Measurement report: Long-term measurements of aerosol precursor concentrations in the Finnish sub-Arctic boreal forest

Abstract. Aerosol particles form in the atmosphere by clustering of certain atmospheric vapors. After growing to larger particles by condensation of low volatile gases, they can affect the Earth’s climate directly by scattering light and indirectly by acting as cloud condensation nuclei. Observations of low-volatility aerosol precursor gases have been reported around the world but longer-term measurement series and any Arctic data sets showing seasonal variation are close to non-existent. In here, we present ~7 months of aerosol precursor gas measurements performed with the nitrate based chemical ionization mass spectrometer (CI-APi-TOF). We deployed our measurements ~150 km North of the Arctic Circle at the continental Finnish sub-Arctic field station, SMEAR I, located in Värriö strict nature reserve. We report concentration measurements of the most common new particle formation related compounds; sulfuric acid (SA), methane sulfonic acid (MSA), iodic acid (IA) and a total concentration of highly oxygenated organic compounds (HOMs). At this remote measurement site, SA is originated both from anthropogenic and biological sources and has a clear diurnal cycle but no significant seasonal variation. MSA shows a more distinct seasonal cycle with concentrations peaking in the summer. Of the measured compounds, iodic acid concentrations are the most stable throughout the measurement period, except in April, when the concentration of IA is significantly higher than during the rest of the year. Otherwise, IA has almost identical daily maximum concentrations in spring, summer and autumn, and on new particle formation event or non-event days. HOMs are abundant during the summer months and low in winter months. Due to the low winter concentrations and their high correlation with ambient air temperature, we suggest that most of HOMs are products of biogenic emissions, most probably monoterpene oxidation products. New particle formation events at SMEAR I happen under relatively low temperatures with a fast temperature rise in the morning followed by decreasing relative humidity during the day. The ozone concentrations are on average ~10 ppbv higher on NPF days than non-event days. During NPF days, we have on average higher SA concentration peaking at noon, higher MSA concentrations in the afternoon and slightly higher IA concentration than during non-event days. All together, these are the first long term measurements of aerosol forming vapors from the SMEAR I in the sub-arctic region, and the results help us to understand atmospheric chemical processes and aerosol formation in the rapidly changing Arctic.

[1]  Stefan K. Weber,et al.  Role of iodine oxoacids in atmospheric aerosol nucleation , 2021, Science.

[2]  P. Zieger,et al.  Aerosols in current and future Arctic climate , 2021, Nature Climate Change.

[3]  T. Petäjä,et al.  Wintertime sub-arctic new particle formation from Kola Peninsula sulphur emissions , 2021 .

[4]  J. Aalto,et al.  Dwarf Shrubs Impact Tundra Soils: Drier, Colder, and Less Organic Carbon , 2020, Ecosystems.

[5]  H. Hakola,et al.  Sesquiterpenes dominate monoterpenes in northern wetland emissions , 2020, Atmospheric Chemistry and Physics.

[6]  P. Crill,et al.  Volatile organic compound fluxes in a subarctic peatland and lake , 2020, Atmospheric Chemistry and Physics.

[7]  M. Schloter,et al.  Origin of volatile organic compound emissions from subarctic tundra under global warming , 2020, Global change biology.

[8]  T. Vesala,et al.  CarbonSink+: Accounting for multiple climate feedbacks from forests , 2020 .

[9]  Jun He,et al.  Iodine speciation and size distribution in ambient aerosols at a coastal new particle formation hotspot in China , 2019, Atmospheric Chemistry and Physics.

[10]  Warren R. L. Cairns,et al.  Diurnal cycle of iodine and mercury concentrations in Svalbard surface snow , 2019 .

[11]  D. Worsnop,et al.  Evaluating the performance of five different 1 chemical ionization techniques for detecting gaseous 2 oxygenated organic species , 2018 .

[12]  I. Riipinen,et al.  Multicomponent new particle formation from sulfuric acid, ammonia, and biogenic vapors , 2018, Science Advances.

[13]  M. Ehn,et al.  Primary Formation of Highly Oxidized Multifunctional Products in the OH-Initiated Oxidation of Isoprene: A Combined Theoretical and Experimental Study. , 2018, Environmental science & technology.

[14]  R. Harrison,et al.  Regions of open water and melting sea ice drive new particle formation in North East Greenland , 2018, Scientific Reports.

[15]  B. Lee,et al.  Atmospheric DMS in the Arctic Ocean and Its Relation to Phytoplankton Biomass , 2018 .

[16]  R. Reynolds,et al.  The NCEP/NCAR 40-Year Reanalysis Project , 1996, Renewable Energy.

[17]  P. Shepson,et al.  Active molecular iodine photochemistry in the Arctic , 2017, Proceedings of the National Academy of Sciences.

[18]  D. Spracklen,et al.  Global modeling of tropospheric iodine aerosol , 2016 .

[19]  T. Petäjä,et al.  How to reliably detect molecular clusters and nucleation mode particles withNeutral cluster and Air Ion Spectrometer (NAIS) , 2016 .

[20]  J. Seinfeld,et al.  Ion-induced nucleation of pure biogenic particles , 2016, Nature.

[21]  T. Petäjä,et al.  Intermediate ions as a strong indicator of new particle formation bursts in a boreal forest , 2016 .

[22]  T. Petäjä,et al.  Characteristics of new-particle formation at three SMEAR stations , 2016 .

[23]  M. Rissanen,et al.  Modeling the Charging of Highly Oxidized Cyclohexene Ozonolysis Products Using Nitrate-Based Chemical Ionization. , 2015, The journal of physical chemistry. A.

[24]  A. Michelsen,et al.  Climate change-induced vegetation change as a driver of increased subarctic biogenic volatile organic compound emissions , 2015, Global change biology.

[25]  Corey J. A. Bradshaw,et al.  Global estimates of boreal forest carbon stocks and flux , 2015 .

[26]  Wolfgang Lucht,et al.  Forest resilience and tipping points at different spatio‐temporal scales: approaches and challenges , 2015 .

[27]  D. Worsnop,et al.  Rapid autoxidation forms highly oxidized RO2 radicals in the atmosphere. , 2014, Angewandte Chemie.

[28]  João Almeida,et al.  Neutral molecular cluster formation of sulfuric acid–dimethylamine observed in real time under atmospheric conditions , 2014, Proceedings of the National Academy of Sciences.

[29]  T. Petäjä,et al.  Trends in atmospheric new-particle formation: 16 years of observations in a boreal-forest environment , 2014 .

[30]  D. R. Hanson,et al.  Stabilization of sulfuric acid dimers by ammonia, methylamine, dimethylamine, and trimethylamine , 2014 .

[31]  H. Kjaergaard,et al.  A large source of low-volatility secondary organic aerosol , 2014, Nature.

[32]  P. Hari,et al.  Trends in new particle formation in eastern Lapland, Finland: effect of decreasing sulfur emissions from Kola Peninsula , 2013 .

[33]  M. Levasseur Impact of Arctic meltdown on the microbial cycling of sulphur , 2013 .

[34]  Erik Swietlicki,et al.  Warming-induced increase in aerosol number concentration likely to moderate climate change , 2013 .

[35]  I. Riipinen,et al.  Direct Observations of Atmospheric Aerosol Nucleation , 2013, Science.

[36]  M. Shaw,et al.  Atmospheric iodine levels influenced by sea surface emissions of inorganic iodine , 2013 .

[37]  J. Curtius,et al.  Calibration of a chemical ionization mass spectrometer for the measurement of gaseous sulfuric acid. , 2012, The journal of physical chemistry. A.

[38]  A. Mirme,et al.  The mathematical principles and design of the NAIS – a spectrometer for the measurement of cluster ion and nanometer aerosol size distributions , 2011 .

[39]  E. Atlas,et al.  Iodine containing species in the remote marine boundary layer: A link to oceanic phytoplankton , 2011 .

[40]  Jorge Lima,et al.  Role of sulphuric acid, ammonia and galactic cosmic rays in atmospheric aerosol nucleation , 2011, Nature.

[41]  Y. Q. Wang,et al.  TrajStat: GIS-based software that uses various trajectory statistical analysis methods to identify potential sources from long-term air pollution measurement data , 2009, Environ. Model. Softw..

[42]  A. Michelsen,et al.  Climatic warming increases isoprene emission from a subarctic heath. , 2008, The New phytologist.

[43]  I. Riipinen,et al.  Toward Direct Measurement of Atmospheric Nucleation , 2007, Science.

[44]  E. Nilsson,et al.  Concentrations and fluxes of aerosol particles during the LAPBIAT measurement campaign at Värriö field station , 2007 .

[45]  I. Riipinen,et al.  Aerosol size distribution measurements at four Nordic field stations: identification, analysis and trajectory analysis of new particle formation bursts , 2007 .

[46]  A. Stohl Characteristics of atmospheric transport into the Arctic troposphere , 2006 .

[47]  H. Hansson,et al.  High Natural Aerosol Loading over Boreal Forests , 2006, Science.

[48]  P. Hari,et al.  Temperature and light dependence of the VOC emissions of Scots pine , 2004 .

[49]  P. Hari,et al.  Atmospheric particle formation events at Värriö measurement station in Finnish Lapland 1998-2002 , 2004 .

[50]  P. Hari,et al.  Atmospheric trace gas and aerosol particle concentration measurements in Eastern Lapland, Finland 1992-2001 , 2003 .

[51]  J. Seinfeld,et al.  Marine aerosol formation from biogenic iodine emissions , 2002, Nature.

[52]  Ari Laaksonen,et al.  Analysis of the growth of nucleation mode particles observed in Boreal forest , 1998 .

[53]  L. Pirjola,et al.  Sulfate aerosol formation in the Arctic boundary layer , 1998 .

[54]  H. Lihavainen,et al.  Observations of ultrafine aerosol particle formation and growth in boreal forest , 1997 .

[55]  P. Hari,et al.  Air pollution in eastern Lapland : challenge for an environmental measurement station , 1994 .

[56]  S. Warren,et al.  Oceanic phytoplankton, atmospheric sulphur, cloud albedo and climate , 1987, Nature.

[57]  Douglas D. Davis,et al.  Iodine - Its possible role in tropospheric photochemistry , 1980 .