Elsevier

Science of The Total Environment

Volume 544, 15 February 2016, Pages 606-616
Science of The Total Environment

Levoglucosan and phenols in Antarctic marine, coastal and plateau aerosols

https://doi.org/10.1016/j.scitotenv.2015.11.166Get rights and content

Highlights

  • Levoglucosan and phenolic compounds were detected in remote Antarctic aerosols.

  • Antarctic samples had different levoglucosan/PC ratios than biomass burning aerosol.

  • Coastal PCs were less oxidized in comparison to those collected on the plateau.

  • The results suggest that PCs have sources other than biomass burning in Antarctica.

Abstract

Due to its isolated location, Antarctica is a natural laboratory for studying atmospheric aerosols and pollution in remote areas. Here, we determined levoglucosan and phenolic compounds (PCs) at diverse Antarctic sites: on the plateau, a coastal station and during an oceanographic cruise. Levoglucosan and PCs reached the Antarctic plateau where they were observed in accumulation mode aerosols (with median levoglucosan concentrations of 6.4 pg m 3 and 4.1 pg m 3, and median PC concentrations of 15.0 pg m 3 and 7.3 pg m 3). Aged aerosols arrived at the coastal site through katabatic circulation with the majority of the levoglucosan mass distributed on larger particulates (24.8 pg m 3), while PCs were present in fine particles (34.0 pg m 3). The low levoglucosan/PC ratios in Antarctic aerosols suggest that biomass burning aerosols only had regional, rather than local, sources. General acid/aldehyde ratios were lower at the coastal site than on the plateau. Levoglucosan and PCs determined during the oceanographic cruise were 37.6 pg m 3 and 58.5 pg m 3 respectively. Unlike levoglucosan, which can only be produced by biomass burning, PCs have both biomass burning and other sources. Our comparisons of these two types of compounds across a range of Antarctic marine, coastal, and plateau sites demonstrate that local marine sources dominate Antarctic PC concentrations.

Introduction

Biomass burning encompasses the combustion of living and dead vegetation, and includes wildfires, prescribed burning (deforestation, shifting cultivation, agriculture waste) and domestic bio-fuel combustion (such as in fireplaces, stoves) (Cheng et al., 2013). Humans intentionally and accidentally ignite fires although volcanic activity and lightning also lead to forest fires (Taylor, 2010). Biomass combustion is the largest source of primary fine carbonaceous particles and the second principal source of trace gases in the global atmosphere (Akagi et al., 2011).

Biomass burning aerosols influence the climate system by affecting the Earth's solar balance (IPCC, 2013, Hobbs et al., 1997), acting as cloud condensation nuclei (Novakov and Corrigan, 1996, Vestin et al., 2007) and influencing snow albedo (IPCC, 2013, Flanner et al., 2007, Ramanathan and Carmichael, 2008). However, the transport, evolution and sinks of many biomass burning aerosols are not well understood. Here, we examine two classes of biomass burning tracers (levoglucosan and phenolic compounds) in Antarctic plateau, coastal, and oceanic sites to determine how distance from biomass burning source regions and subsequent transport and aging affects their concentrations and size distribution.

Antarctica is surrounded by ocean, contains little to no biomass burning sources, lacks stable human settlements, and therefore presents a natural laboratory for investigating biomass burning aerosols after long range transport. We examine the specific biomarker levoglucosan (1,6 anhydro-β-D glucopyranose) as it is an unambiguous product of cellulose combustion produced at temperatures of approximately 250 °C (Kuo et al., 2011). Here, we use levoglucosan as a reference biomass burning tracer due to its specificity and high emission factors (Iinuma et al., 2007, Oros et al., 2006, Oros and Simoneit, 2001a, Oros and Simoneit, 2001b). Although levoglucosan can degrade in the atmosphere by reacting with OH (Hennigan et al., 2010, Hoffmann et al., 2010, Kessler et al., 2010), NO3 and SO4 (Hoffmann et al., 2010), the high concentrations injected into smoke plumes suggest that enough remains to allow using levoglucosan as a biomass burning tracer (Hoffmann et al., 2010). In Arctic aerosols levoglucosan was determined both in conditions influenced by (Stohl et al., 2006, Stohl et al., 2007) and not influenced (Fu et al., 2009, von Schneidemesser et al., 2009, Yttri et al., 2014, Zangrando et al., 2013) by wildfires, while in Antarctica studies only observe levoglucosan in marine aerosols (Hu et al., 2013). Ice core (Gambaro et al., 2008, Kawamura et al., 2012, Legrand et al., 2007, Yao et al., 2013) and snow pit (Hegg et al., 2010, Kehrwald et al., 2012) studies demonstrate that levoglucosan can reconstruct past biomass burning over annual to millennial timescales (Zennaro et al., 2014) in polar locations.

While levoglucosan records cellulose burning, this marker alone cannot determine what type of vegetation burned to produce the smoke aerosols. PCs in atmospheric aerosols may indicate the types of burned plants. Methoxy phenols derive from lignin combustion. Lignin is a biopolymer comprised of three different aromatic alcohols; p-coumaryl, coniferyl and sinapyl alcohols where their proportions differ between the major plant classes. The degradation products from oxidation or burning of lignin are classified as coumaryl, vanillyl and syringyl moieties (Simoneit, 2002). Hardwood (angiosperm) lignin (Oros and Simoneit, 2001b) is enriched in sinapyl alcohol precursors so burning these plants principally produces syringyl and vanillyl moieties. In deciduous tree smoke the main PCs produced include homovanillyl alcohol, vanillic acid, vanillin, and syringic acid. Softwoods (gymnosperms) (Oros and Simoneit, 2001a) contain high proportions of coniferyl alcohol with minor components from sinapyl alcohol and burning produces primarily vanillyl moieties. The dominant phenolic biomarkers in conifer smoke include vanillin, homovanillic acid, vanillic acid, and homovanillyl alcohol. In grasses (gramineae) (Oros et al., 2006) p-coumaryl alcohol is the dominant lignin unit not prevalent in softwood and hardwood. Other significant products from burning grasses are acetosyringone, syringic acid, vanillin and vanillic acid. Methoxy phenols degrade in the atmosphere, where 2-methoxyphenol (guaiacol) and its isomers in the gas-phase react with OH hydroxyradicals (Coeur-Tourneur et al., 2010), while phenols react with 3C (aromatic carbonyl) (Smith et al., 2014) and some methoxy phenols in particulate matter react with O3 (Net et al., 2011), NO3 (Liu et al., 2012), 3C(Yu et al., 2014), OH (Li et al., 2014, Yu et al., 2014), and UV (Li et al., 2014).

Most previous determinations of PCs in aerosols were performed in zones close to residential areas using biomass burning in domestic heating (Bari et al., 2010, Bari et al., 2011, Dutton et al., 2009, Dutton et al., 2010, He et al., 2010, Simpson et al., 2005, Ward et al., 2011) or else in zones heavily impacted from wildfire smoke (Ward et al., 2006). PCs occur in high concentrations near these biomass burning sources, ranging from 10 s to greater than 10,000 pg m 3 (Bari et al., 2010, Bari et al., 2011, Dutton et al., 2009, Dutton et al., 2010, He et al., 2010, Simpson et al., 2005, Ward et al., 2011). In the Arctic, PCs have considerably lower concentrations with mean values (for particle sizes of 10 μm to < 0.49 μm) of 14 pg m 3 (Zangrando et al., 2013). Several studies determine PCs in ice and snow collected in Arctic areas (Hegg et al., 2010, Kawamura et al., 2012, McConnell et al., 2007), suggesting their applicability to Antarctic sites.

This work determines levoglucosan and PCs including vanillic acid (VA), isovanillic acid (IVA), homovanillic acid (HA), syringic acid (SyA), vanillin (VAN), syringaldehyde (SyAH), ferulic acid (FA), p-coumaric acid (PA) and coniferyl aldehyde (CAH) in three different Antarctic environments in order to investigate how transport affects the concentrations, evolution and sinks of these compounds in aerosols. We examine the concentrations and particle size distributions of biomass burning tracers in remote aerosols at the Concordia Station (Dome C) on the East Antarctic plateau during 2011–2012, 2012–2013, the coastal Mario Zucchelli Station in 2010–2011, and marine aerosol samples collected during the R/V Italica oceanographic cruise in the Southern Ocean in 2012 (Fig. 1).

Section snippets

Reagents and standard solutions

HPLC/MS-grade methanol (MeOH) and acetonitrile (ACN) were purchased from Romil LTD (Cambridge, U.K.). The ultrapure water (18.2  cm, 0.01 TOC) was produced by a Purelab Flex (Elga, High Wycombe, U.K.) and formic acid (98%) was obtained by Fluka (Sigma Aldrich, Buchs, Switzerland). Levoglucosan (purity 99%), vanillin (VAN) (≥ 98%), syringic acid (SyA) (≥ 95%), homovanillic acid (HA) (≥ 98%), isovanillic acid (IVA) (97%), p-coumaric acid (PA) (≥ 98%), coniferyl aldehyde (CAH) (98%), were purchased

Levoglucosan and phenolic compounds in total suspended particles over the Southern Ocean

We determined levoglucosan and PCs in aerosol samples collected over the Southern Ocean during the R/V Italica research cruise from January 13 to February 19, 2012 during the trip to and from Mario Zucchelli Station. Sample summaries, and sampling details in Table S2, while Table 1 records atmospheric concentrations of levoglucosan and PCs. Median levoglucosan concentrations were 37.6 pg m 3, ranging from BDL to 224.1 pg m 3 (Fig. S2 and Table S6) and the median phenolic compound concentrations for

Conclusions

Here, we determined that levoglucosan can be detected in remote areas, even in sites as distant from biomass burning sources as Dome C, East Antarctica. Our results indicate that the biomass burning tracer levoglucosan reached the inner Antarctic plateau through long-range transport and was present in accumulation-mode aerosols. At the coastal site levoglucosan was substantially present on coarse particles created by hygroscopic growth. During an oceanographic cruise on the Ross Sea when winds

Acknowledgments

This work was financially supported by the Italian Programma Nazionale di Ricerche in Antartide (PNRA) through the project 2009/A2.11.

The research was also supported by funding from the National Research Council of Italy (CNR) and from ERC Advanced Grant267696, contribution n° 17.

The authors gratefully acknowledge the NOAA Air Resources Laboratory (ARL) for providing the HYSPLIT transport and dispersion model and/or READY website (http://www.ready.noaa.gov) used in this publication.

We

References (99)

  • L.J. Kuo et al.

    Influence of combustion conditions on yields of solvent-extractable anhydrosugars and lignin phenols in chars: implications for characterizations of biomass combustion residues

    Chemosphere

    (2011)
  • J.M. Lobbes et al.

    Biogeochemical characteristics of dissolved and particulate organic matter in Russian rivers entering the Arctic ocean

    Geochim. Cosmochim. Acta

    (2000)
  • D. Mavrocordatos et al.

    Fractal analysis of wood combustion aggregates by contact mode atomic force microscopy

    Atmos. Environ.

    (2002)
  • S. Net et al.

    Heterogeneous reactions of ozone with methoxyphenols, in presence and absence of light

    Atmos. Environ.

    (2011)
  • G.D. Onstad et al.

    Sources of particulate organic matter in rivers from the continental USA: lignin phenol and stable carbon isotope compositions

    Geochim. Cosmochim. Acta

    (2000)
  • S. Opsahl et al.

    Early diagenesis of vascular plant-tissues-lignin and cutin decomposition and biogechemical implications

    Geochim. Cosmochim. Acta

    (1995)
  • D.R. Oros et al.

    Identification and emission factors of molecular tracers in organic aerosols from biomass burning part 1. Temperate climate conifers

    Appl. Geochem.

    (2001)
  • D.R. Oros et al.

    Identification and emission factors of molecular tracers in organic aerosols from biomass burning part 2. Deciduous trees

    Appl. Geochem.

    (2001)
  • D.R. Oros et al.

    Identification and emission factors of molecular tracers in organic aerosols from biomass burning: part 3. Grasses

    Appl. Geochem.

    (2006)
  • V. Pant et al.

    Size distribution of atmospheric aerosols at Maitri, Antarctica

    Atmos. Environ.

    (2011)
  • M.G. Perrone et al.

    Sources of high PM2.5 concentrations in Milan, northern Italy: molecular marker data and CMB modelling

    Sci. Total Environ.

    (2012)
  • B.R.T. Simoneit

    Biomass burning — a review of organic tracers for smoke from incomplete combustion

    Appl. Geochem.

    (2002)
  • R. Udisti et al.

    Sea spray aerosol in central Antarctica. Present atmospheric behaviour and implications for paleoclimatic reconstructions

    Atmos. Environ.

    (2012)
  • E. von Schneidemesser et al.

    Concentrations and sources of carbonaceous aerosol in the atmosphere of summit, Greenland

    Atmos. Environ.

    (2009)
  • G.H. Wang et al.

    Comparison of organic compositions in dust storm and normal aerosol samples collected at Gosan, Jeju Island, during spring 2005

    Atmos. Environ.

    (2009)
  • G.H. Wang et al.

    Molecular composition and size distribution of sugars, sugar-alcohols and carboxylic acids in airborne particles during a severe urban haze event caused by wheat straw burning

    Atmos. Environ.

    (2011)
  • T.J. Ward et al.

    Characterization and evaluation of smoke tracers in PM: results from the 2003 Montana wildfire season

    Atmos. Environ.

    (2006)
  • T.J. Ward et al.

    Organic/elemental carbon and woodsmoke tracer concentrations following a community wide woodstove changeout program

    Atmos. Environ.

    (2011)
  • S. Agarwal et al.

    Size distributions of dicarboxylic acids, ketoacids, alpha-dicarbonyls, sugars, WSOC, OC, EC and inorganic ions in atmospheric particles over northern Japan: implication for long-range transport of siberian biomass burning and east Asian polluted aerosols

    Atmos. Chem. Phys.

    (2010)
  • S.K. Akagi et al.

    Emission factors for open and domestic biomass burning for use in atmospheric models

    Atmos. Chem. Phys.

    (2011)
  • S. Argentini et al.

    Summer boundary-layer height at the plateau site of Dome C, Antarctica

    Bound.-Layer Meteorol.

    (2005)
  • E. Asmi et al.

    Hygroscopicity and chemical composition of antarctic sub-micrometre aerosol particles and observations of new particle formation

    Atmos. Chem. Phys.

    (2010)
  • A.P. Ault et al.

    Size-dependent changes in sea spray aerosol composition and properties with different seawater conditions

    Environ. Sci. Technol.

    (2013)
  • M.A. Bari et al.

    Air pollution in residential areas from wood-fired heating

    Aerosol Air Qual. Res.

    (2011)
  • A.M. Cecchi et al.

    Sorption–desorption of phenolic acids as affected by soil properties

    Biol. Fertil. Soils

    (2004)
  • Y. Cheng et al.

    Biomass burning contribution to Beijing aerosol

    Atmos. Chem. Phys.

    (2013)
  • C. Coeur-Tourneur et al.

    Rate coefficients for the gas-phase reaction of hydroxyl radicals with 2-methoxyphenol (guaiacol) and related compounds

    J. Phys. Chem. A

    (2010)
  • R.R. Draxler et al.

    HYSPLIT (HYbrid Single-Particle Lagrangian Integrated Trajectory) Model Access Via NOAA ARL READY Website (http://www.arl.noaa.gov/HYSPLIT.php)

    (2013)
  • I. Fattori et al.

    Chemical composition and physical features of summer aerosol at Terra Nova Bay and Dome C, Antarctica

    J. Environ. Monitor.

    (2005)
  • M. Fiebig et al.

    Tracing biomass burning aerosol from South America to troll research station, Antarctica

    Geophys. Res. Lett.

    (2009)
  • M.G. Flanner et al.

    Present-day climate forcing and response from black carbon in snow

    J. Geophys. Res.-Atmos.

    (2007)
  • P.Q. Fu et al.

    Photochemical and other sources of organic compounds in the Canadian high Arctic aerosol pollution during winter–spring

    Environ. Sci. Technol.

    (2009)
  • P.Q. Fu et al.

    Molecular characterization of urban organic aerosol in tropical India: contributions of primary emissions and secondary photooxidation

    Atmos. Chem. Phys.

    (2010)
  • A. Gambaro et al.

    Direct determination of levoglucosan at the picogram per milliliter level in antarctic ice by high-performance liquid chromatography/electrospray ionization triple quadrupole mass spectrometry

    Anal. Chem.

    (2008)
  • B. Graham et al.

    Water-soluble organic compounds in biomass burning aerosols over Amazonia —1. Characterization by NMR and GC-MS

    J. Geophys. Res. Atmos.

    (2002)
  • K. Hara et al.

    Haze episodes at Syowa Station, coastal Antarctica: where did they come from?

    J. Geophys. Res. Atmos.

    (2010)
  • S.B. Hawthorne et al.

    PM-10 high-volume collection and quantitation of semivolatile and nonvolatile phenols, methoxylated phenols, alkanes, and polycyclic aromatic-hydrocarbons from winter urban air and their relationship to wood smoke emissions

    Environ. Sci. Technol.

    (1992)
  • J. He et al.

    Composition of semi-volatile organic compounds in the urban atmosphere of Singapore: influence of biomass burning

    Atmos. Chem. Phys.

    (2010)
  • D.A. Hegg et al.

    Sources of light-absorbing aerosol in Arctic snow and their seasonal variation

    Atmos. Chem. Phys.

    (2010)
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