–∼1.4) Jun–Sep 1988 Galloway [44] Arabian Sea <dl–6.1 1.6–4.4 0.018–0.78 Gibb et al. [45] Aug-Oct 1994 Arabian sea 2.6–4.5 3.7–17.5 0.12–0.9 Gibb et al. [45] Nov-Dec 1994 Mace Head Facchini et al. 1(<1–8) (<1–12) Oct–Mar 2006 [20] Mace Head Facchini et al. 10 (2–24) 16 (4–32) Apr–Sep 2006 [20] North Atlantic Facchini et al. 9 (4–13) 12 (7–24) Jun 2006 [20] Cape Verde May 0.06 Mul ¨ ler et al. 0.02 (0.01–0.03) 0.21(0.13–0.36) 2007 (0.005–0.11) [51] Cape Verde Jun Muller et al. 0.03 (0.01–0.12) 0.21(0.05–0.39) 0.07 (0.06–0.14) 2007 [51] Cape Verde Dec 0.15 Mul ¨ ler et al. 0.54 (0.1–1.4) 0.29 (0.09–0.76) 2007 (0.002–0.52) [51] North Pacific Sorooshian et al. 14–35 Jul-Aug 2007 [19] DMA in submicron marine aerosol chemical composition over 6% biologically productive, high latitude, marine regions, in DEA both hemispheres. Moreover, it has been demonstrated that Uncharacterized 10% 22% marine organic aerosol chemical composition is the complex result of different primary and secondary sources. Most recent results on sea spray composition suggest NB that in conditions of intense oceanic biological productivity, PA Uncharacterized submicron primary marine aerosol can contain a consid- 4% NB 16% erable fraction of OM. Further studies are necessary to obtain deeper insight into the space/time variability of the MDA ocean primary organics production potential worldwide. Important advances can be obtained by coupling modeling MSA with new satellite chlorophyll, dissolved and particulate 11% Uncharacterized MDA organic carbon measurement instruments, as attempted for Oxalic acid 28% the first time by O’Dowd et al. [54] and Vignati et al. [4]. 3% In fact, although much information has been gathered on Figure 3: WSOC chemical composition representative of spring- the DMS oxidation cycle, and several predictive tools are summer conditions over the Atlantic Ocean, obtained by combining available to model secondary products, like MSA and nss- HPLC-TOC and IC (see text for more details). Percentages indicate sulfate over the oceans, only raw empiric instruments are the contribution of each compound or chemical macroclass in available to predict primary organic aerosol emissions as a terms of carbon. function of oceanic biological productivity. To date, little is known about sea spray organic chemical composition, lifetime and fate in the marine boundary layer. by NMR functional group analysis (Decesari et al., in Further investigation is required to address this issue, that preparation), showing aliphatic moieties substituted with can also help to fill the gap between observed and modeled oxygenated groups, like carbonyls/carboxyls and, in analogy SOA in the MBL. with the findings of Russell et al. [39], hydroxyl groups. As for secondary organics in the MBL, although several classes of compounds have been identified in different marine environments as typical marine SOA components 6. Conclusions (MSA, alkylammonium salts, dicarboxylic acids), most marine aerosol WSOC remains uncharacterized at the Studies performed during the past years strongly suggest that biogenic organic compounds play an important role molecular level. Closer investigation of marine aerosol 8 Advances in Meteorology WSOC chemical composition is needed to achieve a better [10] C. Oppo, S. Bellandi, N. Degli Innocenti, et al., “Surfactant components of marine organic matter as agents for biogeo- knowledge on SOA formation routes in the MBL. Deeper chemical fractionation and pollutant transport via marine insight into marine aerosol organics chemical composition aerosols,” Marine Chemistry, vol. 63, no. 3-4, pp. 235–253, is expected from the new high time resolution aerosol measurement instrumentats, namely AMS, only seldom [11] T. L. Eliason, J. B. Gilman, and V. Vaida, “Oxidation of applied to the clean MBL so far [55–57]. organic films relevant to atmospheric aerosols,” Atmospheric Furthermore, an important fraction of marine SOA, Environment, vol. 38, no. 9, pp. 1367–1378, 2004. WSON, is still mostly uncharacterized. A fraction of the [12] S. F. Maria, L. M. Russell, M. K. Gilles, and S. C. B. 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Primary and Secondary Organic Marine Aerosol and Oceanic Biological Activity: Recent Results and New Perspectives for Future Studies

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Hindawi Publishing Corporation Advances in Meteorology Volume 2010, Article ID 310682, 10 pages doi:10.1155/2010/310682 Research Article Primary and Secondary Organic Marine Aerosol and Oceanic Biological Activity: Recent Results and New Perspectives for Future Studies 1 1 1 1 1 Matteo Rinaldi, Stefano Decesari, Emanuela Finessi, Lara Giulianelli, Claudio Carbone, 1 2 2 1 Sandro Fuzzi, Colin D. O’Dowd, Darius Ceburnis, and Maria Cristina Facchini Institute of Atmospheric Sciences and Climate, National Research Council, Via P. Gobetti 101, 40129 Bologna, Italy School of Physics and Centre for Climate and Air Pollution Studies, Environmental Change Institute, National University of Ireland, University Road, Galway, Ireland Correspondence should be addressed to Matteo Rinaldi, m.rinaldi@isac.cnr.it Received 15 February 2010; Accepted 6 April 2010 Academic Editor: Markus D. Petters Copyright © 2010 Matteo Rinaldi et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. One of the most important natural aerosol systems at the global level is marine aerosol that comprises both organic and inorganic components of primary and secondary origin. The present paper reviews some new results on primary and secondary organic marine aerosol, achieved during the EU project MAP (Marine Aerosol Production), comparing them with those reported in the recent literature. Marine aerosol samples collected at the coastal site of Mace Head, Ireland, show a chemical composition trend that is influenced by the oceanic biological activity cycle, in agreement with other observations. Laboratory experiments show that sea- spray aerosol from biologically active sea water can be highly enriched in organics, and the authors highlight the need for further studies on the atmospheric fate of such primary organics. With regard to the secondary fraction of organic aerosol, the average chemical composition and molecular tracer (methanesulfonic-acid, amines) distribution could be successfully characterized by adopting a multitechnique analytical approach. 1. Introduction In recent years, particular interest has focused on the marine aerosol organic fraction, its biogenic origin and The literature contains a great deal of evidence that large the possible sources and mechanisms responsible for the sectors of the marine atmosphere are influenced by continen- high concentrations of organics observed in the submicron tal outflows (natural or anthropogenic) and by ship exhaust size fraction [6–8]. Figure 1 summarizes schematically the emissions [1, 2]. However, the ocean is an important source main potential formation pathways of organic aerosol in the of fine particles, and in background marine regions aerosol marine boundary layer (MBL). Marine aerosol can derive populations are dominated by natural marine particles [3, 4]. both from primary or secondary processes. Primary aerosol Given the ocean’s extension, marine aerosol constitutes one production derives from the interaction of wind with the of the most important natural aerosol systems at the global ocean surface and results in the mechanical production level. It contributes significantly to the Earth’s radiative of sea spray aerosol. Traditionally, sea spray has been budget, biogeochemical cycling, with impacts on ecosystems assumed to be composed of sea salt and water, with water and also on regional air quality [5]. The knowledge of reaching the equilibrium with the vapor phase after ejection. particle chemical composition, as a function of size, is Nevertheless, the hypothesis that sea spray may become necessary for understanding and predicting the marine enriched in organic matter (OM) when the sea surface is aerosol properties relevant to climate, for example, their characterized by high concentrations of biogenic OM, dates ability to act as cloud condensation nuclei (CCN) and to influence the cloud droplet number concentration (CDNC) back to the 1960s [9]. The result of the said process is an over background ocean regions. internally mixed primary marine aerosol composed of sea 2 Advances in Meteorology POA oxidation SOA NPF Liquid phase reactions Oxidation POA-containing Condensation onto pre- sea-spray existing particles BVOCs Surface film Degradation of organic surface film DOC, POC Emission of LMW metabolites Figure 1: Diagram summarizing primary and secondary organic aerosol main formation routes in the marine boundary layer. DOC, POC and POA stand for Dissolved Organic Carbon, Particulate Organic Carbon and Primary Organic Aerosol, respectively salt and organics, in which the organic fraction can be a significantly to the submicrometer aerosol mass. Their results major component [10]. are consistent with the evidence that cloud condensation Secondary organic aerosol (SOA) can form in the MBL nuclei (CCN) concentration in remote marine regions through anumberofdifferent processes. Biogenic volatile follows a seasonal trend, with maxima in spring-summer organic compounds (BVOCs), emitted by the sea surface, [18] and with the more recent findings of Sorooshian et al. or their oxidation products, can be involved in new particle [19], who observed increased average CCN activity during formation (NPF) events via nucleation of stable clusters periods of higher chlorophyll-a levels, probably as a result of of 0.5–1 nm in size (such clusters can grow to larger sizes aerosol size distribution and composition changes over the via condensation/coagulation processes). BVOCs and related North Pacific Ocean. oxidation products can also condense on preexisting particles During the EU Project MAP (Marine Aerosol Produc- and droplets, contributing to the particulate mass. SOA can tion; http://macehead.nuigalway.ie/map/) coastal and open also derive from the chemical transformation of primary ocean aerosol measurements, together with field-lab exper- or secondary components present in the condensed phase. iments, were carried out to achieve a better understanding Such transformations may take place at the particle surface of marine organic aerosol sources, chemical properties and [11, 12] or in the aqueous phase [13, 14], and may also effects on the climate system and on atmospheric chemistry. involve a further step through the gas phase, in which In the present paper, some of the main MAP results semivolatile aerosol components can be oxidized to form are discussed, and compared with parallel results recently new condensable products. The best known SOA component published in the literature. In particular, the observed in marine aerosol is methanesulfonic acid (MSA), resulting aerosol chemical composition seasonal trend and a WSOC from the atmospheric oxidation of dimethylsulphide (DMS) chemical composition representative of the HBA period, [15, 16]. Very recently, other formation processes, involving never published before, are presented. different precursors, such as biogenic isoprene [7], have been postulated. In spite of this, the observed high concen- 2. Experimental Approach trations of oxidized OM in marine aerosol largely remain unexplained, suggesting that other formation processes and In the MAP framework, marine aerosol samples were col- alternative SOA components should be considered. lected at Mace Head Atmospheric Research Station. Located To date, the most complete size segregated chemical on the west coast of Ireland, the station is unique in Europe, characterisation of unperturbed marine aerosols is that offering westerly exposure to the North Atlantic Ocean provided by O’Dowd et al. [6] and Cavalli et al. [17], and the opportunity to study atmospheric composition based on measurements performed at Mace Head (Ireland). under Northern Hemispheric background conditions. The They show that marine aerosol chemical composition is site location, at 53 degrees 20 minutes N, 9 degrees 54 influenced by the oceanic yearly biological cycle and that, minutes W, is in the path of the mid-latitude cyclones which during periods of high biological oceanic activity (HBA), frequently traverse the North Atlantic. The main Atlantic the organic fraction (mainly water insoluble) can contribute shipping routes are over 150 km away, while the transatlantic Advances in Meteorology 3 air corridors are over 80 km away. The site characteristics Table 1: Median, minimum and maximum (in brackets) relative contribution of the main marine aerosol components to the are ideal for carrying out marine background aerosol and analyzed total mass, expressed as percentages. Median values are trace gas measurements. The sampling took place through- reported only when greater than zero. “n” indicates the number of out 2006, while, during an intensive observation period, samples. coinciding with peak oceanic biological activity (June-July 2006), measurements were also performed onboard the [%] HBA (n = 5) LBA (n = 7) oceanographic vessel Celtic Explorer sailing off the Irish −2 nssSO 50 (38–57) 22 (5–27) coast. NH 7 (6–9) 1 (0–3) Details on the adopted clean sector aerosol sampling NO (0–1) 1 (1–2) strategy and instrumentation can be found in previously WSOM 23 (11–33) 6 (0–11) published papers [20, 21]. Laboratory experiments for sea salt 20 (6–25) 65 (59–77) the production of artificial sea spray aerosol from highly −3 WIOM 7 (2–10) 6 (2–17) biologically active ([chlorophyll-a] = 1.4 ± 0.8 mg m ), freshly collected, sea water were performed onboard the Celtic Explorer. Full details on the experiment, including the sea water chemical characterization, and the sample analysis Parallel laboratory experiments during the same project are described in [22]. [22] showed that nascent submicron marine organics from A complete suite of chemical characterization techniques bubble bursting mainly comprise (94%) WIOM. Moreover, were applied to both ambient and laboratory aerosol sam- the pattern of WIOM and sea-salt content in the different ples: ion chromatography (IC), for the determination of size intervals observed in the laboratory experiments was inorganic water soluble ions, amines and organic acids, and similar to that measured in atmospheric marine aerosol solid/liquid phase elemental analyses, for the determination samples collected during periods of HBA, thus pointing of water soluble organic carbon (WSOC), water soluble to a WIOM/sea-salt fingerprint associated with submicron organic nitrogen (WSON) and water insoluble organic primary marine aerosol production in biologically rich carbon (WIOC). Full details on sample handling and analysis waters. The indirect consequence of this observation is that can be found in [20, 21]. WSOM observed in HBA will derive mainly from secondary The organic chemical characterization was achieved processes. A secondary formation route for WSOM is also through proton nuclear magnetic resonance ( HNMR) supported by the findings of a recent experiment performed spectroscopy [21–23] and by the anion-exchange high per- at Mace Head [25], in which downward fluxes, characteristic formance liquid chromatography (HPLC-TOC) technique of chemical species forming through secondary processes, −2 described by Mancinelli et al. [24]. Using HPLC-TOC, it is were measured for submicron aerosol nssSO and WSOM. possible to speciate WSOC into four macroclasses: neutral- The seasonal trend of the main component concentra- basic compounds (NB), mono-acids (MA), di-acids (DA) tions in submicron size range exhibits maxima in spring and poly-acids (PA, representative of humic-like substances), and summer (HBA) and minima during winter (LBA), with and to quantify each fraction in terms of organic carbon the exception of sea salt (Figure 2), in good agreement content. with Mace Head aerosol climatology for the 2002–2004 Here, the acronym WSOM (water soluble organic mat- period [26], thus suggesting a dependence of submicron ter) is used to indicate the estimated mass of WSOC, aerosol chemical composition on the seasonal cycle of the obtained multiplying WSOC by a conversion factor of 1.8, North Atlantic biological activity. Similar results showing derived from the functional group composition of WSOC maximum concentration in spring-summer in conjunction [21]. Similarly, WIOM (water insoluble organic matter) was with phytoplankton activity in surface sea water, have obtained by multiplying WIOC by a conversion factor of 1.4, been reported by several investigators for MSA [27, 28] −2 according to the functional group composition observed by and nssSO [29]. The maxima observed in atmospheric 1 −2 + H NMR in sea spray organic aerosols [22]. concentrations for nssSO ,MSA andNH can be attributed 4 4 to the increase in the emission of gaseous precursors, mainly DMS [16, 30]and NH [31], produced by the marine biota during the HBA period, and to the concurrent enhanced 3. Marine Aerosol Chemical Composition photochemical activity of the atmosphere [32]. In analogy, the WSOC spring-summer peak can be attributed to the during the 1-Year Sampling Campaign increased emission of volatile organic compounds (VOCs) at Mace Head by the marine biota and to the concurrently enhanced Figure 2 shows the chemical composition of the submicron photo-oxidative capacity of the atmosphere, generating low aerosol samples collected during 2006 at Mace Head. Table 1 vapor pressure oxidation products which can condense on reports the percentage contribution of each of the main preexisting particles. Another potential path for WSOC submicron aerosol components, in the HBA and LBA (low production could be through the aging process of the biological activity) periods. Marine aerosol mainly com- insoluble primary fraction, obviously more efficient during −2 + prised a mixture of sea salt of primary origin, nssSO ,NH , period of high photochemical activity. 4 4 NO , clearly secondary components, and soluble (WSOM) Submicron aerosol chemical composition is different and insoluble (WIOM) organic compounds. during HBA with respect to the LBA period. During HBA the 4 Advances in Meteorology −3 1.5 comparable (∼0.2 μgm ), suggesting a lower influence of LBA HBA LBA the primary source in MAP samples. Sciare et al. [33] also reported marked seasonal trends for marine aerosol collected at Amsterdam Island (Southern Indian Ocean). WIOC, MSA and nMSA-WSOC (WSOC not deriving from MSA) showed concentration enhancement 0.5 during the austral summer. Moreover, it was found that marine aerosol organics were mainly accounted for by WIOC, in agreement with the previous observation in the North Atlantic [6]. The investigators also pointed out the likely biogenic origin of marine aerosol organics, evidencing its main source in a very productive oceanic area located around 40 S. It must be concluded that submicron marine aerosol chemical composition can be extremely variable over the year and, probably, from year to year, depending Sampling interval Sea salt Ammonium on the predominance of the primary source with respect Nitrate WSOM to secondary ones, ocean dynamic conditions, influence of nss-sulphate WIOM different oceanic source regions and atmospheric photo- chemical activity. These studies demonstrate the importance Figure 2: Seasonal evolution of submicron marine aerosol chemical of biogenic organic aerosols over the ocean, at high latitudes composition observed through the twelve samples collected at ◦ ◦ (<40 Sand >40 N), during periods of high biological Mace Head during MAP. The horizontal axis reports the nominal productivity. sampling time for each sample, that is, the time during which the filter/substrate has been exposed (the actual sampling time In the following paragraphs, the most recent findings depended on the occurrence of the clean sector conditions during on primary and secondary biogenic organics in submicron the exposition time). Samples are grouped in HBA and LBA period marine aerosol are discussed. to evidence the differences between the two periods. 4. Primary Organic Aerosol and Its Evolution in theMarineBoundaryLayer −2 greater part of the mass was accounted for by nssSO and −2 WSOM: nssSO median contribution to the total analyzed Several attempts to quantify and characterize sea spray mass was 50% (ranging from 38 to 57%), that of WSOM organics have recently been carried out. Keene et al. [34] 23% (11%–33%). Conversely, in the LBA period sea salt reported high enrichment factors for water soluble organics, accounts for the greater part of the analyzed submicron mass, in nascent lab-produced sea spray particles, with respect to with a median contribution of 65% (59%–77%), while the sea water. WSOC was highly enriched in all aerosol size −2 contributions of nssSO andWSOMare reducedto22% fractions and the greatest enrichments were associated with (5%–27%) and 6% (0%–11%), respectively. Water insoluble the smallest size fraction (about 80% of aerosol mass was organics contributed almost equally to the analyzed total organic at 0.13 μm). The authors concluded that bursting submicron mass during the HBA and LBA periods. bubbles at the ocean surface produce significant numbers Submicron organics were clearly dominated by WSOM of subμm, hygroscopic, organic-dominated aerosols, thereby during the HBA period, while the contribution of soluble and supporting the hypothesis that this pathway is a potentially insoluble organic compounds was comparable during the important global source of climate relevant particles. LBA period. This picture of marine aerosol is different from Facchini et al. [22] similarly reported a high contribution the one reported by O’Dowd et al. [6], who observed at Mace of organic matter in nascent submicron sea spray particles, Head a submicron aerosol chemical composition dominated up to 77 ± 5% in the 0.125–0.25 μmsizerange (Table 2), by water insoluble organic species during the HBA period. although their analysis discriminated between water soluble Such discrepancy could be due to a different location of and insoluble organic carbon, finding a dominant contribu- highly biologically productive waters with respect to the tion of WIOM (up to 94 ± 4% of OC in the 0.125–0.25 μm Irish coast during MAP [21], or to different meteorological size range). Moreover, Facchini et al. [22] highlighted that conditions encountered in the sampling periods: most of sea spray organics tend to aggregate and form colloids or the samples discussed in the present work were collected in suspended particles, making the definition of water solubility summer, when the photochemical activity is at its maximum, a complex issue. Whether the difference in the results of the while most of the 2002 samples reported in O’Dowd et two experiments is attributable only to the different organic al. [6] were collected during spring and autumn, when sea carbon measurement approach, or also to differences in the spray production is higher. The main difference between the chemical properties of the sea water used for generating two datasets, indeed, regards WIOM absolute concentration aerosol particles by bubble bursting (oligotrophic Sargasso −3 during the HBA period (∼0.6 μgm in 2002 and less than Sea versus North Atlantic Ocean during algal bloom) is still −3 0.1 μgm during MAP, averagely), while WSOM one is an issue of debate. −3 (μgm ) 11–18 Jan 06 18–22 Jan 06 10–20 Feb 06 29 Mar–04 Apr 06 12–26 Apr 06 12–19 Jun 06 19–28 Jun 06 28 Jun–05 Jul 06 03–08 Sep 06 05–11 Oct 06 15–22 Nov 06 04–11 Dec 06 Advances in Meteorology 5 Furthermore, Modini et al. [35] presented the results of between primary and secondary organic aerosol components a similar experiment in which the organic volume contri- were also provided by Jimenez et al. [41], who showed, in bution in lab-produced sea spray particles, indirectly deter- a recent chamber experiment, how aerosolized squalane, a mined by volatility/hygroscopicity tandem measurements proxy for the refractory fraction of primary marine organic (HV-TDMA), was estimated to be (8 ± 6%) in the 71–77 nm aerosol, was subjected to photochemical ageing, showing size range, corresponding to a mass contribution of only 4%. mass spectral features progressively transforming into those Such results may be conditioned by the interpretation of HV- of oxidized organic aerosols, which are ubiquitous in the TDMA measurements to calculate the organic fraction, or atmosphere. by the use of coastal waters (potentially high in terrestrial runoff ) for spray generation. However, they could also be evidence of a high system variability, stressing the necessity 5. Advances in Marine SOA Chemical forfurtherinvestigation. Characterization Several papers have reported the presence of carbo- hydrate-like material in marine particles, attributing this to New results on marine WSOC chemical composition have primary sea spray processes. been obtained over past years, allowing the identification of Bigg and Leck [36] observed the presence of complex typical marine SOA components, other than MSA and DMS structures behaving as lipopolysaccharides in submicron oxidation products. marine aerosol. Facchini et al. [22] evidenced the presence The presence of amines and aminoacids over the oceans of hydroxyl groups, both in water soluble and insoluble sea has been sporadically reported since the 1980s in rain spray OM, using HNMR analyses. These hydroxyl signals samples over the ocean [42–44]. Gibb et al. [45] reported the were always associated in the NMR spectra to important presence of monomethylammonium (MMA ), dimethylam- + + signals due to aliphatic chains with terminal methyls, typical monium (DMA ) and trimethylammonium (TMA ) salts in of lipids. Moreover, the HNMR spectra of oceanic water aerosol particles collected in unpolluted conditions over the closely resembled that of nascent aerosol, and were in agree- Arabian Sea. The authors attributed the presence of aerosol ment with several observations in the literature reporting the phase alkyl ammonium salts to secondary production, due presence in oceanic waters of phytoplankton exudates with a to the condensation of gaseous alkyl amines emitted by the composition dominated by lipopolysaccharides [37, 38]. sea, in analogy with NH . More recently, this hypothesis has Very recently Russell et al. [39]observedanocean- been strengthened by evidence that alkyl amines participate derived component, in marine aerosol, dominated by in SOA formation in many different environments through carbohydrate-like material, based on multi-technique mea- reaction with acids [46–48]. surements of submicron marine aerosol over the North Facchini et al. [20] highlighted the importance of alkyl- Atlantic and Arctic Oceans and on Positive Matrix Factor- ammonium salts as submicron marine aerosol components, ization data elaboration. According to these authors, the and reported dimethyl and diethyl-ammonium salts (DMA primary marine signal in submicron marine aerosol is made and DEA ) concentrations ranging, together between <0.4 −3 on average for 88% of hydroxyl groups. Although the low and 56 ng m over the North Atlantic Ocean during the signal-to-noise ratio of the spectra made difficult a precise HBA period, turning out to be the most abundant organic quantification of the carbohydrate-like material, HNMR species, second only to MSA, in submicron marine particles. analyses exclude a contribution as high as the one observed Alkyl-ammonium salts represented on average 11% of the by Russell et al. [39] for these components in the North marine SOA and a dominant fraction (35% on average) of Atlantic during periods of HBA. aerosol water soluble organic nitrogen (WSON). Such new, often contrasting results on primary organics The above cited paper presents considerable evidence + + in marine aerosol reflect the limits of current knowledge that DMA and DEA are secondary aerosol components, on this topic. Furthermore, the fate of primary organics in originating from biogenic precursors emitted by the ocean. the atmosphere is even more uncertain, and few data are Their size distributions exhibited maxima in the accu- available on sea spray organic oxidation routes, rates and mulation mode, as is also the case of other well known −2 + products. Zhou et al. [40] evidenced that OM in marine secondary components (nssSO ,NH , MSA), supporting 4 4 aerosols plays a dual role, being an important precur- the hypothesis that a gas-to-particle conversion process is sor/source and a dominant sink for the OH radical, leading responsible for the accumulation of alkyl-ammonium salts to the degradation of OM, and the likely production of a in the fine aerosol fraction. The most likely hypothesis is series of low-molecular weight (LMW) organic compounds. that gaseous dimethylamine and diethylamine react with Therefore, primary and secondary organic components must sulphuric acid or acidic sulphates, accumulating within be considered as closely correlated in marine aerosol, as the aerosol particles in close analogy with ammonia. Regarding oxidation products of biogenic primary organics in marine the precursor origin, a main anthropogenic source of gaseous aerosol particles can lead to the production of both oxidized alkyl-amines over the ocean can be excluded, because the + + aerosol components (belonging to the broad category of aerosol DMA and DEA concentrations measured at Mace SOA) and of volatile LMW products, which can partition Head, were always higher in clean marine samples (roughly into the gas phase and influence the multiphase photochem- double) than in polluted air masses, in analogy with MSA. ical evolution of the marine troposphere (including SOA Like other reduced biogenic gases (DMS, CH ) and in formation). Supporting evidence of this gliding boundary analogy with NH ,DMA andDEA couldbethe endproducts 3 6 Advances in Meteorology Table 2: Summary of the sea spray OM contribution measured in the most recent sea spray production laboratory experiments. Max OM mass Particle diameter Sea water sampling site Notes Reference contribution [%] [nm] Only WSOC Sargasso Sea ∼80 130 measured. No Keene et al. [34] (oligotrophic) filtration WSOC and WIOC North Atlantic Ocean 77 ± 5 125–250 measured. Facchini et al. [22] (algal bloom) Filtration. Moreton Bay (Australia) 4 71–77 Coastal water Modini et al. [35] of microbial turnover of marine labile OM [45, 49, 50]. Notwithstanding recent improvements, current knowl- Furthermore, alkyl-ammonium ions in submicron aerosol edge on the chemical composition of marine SOA remains particles showed the typical seasonal variation of biogenic limited, and further research is required to address the many components, with high concentrations measured in the HBA unresolved issues. During MAP a multi-technique approach period, and much lower concentrations in the LBA period was deployed to characterize marine WSOC. Coupling (Table 3). HPLC-TOC and IC, it was possible to achieve an almost- Table 3 summarizes the marine aerosol alkylammonium complete chemical characterization of submicron marine ion concentration data so far available: two very recent WSOC, on a selected subset of samples (5, from both papers confirm the findings of Facchini et al. [20]. Mul ¨ ler Mace Head and Celtic Explorer sampling) representative of + + et al. [51] reported monomethylammonium (MA ), DMA the HBA period (Figure 3). Marine aerosol WSOC can be and DEA at non-negligible concentrations in submicrom- divided into three chemical macroclasses based on acid-base eter particles at Cape Verde, during algal blooms in 2007, properties: neutral-basic compounds (NB), accounting for attributing them to secondary formation processes. More- 32 (±8) % of WSOC, mono-diacids (MDA), contributing over, high levels of amines were observed in coincidence 42 (±9) %, and polyacids (PA), accounting for 4 (±3) %. with high near surface Chlorophyll-a concentrations. Finally, Averagely 22 (±11) % of WSOC escaped this classification, Sorooshian et al. [19] also observed DEA in submicron probably as a result of strong and irreversible binding with particles over the North Pacific Ocean, with concentrations the HPLC column: this fraction is labeled “uncharacterized” rather well correlated to the chlorophyll-a sea surface in the Figure. From the HPLC-TOC macroclasses average concentration. contribution, the average contribution of each compound, Besides alkylammonium salts and MSA, carboxylic and identified by IC, has been subtracted, obtaining the classi- di-carboxylic acids have been identified in marine aerosol fication of Figure 3. Only 30% of WSOC was characterized [52, 53 and references therein], found to account for less at the molecular level by IC, with MSA (11 ± 5%) and than 10% of total particulate organic carbon in remote oxalic acid (3 ± 2%) being the only two MDA components marine environments. The above mentioned papers attribute identified. This leaves more than a half of the dominant class a secondary origin to detected di-carboxylic acids, citing of compounds still uncharacterized, although it is likely that oxalic acid as the most abundant one. However, oxidized other LMW dicarboxylic acids, like malonic and succinic organics, such as C –C carboxylic or di-carboxylic acids, acid, not identified by IC, can account together for another 5 10 can also be produced by the oxidative degradation of primary 1%-2%. As for the NB compounds, 6 ± 7and 10 ± 12% + + particles generated by sea spray and rich in fatty acids [52]. of the WSOC can be ascribed to DMA and DEA , leaving Recent instrumental advances have allowed a deeper about 15% of WSOC as uncharacterized NB compounds. insight into organic marine aerosol chemical composi- In WSOC extracted from marine aerosol collected during tion. Using liquid chromatography/negative ion electrospray MAP, HPLC analysis showed the occurrence of fulvic-like ionization mass spectrometry, Claeys et al. [53]inves- material (polyacids macroclass), in lower concentrations tigated marine organic aerosol chemical composition at than suggested by previous studies, that is, 22% [17]. The Amsterdam Island (Southern Indian Ocean), reporting a finding indicates that primary emissions of fulvic substances WSOC contribution of 32 ± 12% to submicron OC. About from seawater did not make a major contribution to 25% of WSOC was characterized and attributed to MSA marine water-soluble aerosols during MAP. This picture (17%–21%), oxalate (5 ± 2%), malonate (1.8 ± 0.9%) of submicron marine aerosol WSOC is coherent with the and organosulphates (0.8 ± 1.5%). The organosulphates hypothesis of its mainly secondary origin, even though characterized in Claeys et al. [53] can be considered tracers the uncharacterized fraction escaping classification in NB, for an SOA formation process that is specific to the marine MDA and PA may be due to the contribution of primarily environment, that is, oxidation of marine biomass. More emitted, aggregate forming, organic matter, similar to that specifically, the organosulfates correspond to sulfate esters characterized in laboratory experiments on nascent sea spray –C hydroxyl carboxylic acids, which are attributed to of C aerosol by Facchini et al. [22]. 9 13 oxidation of unsaturated fatty acid residues present in algal Information on the chemical composition of the unchar- cell membranes. acterized fractions of NB, MDA and PA has been derived Advances in Meteorology 7 Table 3: Alkylammonium ions aerosol concentration range (in brackets) and median value (when available) reported in the literature for −3 the marine environment. All concentrations are in ng m . All data refer to submicron particles except for Mul ¨ ler et al. [51], whosesizecut was 0.14–0.42 μm, and Gorzelska and Galloway [44], who did not report any particle size information. + −3 + −3 + −3 + −3 + −3 Location MA [ng m ]DMA [ng m ] TMA [ng m ]EA [ng m ]DEA [ng m ] Reference North Atlantic Gorzelska & (<dl–3.9) (<dl–∼1.4) Jun–Sep 1988 Galloway [44] Arabian Sea <dl–6.1 1.6–4.4 0.018–0.78 Gibb et al. [45] Aug-Oct 1994 Arabian sea 2.6–4.5 3.7–17.5 0.12–0.9 Gibb et al. [45] Nov-Dec 1994 Mace Head Facchini et al. 1(<1–8) (<1–12) Oct–Mar 2006 [20] Mace Head Facchini et al. 10 (2–24) 16 (4–32) Apr–Sep 2006 [20] North Atlantic Facchini et al. 9 (4–13) 12 (7–24) Jun 2006 [20] Cape Verde May 0.06 Mul ¨ ler et al. 0.02 (0.01–0.03) 0.21(0.13–0.36) 2007 (0.005–0.11) [51] Cape Verde Jun Muller et al. 0.03 (0.01–0.12) 0.21(0.05–0.39) 0.07 (0.06–0.14) 2007 [51] Cape Verde Dec 0.15 Mul ¨ ler et al. 0.54 (0.1–1.4) 0.29 (0.09–0.76) 2007 (0.002–0.52) [51] North Pacific Sorooshian et al. 14–35 Jul-Aug 2007 [19] DMA in submicron marine aerosol chemical composition over 6% biologically productive, high latitude, marine regions, in DEA both hemispheres. Moreover, it has been demonstrated that Uncharacterized 10% 22% marine organic aerosol chemical composition is the complex result of different primary and secondary sources. Most recent results on sea spray composition suggest NB that in conditions of intense oceanic biological productivity, PA Uncharacterized submicron primary marine aerosol can contain a consid- 4% NB 16% erable fraction of OM. Further studies are necessary to obtain deeper insight into the space/time variability of the MDA ocean primary organics production potential worldwide. Important advances can be obtained by coupling modeling MSA with new satellite chlorophyll, dissolved and particulate 11% Uncharacterized MDA organic carbon measurement instruments, as attempted for Oxalic acid 28% the first time by O’Dowd et al. [54] and Vignati et al. [4]. 3% In fact, although much information has been gathered on Figure 3: WSOC chemical composition representative of spring- the DMS oxidation cycle, and several predictive tools are summer conditions over the Atlantic Ocean, obtained by combining available to model secondary products, like MSA and nss- HPLC-TOC and IC (see text for more details). Percentages indicate sulfate over the oceans, only raw empiric instruments are the contribution of each compound or chemical macroclass in available to predict primary organic aerosol emissions as a terms of carbon. function of oceanic biological productivity. To date, little is known about sea spray organic chemical composition, lifetime and fate in the marine boundary layer. by NMR functional group analysis (Decesari et al., in Further investigation is required to address this issue, that preparation), showing aliphatic moieties substituted with can also help to fill the gap between observed and modeled oxygenated groups, like carbonyls/carboxyls and, in analogy SOA in the MBL. with the findings of Russell et al. [39], hydroxyl groups. As for secondary organics in the MBL, although several classes of compounds have been identified in different marine environments as typical marine SOA components 6. Conclusions (MSA, alkylammonium salts, dicarboxylic acids), most marine aerosol WSOC remains uncharacterized at the Studies performed during the past years strongly suggest that biogenic organic compounds play an important role molecular level. 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