Peatland Wildfires Enhance Nitrogen-Containing Organic Compounds in Marine Aerosols over the Western Pacific.

Peatland wildfires contribute significantly to the atmospheric release of light-absorbing organic carbon, often referred to as brown carbon. In this study, we examine the presence of nitrogen-containing organic compounds (NOCs) within marine aerosols across the Western Pacific Ocean, which are influenced by peatland fires from Southeast Asia. Employing ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in electrospray ionization (ESI) positive mode, we discovered that NOCs are predominantly composed of reduced nitrogenous bases, including CHN+ and CHON+ groups. Notably, the count of NOC formulas experiences a marked increase within plumes from peatland wildfires compared to those found in typical marine air masses. These NOCs, often identified as N-heterocyclic alkaloids, serve as potential light-absorbing chromophores. Furthermore, many NOCs demonstrate pyrolytic stability, engage in a variety of substitution reactions, and display enhanced hydrophilic properties, attributed to chemical processes such as methoxylation, hydroxylation, methylation, and hydrogenation that occur during emission and subsequent atmospheric aging. During the daytime atmospheric transport, aging of aromatic N-heterocyclic compounds, particularly in aliphatic amines prone to oxidation and reactions with amine, was observed. The findings underscore the critical role of peatland wildfires in augmenting nitrogen-containing organics in marine aerosols, underscoring the need for in-depth research into their effects on marine ecosystems and regional climatic conditions.

Geochemical studies of low molecular weight organic acids in the atmosphere: sources, formation pathways, and gas/particle partitioning.

Low molecular weight monocarboxylic acids (LMW monoacids, C1-C10) are the most abundant gaseous organic compound class in the atmosphere. Formic or acetic acid is the dominant volatile organic compound (VOC) in Earth's atmosphere. They can largely contribute to rainwater acidity, especially in the tropical forest, and react with alkaline metals, ammonia, and amines, contributing to new particle formation and secondary organic aerosol production. Gaseous and particulate LMW monoacids were abundantly reported in China. They can be directly emitted from fossil fuel combustion and biomass burring; however, the secondary formation is more important than primary emissions via the photochemical oxidation of anthropogenic and biogenic VOCs. In this paper, we review the distributions of LMW monoacids from urban, mountain, and marine sites as well as from rainwater and alpine snow samples and discuss their sources and formation mechanisms in the atmosphere. We also discuss their importance as cloud condensation nuclei (CCN) and provide future perspectives of LMW monoacids study in the warming world.

Aerosol Proteinaceous Matter in Coastal Okinawa, Japan: Influence of Long-Range Transport and Photochemical Degradation.

The characteristics, sources, and atmospheric oxidation processes of marine aerosol proteinaceous matter (APM), including total proteins and free amino acids (FAAs), were investigated using a set of 1 year total suspended particulate (TSP) samples collected in the coastal area of Okinawa Island in the western North Pacific rim. The concentrations of APM at this site (total proteins: 0.16 ± 0.10 µg m-3 and total FAAs: 9.7 ± 5.6 ng m-3, annual average) are comparable to those of marine APM. The major FAA species of APM are also similar to previously reported marine APM with glycine as the dominant species (31%). Based on the different seasonal trends and weak correlations of total proteins and FAAs, we found that they were contributed by different sources, especially with the influence of long-range transport from the Asian continent of northern China and Mongolia and the oceanic area of the Bohai Sea, Yellow Sea, and East China Sea. The photochemical oxidation processes of high-molecular-weight proteins releasing FAAs (especially glycine) were also considered as an important factor influencing the characteristics of APM at this site. In addition, we propose a degradation process based on the correlation with ozone and ultraviolet radiation, emphasizing their roles in the degradation of proteins. Our findings help to deepen the understanding of atmospheric photochemical reaction processes of organic aerosols.

Distinctive Sources Govern Organic Aerosol Fractions with Different Degrees of Oxygenation in the Urban Atmosphere.

Understanding how the sources of an atmospheric organic aerosol (OA) govern its burden is crucial for assessing its impact on the environment and adopting proper control strategies. In this study, the sources of OA over Beijing were assessed year-around based on the combination of two separation approaches for OA, one from chemical fractionation into the high-polarity fraction of water-soluble organic matter (HP-WSOM), humic-like substances (HULIS), and water-insoluble organic matter (WISOM), and the other from statistical grouping using positive matrix factorization (PMF) of high-resolution aerosol mass spectra. Among the three OA fractions, HP-WSOM has the highest O/C ratio (1.36), followed by HULIS (0.56) and WISOM (0.17). The major sources of different OA fractions were distinct: HP-WSOM was dominated by more oxidized oxygenated OA (96%); HULIS by cooking-like OA (40%), less oxidized oxygenated OA (27%), and biomass burning OA (21%); and WISOM by fossil fuel OA (77%). In addition, our results provide evidence that mass spectral-based PMF factors are associated with specific substructures in molecules. These structures are further discussed in the context of the FT-IR results. This study presents an overall relationship of OA groups monitored by chemical and statistical approaches for the first time, providing insights for future source apportionment studies.

Impacts of Chemical Degradation on the Global Budget of Atmospheric Levoglucosan and Its Use As a Biomass Burning Tracer.

Levoglucosan has been widely used to quantitatively assess biomass burning's contribution to ambient aerosols, but previous such assessments have not accounted for levoglucosan's degradation in the atmosphere. We develop the first global simulation of atmospheric levoglucosan, explicitly accounting for its chemical degradation, to evaluate the impacts on levoglucosan's use in quantitative aerosol source apportionment. Levoglucosan is emitted into the atmosphere from the burning of plant matter in open fires (1.7 Tg yr-1) and as biofuels (2.1 Tg yr-1). Sinks of atmospheric levoglucosan include aqueous-phase oxidation (2.9 Tg yr-1), heterogeneous oxidation (0.16 Tg yr-1), gas-phase oxidation (1.4 × 10-4 Tg yr-1), and dry and wet deposition (0.27 and 0.43 Tg yr -1). The global atmospheric burden of levoglucosan is 19 Gg with a lifetime of 1.8 days. Observations show a sharp decline in levoglucosan's concentrations and its relative abundance to organic carbon aerosol (OC) and particulate K+ from near-source to remote sites. We show that such features can only be reproduced when levoglucosan's chemical degradation is included in the model. Using model results, we develop statistical parametrizations to account for the atmospheric degradation in levoglucosan measurements, improving their use for quantitative aerosol source apportionment.

Nitrogen Speciation and Isotopic Composition of Aerosols Collected at Himalayan Forest (3326 m a.s.l.): Seasonality, Sources, and Implications.

Nitrogenous aerosols are ubiquitous in the environment and thus play a vital role in the nutrient balance as well as the Earth's climate system. However, their abundance, sources, and deposition are poorly understood, particularly in the fragile and ecosensitive Himalayan and Tibetan Plateau (HTP) region. Here, we report concentrations of nitrogen species and isotopic composition (δ15N) in aerosol samples collected from a forest site in the HTP (i.e., Southeast Tibet). Our results revealed that both organic and inorganic nitrogen contribute almost equally with high abundance of ammonium nitrogen (NH4+-N) and water-insoluble organic nitrogen (WION), contributing ∼40% each to aerosol total nitrogen (TN). The concentrations and δ15N exhibit a significant seasonality with ∼2 times higher in winter than in summer with no significant diurnal variations for any species. Moreover, winter aerosols mainly originated from biomass burning emissions from North India and East Pakistan and reached the HTP through a long-range atmospheric transport. The TN dry deposition and total deposition fluxes were 2.04 kg ha-1 yr-1 and 6.12 kg ha-1 yr-1 respectively. Our results demonstrate that the air contamination from South Asia reach the HTP and is most likely impacting the high altitude ecosystems in an accepted scenario of increasing emissions over South Asia.

Secondary Organic Aerosol Formation over Coastal Ocean: Inferences from Atmospheric Water-Soluble Low Molecular Weight Organic Compounds.

A lack of consensus on the distributions and formation pathways of secondary organic aerosols (SOA) over oceanic regions downwind of pollution sources limits our ability to assess their climate impact globally. As a case study, we report here on water-soluble SOA components such as dicarboxylic acids, oxocarboxylic acids, and α-dicarbonyls in the continental outflows from the Indo-Gangetic Plain (IGP) and Southeast Asia (SEA) to the Bay of Bengal. Oxalic acid (C2) is the dominant species followed by succinic (C4) and glyoxylic acids (ωC2) in the outflow. Nonsea-salt SO42- also dominates (∼70%) total water-soluble inorganic constituents and correlates well with aerosol liquid water content (LWC) and C2, indicating their production through aqueous phase photochemical reactions. Furthermore, mass ratios of dicarboxylic acids (C2/C4, C2/ωC2), and their relative abundances in water-soluble organic carbon and total organic carbon are quite similar between the two continental (IGP and SEA) outflows, indicating the formation of SOA through aqueous phase photochemical reactions in LWC-enriched aerosols, largely controlled by anthropogenic SO42-.

Distributions of Polycyclic Aromatic Hydrocarbons, Aromatic Ketones, Carboxylic Acids, and Trace Metals in Arctic Aerosols: Long-Range Atmospheric Transport, Photochemical Degradation/Production at Polar Sunrise.

The distributions, correlations, and source apportionment of aromatic acids, aromatic ketones, polycyclic aromatic hydrocarbons (PAHs), and trace metals were studied in Canadian high Arctic aerosols. Nineteen PAHs including minor sulfur-containing heterocyclic PAH (dibenzothiophene) and major 6 carcinogenic PAHs were detected with a high proportion of fluoranthene followed by benzo[k]fluoranthene, pyrene, and chrysene. However, in the sunlit period of spring, their concentrations significantly declined likely due to photochemical decomposition. During the polar sunrise from mid-March to mid-April, benzo[a]pyrene to benzo[e]pyrene ratios significantly dropped, and the ratios diminished further from late April to May onward. These results suggest that PAHs transported over the Arctic are subjected to strong photochemical degradation at polar sunrise. Although aromatic ketones decreased in spring, concentrations of some aromatic acids such as benzoic and phthalic acids increased during the course of polar sunrise, suggesting that aromatic hydrocarbons are oxidized to result in aromatic acids. However, PAHs do not act as the major source for low molecular weight (LMW) diacids such as oxalic acid that are largely formed at polar sunrise in the arctic atmosphere because PAHs are 1 to 2 orders of magnitude less abundant than LMW diacids. Correlations of trace metals with organics, their sources, and the possible role of trace transition metals are explained.

Structural and Light-Absorption Characteristics of Complex Water-Insoluble Organic Mixtures in Urban Submicrometer Aerosols.

Submicrometer aerosols in the urban atmosphere of Nagoya, Japan, were collected in late winter and early spring, and the water-insoluble organic matter (WISOM) in the samples were fractionated into six subfractions based on their polarities by using solvent and normal-phase solid-phase extractions: nonpolar (F1), low-polar (F2 and F3), and medium-polar (F4, F5, and F6) fractions. The overall structural characteristics of these subfractions were then analyzed using Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and high-resolution aerosol mass spectrometry. Quantitative information related to the overall chemical characteristics of the WISOM in the different polarity fractions, including their elemental compositions, the relative abundances of different functional groups and their fragments from electron impact ionization, was obtained. These water-insoluble fractions accounted for half of the total light absorption by the extracted aerosol matter at 400 nm. The contributions of the medium-polar fractions to both the total organic carbon and light absorption by the extracts were dominant among the contributions from the six subfractions. Large molecules with aromatic and heteroatomic (O and N) groups, including charge transfer complexes, might have greatly contributed to the light absorption by the fraction F4, which is the largest fraction of the extracted water-insoluble organic matter.

High Contribution of Nonfossil Sources to Submicrometer Organic Aerosols in Beijing, China.

Source apportionment of organic carbon (OC) and elemental carbon (EC) from PM1 (particulate matter with a diameter equal to or smaller than 1 µm) in Beijing, China was carried out using radiocarbon (14C) measurement. Despite a dominant fossil-fuel contribution to EC due to large emissions from traffic and coal combustion, nonfossil sources are dominant contributors of OC in Beijing throughout the year except during the winter. Primary emission was the most important contributor to fossil-fuel derived OC for all seasons. A clear seasonal trend was found for biomass-burning contribution to OC with the highest in autumn and spring, followed by winter and summer. 14C results were also integrated with those from positive matrix factorization (PMF) of organic aerosols from aerosol mass spectrometer (AMS) measurements during winter and spring. The results suggest that the fossil-derived primary OC was dominated by coal combustion emissions whereas secondary OC was mostly from fossil-fuel emissions. Taken together with previous 14C studies in Asia, Europe and USA, a ubiquity and dominance of nonfossil contribution to OC aerosols is identified not only in rural/background/remote regions but also in urban regions, which may be explained by cooking contributions, regional transportation or local emissions of seasonal-dependent biomass burning emission. In addition, biogenic and biomass burning derived SOA may be further enhanced by unresolved atmospheric processes.

Chemical Constituents of Carbonaceous and Nitrogen Aerosols over Thumba Region, Trivandrum, India.

Aerosol filter samples collected at a tropical coastal site Thumba over Indian region were analysed for water-soluble ions, total carbon and nitrogen, organic carbon (OC), elemental carbon (EC), and water-soluble organic carbon/nitrogen and their sources for different seasons of the year. For the entire study period, the order of abundance of ions showed the dominance of secondary ions, such as SO42-, NO3-, and NH4+. On average, Mg2+ (56%), K+ (11%), SO42- (8.8%), and Ca2+ (8.1%) contributions were from maritime influence. There was significant chloride depletion due to enhanced levels of inorganic acids, such as SO42- and NO3-. Total carbon contributed 21% of the aerosol total suspended particulate matter in which 85% is organic carbon. Primary combustion-generated carbonaceous aerosols contributed 41% of aerosol mass for the entire study period. High average ratios of OC/EC (5.5 ± 1.8) and WSOC/OC (0.38 ± 0.11) suggest that organic aerosols are predominantly comprised of secondary species. In our samples, major fraction (89 ± 9%) was found to be inorganic nitrate in total nitrogen (TN). Good correlations (R 2 ≥ 0.82) were observed between TN with NO3- plus NH4+, indicating that nitrate and ammonium ions account for a significant portion of TN. The temporal variations in the specific carbonaceous aerosols and air mass trajectories demonstrated that several pollutants and/or their precursor compounds are likely transported from north western India and the oceanic regions.

Identification of hydroxy- and keto-dicarboxylic acids in remote marine aerosols using gas chromatography/quadruple and time-of-flight mass spectrometry.

RATIONALE: The identification of hydroxy- and keto-dicarboxylic acids (diacids) in remote marine aerosol samples is important for a better understanding of the composition of organic particulate matter, as this chemical composition is essential for predicting the effects on climate, air quality, and human health. Molecular characterization of these compounds provides insights into sources and formation pathways of organic aerosols. METHODS: The method of chemical derivatization followed by gas chromatography-flame ionization detection (GC-FID), gas chromatography/quadruple mass spectrometry (GC/QMS) and gas chromatography/time-of-flight mass spectrometry (GC/TOFMS) was used to identify hydroxy- and keto-diacids in remote marine aerosols. Atmospheric samples were collected at Chichijima Island in the western North Pacific and the diacids and related compounds were extracted with organic-free ultrapure water. A two-step derivatization technique was employed, using 14% BF3 /n-butanol for the butylation of carboxyl groups and acidic ketones followed by N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) for the trimethylsilylation of hydroxyl groups. RESULTS: Several new peaks were detected in the gas chromatogram after trimethylsilylation of the dibutyl ester fraction. Based on mass spectral interpretation with authentic standards, we successfully identified and quantified a homologous series of hydroxydiacids, including tartaric and oxaloacetic acids. In addition, transformation of oxaloacetic acid into its enol form was elucidated. CONCLUSIONS: Utilizing GC-FID, GC/QMS and GC/TOFMS, hydroxy- and keto-diacids were identified in the remote marine aerosols. A complete structural characterization was achieved with extensive mass spectral analysis. Molecular distributions of hydroxydiacids generally showed the predominance of malic acid followed by tartronic acid. We consider that these hydroxydiacids are important intermediates in the atmospheric oxidation of organic aerosols to result in smaller diacids. Copyright © 2016 John Wiley & Sons, Ltd.

Fossil and Nonfossil Sources of Organic and Elemental Carbon Aerosols in the Outflow from Northeast China.

Source quantification of carbonaceous aerosols in the Chinese outflow regions still remains uncertain despite their high mass concentrations. Here, we unambiguously quantified fossil and nonfossil contributions to elemental carbon (EC) and organic carbon (OC) of total suspended particles (TSP) from a regional receptor site in the outflow of Northeast China using radiocarbon measurement. OC and EC concentrations were lower in summer, representing mainly marine air, than in other seasons, when air masses mostly traveled over continental regions in Mongolia and northeast China. The annual-mean contribution from fossil-fuel combustion to EC was 76 ± 11% (0.1-1.3 µg m(-3)). The remaining 24 ± 11% (0.03-0.42 µg m(-3)) was attributed to biomass burning, with slightly higher contribution in the cold period (∼31%) compared to the warm period (∼21%) because of enhanced emissions from regional biomass combustion sources in China. OC was generally dominated by nonfossil sources, with an annual average of 66 ± 11% (0.5-2.8 µg m(-3)), approximately half of which was apportioned to primary biomass-burning sources (34 ± 6%). In winter, OC almost equally originated from primary OC (POC) emissions and secondary OC (SOC) formation from fossil fuel and biomass-burning sources. In contrast, summertime OC was dominated by primary biogenic emissions as well as secondary production from biogenic and biomass-burning sources, but fossil-derived SOC was the smallest contributor. Distinction of POC and SOC was performed using primary POC-to-EC emission ratios separated for fossil and nonfossil emissions.

Molecular Markers of Secondary Organic Aerosol in Mumbai, India.

Biogenic secondary organic aerosols (SOA) are generally considered to be more abundant in summer than in winter. Here, polar organic marker compounds in urban background aerosols from Mumbai were measured using gas chromatography-mass spectrometry. Surprisingly, we found that concentrations of biogenic SOA tracers at Mumbai were several times lower in summer (8-14 June 2006; wet season; n = 14) than in winter (13-18 February 2007; dry season; n = 10). Although samples from less than 10% of the season are extrapolated to the full season, such seasonality may be explained by the predominance of the southwest summer monsoon, which brings clean marine air masses to Mumbai. While heavy rains are an important contributor to aerosol removal during the monsoon season, meteorological data (relative humidity and T) suggest no heavy rains occurred during our sampling period. However, in winter, high levels of SOA and their day/night differences suggest significant contributions of continental aerosols through long-range transport together with local sources. The winter/summer pattern of SOA loadings was further supported by results from chemical transport models (NAQPMS and GEOS-Chem). Furthermore, our study suggests that monoterpene- and sesquiterpene-derived secondary organic carbon (SOC) were more significant than those of isoprene- and toluene-SOC at Mumbai.

Characterization of Chromophoric Water-Soluble Organic Matter in Urban, Forest, and Marine Aerosols by HR-ToF-AMS Analysis and Excitation-Emission Matrix Spectroscopy.

Chromophoric water-soluble organic matter in atmospheric aerosols potentially plays an important role in aqueous reactions and light absorption by organics. The fluorescence and chemical-structural characteristics of the chromophoric water-soluble organic matter in submicron aerosols collected in urban, forest, and marine environments (Nagoya, Kii Peninsula, and the tropical Eastern Pacific) were investigated using excitation-emission matrices (EEMs) and a high-resolution aerosol mass spectrometer. A total of three types of water-soluble chromophores, two with fluorescence characteristics similar to those of humiclike substances (HULIS-1 and HULIS-2) and one with fluorescence characteristics similar to those of protein compounds (PLOM), were identified in atmospheric aerosols by parallel factor analysis (PARAFAC) for EEMs. We found that the chromophore components of HULIS-1 and -2 were associated with highly and less-oxygenated structures, respectively, which may provide a clue to understanding the chemical formation or loss of organic chromophores in atmospheric aerosols. Whereas HULIS-1 was ubiquitous in water-soluble chromophores over different environments, HULIS-2 was abundant only in terrestrial aerosols, and PLOM was abundant in marine aerosols. These findings are useful for further studies regarding the classification and source identification of chromophores in atmospheric aerosols.

Long-term (2001-2012) observation of the modeled hygroscopic growth factor of remote marine TSP aerosols over the western North Pacific: impact of long-range transport of pollutants and their mixing states.

In order to assess the seasonal and annual variability of long-range transported anthropogenic pollutants from East Asia and their effect on the hygroscopicity and precipitation process over the western North Pacific, we conducted long-term calculations of bulk hygroscopicity, g(90%)ZSR, based on the ZSR model using chemical composition data from 2001-2012 at Chichijima Island. We found that sea-salts (Na(+) and Cl(-)) are the major mass fraction (65%) of the total water-soluble matter followed by SO4(2-) (20%) and WSOM (6%). The seasonal variation of g(90%)ZSR was high in summer to autumn and low in winter to spring months, probably due to the influence of the long-range transport of anthropogenic SO4(2-), dust, and organics from East Asia and their interaction with sea-salts through heterogeneous reactions. On the other hand, annual variations of g(90%)ZSR showed a decrease from 2001 to 2006 and then an increase from 2007 to 2012. Interestingly, the annual variations in SO4(2-) mass fractions showed an increase from 2001 to 2006 and then a decrease from 2007 to 2012, demonstrating that SO4(2-) seriously suppresses the hygroscopic growth of sea-salt particles over the western North Pacific. This is further supported by the strong negative correlation between SO4(2-) and g(90%)ZSR. Based on the MODIS satellite data, the present study demonstrates that long-range transported anthropogenic pollutants from East Asia to the North Pacific can act as efficient cloud condensation nuclei but significantly suppress the precipitation by reducing the size of cloud droplets over the western North Pacific.

Secondary production of organic aerosols from biogenic VOCs over Mt. Fuji, Japan.

We investigated organic molecular compositions of summertime aerosols collected at the summit of Mt. Fuji (3776 m a.s.l.) in July-August 2009. More than 120 organic species were identified using GC/MS. Concentrations of both primary and secondary organic aerosol (SOA) tracers in whole-day samples were 4-20 times higher than those in nighttime samples, suggesting that valley breeze is an efficient mechanism to uplift the aerosols and precursors from the ground surface to mountaintop in daytime. Using a tracer-based method, we estimated the concentrations of secondary organic carbon (SOC) derived from isoprene, α/ß-pinene, and ß-caryophyllene to be 2.2-51.2 ngC m(-3) in nighttime and 227-1120 ngC m(-3) during whole-day. These biogenic SOCs correspond to 0.80-31.9% and 26.8-57.4% of aerosol organic carbon in nighttime and whole-day samples, respectively. This study demonstrates that biogenic SOA, which is controlled by the valley breeze, is a significant fraction of free tropospheric aerosols over Mt. Fuji in summer.

Historical trends of atmospheric black carbon on tibetan plateau as reconstructed from a 150-year lake sediment record.

Black carbon (BC) is one of the key components causing global warming. Especially on the Tibetan Plateau (TP), reconstructing BC's historical trend is essential for better understanding its anthropogenic impact. Here, we present results from high altitude lake sediments from the central TP. The results provide a unique history of BC over the past 150 years, from the preindustrial to the modern period. Although BC concentration levels in the Nam Co Lake sediments were lower than those from other high mountain lakes, the temporal trend of BC fluxes clearly showed a recent rise, reflecting increased emissions from anthropogenic activities. The BC records were relatively constant until 1900, then began to gradually increase, with a sharp rise beginning around 1960. Recent decades show about 2.5-fold increase of BC compared to the background level. The emission inventory in conjunction with air mass trajectories further demonstrates that BC in the Nam Co Lake region was most likely transported from South Asia. Rapid economic development in South Asia is expected to continue in the next decades; therefore, the influence of BC over the TP merits further investigations.

A year-round observation of δ13C of dicarboxylic acids and related compounds in fine aerosols: Implications from Central European background site.

Isotopic analysis of specific compounds in aerosols can be a useful tool when studying atmospheric processes. Here, we present the results of stable carbon isotope ratio (δ13C) measurements performed on a one-year set (n = 96, Sep. 2013-Aug. 2014) of dicarboxylic acids and related compounds in PM1 at a rural Central European background site, Kosetice (Czech Republic). The most 13C enriched acid was oxalic (C2, annual average = -16.6 ± 5.0‰) followed by malonic (C3, avg. = -19.9 ± 6.6‰) and succinic (C4, avg. = -21.3 ± 4.6‰) acids. Thus, δ13C values decreased with an increase in carbon numbers. Azelaic acid (C9, avg. = -27.2 ± 3.6‰) was found to be the least 13C enriched. A comparison of δ13C of dicarboxylic acids from other background sites, especially in Asia, shows similar values to those from the European site. This comparison also showed that C2 is more 13C enriched at background sites than at urban ones. In general, we did not observe significant seasonal differences in δ13C values of dicarboxylic acids at the Central European station. We observed statistically significant differences (p value < 0.05) between winter and summer δ13C values solely for C4, glyoxylic acid (ωC2), glutaric acid (C5) and suberic acid (C8). The only significant correlations between δ13C of C2 and δ13C of C3 were found in spring and summer, suggesting that the oxidation of C3 to C2 is significant in these months with a strong contribution from biogenic aerosols. The strongest season-independent annual correlation was observed in δ13C values between C2 and C4, the two dominant dicarboxylic acids. Therefore, C4 appears to be the main intermediate precursor of C2 throughout the whole year.

Seasonal characteristics of biogenic secondary organic aerosol tracers in a deciduous broadleaf forest in northern Japan.

We collected total suspended particulate (TSP) samples from January 2010 to December 2010 at Sapporo deciduous forest to understand the oxidation processes of biogenic volatile organic compounds (BVOCs). The gas chromatography-mass spectrometric technique was applied to determine biogenic secondary organic aerosols (BSOAs) in the TSP samples. We found the predominance of the isoprene SOA (iSOA) tracers (20.6 ng m-3) followed by α/ß-pinene SOA (pSOA) tracers (8.25 ng m-3) and ß-caryophyllene SOA (cSOA) tracer (1.53 ng m-3) in the forest aerosols. The results showed large isoprene fluxes and relatively high levels of oxidants in the forest atmosphere. The iSOA and pSOA tracers showed a clear seasonal trend with summer and autumn maxima and winter and spring minima. Their seasonal trends were mainly controlled by BVOCs emission from the local broadleaf deciduous forest. Additionally, the regional level of isoprene emissions from the oceanic sources may also be contributed during summertime aerosols. cSOA tracer showed high concentrations in the winter and spring, possibly due to an additional contribution of biomass burning (BB) aerosols from the local or regional BB activities. The biogenic secondary organic carbon (BSOC) was contributed mainly by the oxidation products of isoprene (136 ngC m-3) followed by ß-caryophyllene (63.0 ngC m-3) and α/ß-pinene (35.9 ngC m-3). The mass concentration ratio (0.92) of pinonic acid + pinic acid and 3-methyl-1,2,3-butanetricarboxylic acid ((PNA + PA)/3-MBTCA) indicates the photochemical transformation of first-generation oxidation products to the higher generation oxidation products. The average ratios of isoprene to α/ß-pinene (1.64) and ß-caryophyllene (18.6) oxidation products suggested a large difference in the emissions of isoprene and α/ß-pinene compared to ß-caryophyllene. The cSOA tracers in the forest aerosols are also contributed by BB during the winter and spring. Positive matrix factorization analyses of the BSOA tracers confirmed that organic aerosols of deciduous forests are mostly related to isoprene emissions. This study suggests that isoprene is a more significant precursor for the BSOA than α/ß-pinene and ß-caryophyllene in a broadleaf deciduous forest.