Sanna Saarikoski

The Molecular Identification of Organic Compounds in the Atmosphere: State of the Art and Challenges

Atmosphere: State of the Art and Challenges Barbara Nozier̀e,*,† Markus Kalberer,*,‡ Magda Claeys,* James Allan, Barbara D’Anna,† Stefano Decesari, Emanuela Finessi, Marianne Glasius, Irena Grgic,́ Jacqueline F. Hamilton, Thorsten Hoffmann, Yoshiteru Iinuma, Mohammed Jaoui, Ariane Kahnt, Christopher J. Kampf, Ivan Kourtchev,‡ Willy Maenhaut, Nicholas Marsden, Sanna Saarikoski, Jürgen Schnelle-Kreis, Jason D. Surratt, Sönke Szidat, Rafal Szmigielski, and Armin Wisthaler †Ircelyon/CNRS and Universite ́ Lyon 1, 69626 Villeurbanne Cedex, France ‡University of Cambridge, Cambridge CB2 1EW, United Kingdom University of Antwerp, 2000 Antwerp, Belgium The University of Manchester & National Centre for Atmospheric Science, Manchester M13 9PL, United Kingdom Istituto ISAC C.N.R., I-40129 Bologna, Italy University of York, York YO10 5DD, United Kingdom University of Aarhus, 8000 Aarhus C, Denmark National Institute of Chemistry, 1000 Ljubljana, Slovenia Johannes Gutenberg-Universitaẗ, 55122 Mainz, Germany Leibniz-Institut für Troposphar̈enforschung, 04318 Leipzig, Germany Alion Science & Technology, McLean, Virginia 22102, United States Max Planck Institute for Chemistry, 55128 Mainz, Germany Ghent University, 9000 Gent, Belgium Finnish Meteorological Institute, FI-00101 Helsinki, Finland Helmholtz Zentrum München, D-85764 Neuherberg, Germany University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States University of Bern, 3012 Bern, Switzerland Institute of Physical Chemistry PAS, Warsaw 01-224, Poland University of Oslo, 0316 Oslo, Norway

Size Distribution Measurement of Carbonaceous Particulate Matter Using a Low Pressure Impactor with Quartz Fiber Substrates

The collection characteristics of a small deposit area low pressure impactor (SDI) were studied in order to employ the impactor for size distribution measurements of carbonaceous matter. In this work, the SDI was calibrated for soft and porous quartz substrate material in a series of laboratory experiments. The collection efficiency curves were measured by using monodisperse dioctyl sebacate particles and by applying two different detection methods. One method was based on the detection of current carried by charged test particles, and the other measured number concentrations of particles in bipolar charge equilibrium by two condensation particle counters. Concerning the particle size corresponding to a 50% collection efficiency (D 50 ), significant shifts toward smaller particle sizes were found for the quartz fiber substrates compared with the flat plates. Also the shapes of the collection efficiency curves differed considerably: quartz substrate gave less steep curves than plain impaction plates. The new calibration was applied to field data from urban and rural sites. Compared with the original calibration of the SDI, the new calibration changed the measured size distributions of organic and elemental carbon. In addition, a reasonable size-segregated mass closure was achieved by combining data from thermal-optical analysis and ion-chromatography.

Physical and Chemical Characterization of Real-World Particle Number and Mass Emissions from City Buses in Finland.

Exhaust emissions of 23 individual city buses at Euro III, Euro IV and EEV (Enhanced Environmentally Friendly Vehicle) emission levels were measured by the chasing method under real-world conditions at a depot area and on the normal route of bus line 24 in Helsinki. The buses represented different technologies from the viewpoint of engines, exhaust after-treatment systems (ATS) and fuels. Some of the EEV buses were fueled by diesel, diesel-electric, ethanol (RED95) and compressed natural gas (CNG). At the depot area the emission factors were in the range of 0.3-21 × 10(14) # (kg fuel)(-1), 6-40 g (kg fuel)(-1), 0.004-0.88 g (kg fuel)(-1), 0.004-0.56 g (kg fuel)(-1), 0.01-1.2 g (kg fuel)(-1), for particle number (EFN), nitrogen oxides (EFNOx), black carbon (EFBC), organics (EFOrg), and particle mass (EFPM1), respectively. The highest particulate emissions were observed from the Euro III and Euro IV buses and the lowest from the ethanol and CNG-fueled buses, which emitted BC only during acceleration. The organics emitted from the CNG-fueled buses were clearly less oxidized compared to the other bus types. The bus line experiments showed that lowest emissions were obtained from the ethanol-fueled buses whereas large variation existed between individual buses of the same type indicating that the operating conditions by drivers had large effect on the emissions.

Wintertime Aerosol Chemistry in Sub-Arctic Urban Air

Measurements of submicron particulate matter (PM) were performed at an urban background station, in Helsinki, Finland during wintertime to investigate the chemical characteristics and sources of PM1. The PM1 was dominated by sulfate and organics. The source apportionment indicated that organic aerosol (OA) was a mixture from local sources (biomass burning (BBOA), traffic, coffee roaster (CROA)), secondary compounds formed in local wintertime conditions (nitrogen containing OA (NOA), semivolatile oxygenated OA (SV-OOA), and regional and long-range transported compounds (low volatile oxygenated OA, LV-OOA). BBOA was dominated by the fragments C2H4O2 + and C3H4O2 + (m/z 60.021 and 73.029) from levoglucosan, or other similar sugar components, comprising on average 32% of the BBOA mass concentration. The ratio between fragments C2H4O2 +/C3H4O2 + was significantly lower for CROA (=1.1) when compared to BBOA (=2.1), indicating that they consisted of different sugar compounds. In addition, a component containing substantial amount of nitrogen compounds (NOA) was observed in a sub-arctic region for the first time. The NOA contribution to OA ranged from 1% to 29% and elevated concentrations were observed when ambient relative humidity was high and the visibility low. Low solar radiation and temperature in wintertime were observed to influence the oxidation of compounds. A change in aerosol composition, with an increase of LV-OOA and decrease in BBOA, SV-OOA and NOA was noticed during the transition from wintertime to springtime. Size distribution measurements with high-time resolution enabled chemical characterization of externally mixed aerosol from different sources. Aged regional long-range transported aerosols were dominant at around 0.5 μm (vacuum aerodynamic diameter), whereas traffic and CROA emissions dominated at around 120 nm. Copyright 2014 American Association for Aerosol Research

Traffic is a major source of atmospheric nanocluster aerosol

Significance We report the significant presence of traffic-originated nanocluster aerosol (NCA) particles in a particle diameter range of 1.3–3.0 nm of urban air, determine the emission factors for the NCA, and evaluate its global importance. Our findings are important because they significantly update the current understanding of atmospheric aerosol in urban areas. They demonstrate that in urban air, extremely small particles form a significant fraction of the total particle number and are a direct result of anthropogenic emissions, that is, the emissions from road traffic. Thus, our findings also imply that in urban areas, an atmospheric nucleation process is not necessary for the formation of a large number of particles that affect population health and climate. In densely populated areas, traffic is a significant source of atmospheric aerosol particles. Owing to their small size and complicated chemical and physical characteristics, atmospheric particles resulting from traffic emissions pose a significant risk to human health and also contribute to anthropogenic forcing of climate. Previous research has established that vehicles directly emit primary aerosol particles and also contribute to secondary aerosol particle formation by emitting aerosol precursors. Here, we extend the urban atmospheric aerosol characterization to cover nanocluster aerosol (NCA) particles and show that a major fraction of particles emitted by road transportation are in a previously unmeasured size range of 1.3–3.0 nm. For instance, in a semiurban roadside environment, the NCA represented 20–54% of the total particle concentration in ambient air. The observed NCA concentrations varied significantly depending on the traffic rate and wind direction. The emission factors of NCA for traffic were 2.4·1015 (kgfuel)−1 in a roadside environment, 2.6·1015 (kgfuel)−1 in a street canyon, and 2.9·1015 (kgfuel)−1 in an on-road study throughout Europe. Interestingly, these emissions were not associated with all vehicles. In engine laboratory experiments, the emission factor of exhaust NCA varied from a relatively low value of 1.6·1012 (kgfuel)−1 to a high value of 4.3·1015 (kgfuel)−1. These NCA emissions directly affect particle concentrations and human exposure to nanosized aerosol in urban areas, and potentially may act as nanosized condensation nuclei for the condensation of atmospheric low-volatile organic compounds.

Size distribution, chemical composition, and hygroscopicity of fine particles emitted from an oil-fired heating plant.

Heavy fuel oil (HFO) is a commonly used fuel in industrial heating and power generation and for large marine vessels. In this study, the fine particle emissions of a 47 MW oil-fired boiler were studied at 30 MW power and with three different fuels. The studied fuels were HFO, water emulsion of HFO, and water emulsion of HFO mixed with light fuel oil (LFO). With all the fuels, the boiler emitted considerable amounts of particles smaller than 200 nm in diameter. Further, these small particles were quite hygroscopic even as fresh and, in the case of HFO+LFO emulsion, the hygroscopic growth of the particles was dependent on particle size. The use of emulsions and the addition of LFO to the fuel had a reducing effect on the hygroscopic growth of particles. The use of emulsions lowered the sulfate content of the smallest particles but did not affect significantly the sulfate content of particles larger than 42 nm and, further, the addition of LFO considerably increased the black carbon content of particulate matter. The results indicate that even the fine particles emitted from HFO based combustion can have a significant effect on cloud formation, visibility, and air quality.

Natural Gas Engine Emission Reduction by Catalysts

In order to meet stringent emission limits, after-treatment systems are increasingly utilized in natural gas engine applications. In this work, two catalyst systems were studied in order to clarify how the catalysts affect, e.g. hydrocarbons, NOx and particles present in natural gas engine exhaust. A passenger car engine modified to run with natural gas was used in a research facility with possibilities to modify the exhaust gas properties. High NOx reductions were observed when using selective catalytic reduction, although a clear decrease in the NOx reduction was recorded at higher temperatures. The relatively fresh methane oxidation catalyst was found to reach reductions greater than 50% when the exhaust temperature and the catalyst size were sufficient. Both the studied catalyst systems were found to have a significant effect on particulate emissions. The observed particle mass reduction was found to be due to a decrease in the amount of organics passing over the catalyst. However, especially at high exhaust temperatures, high nanoparticle concentrations were observed downstream of the catalysts together with higher sulphate concentrations in particles. This study contributes to understanding emissions from future natural gas engine applications with catalysts in use.

Investigating the chemical species in submicron particles emitted by city buses

ABSTRACT Detailed chemical characterization of exhaust particles from 23 individual city buses was performed in Helsinki, Finland. Investigated buses represented different technologies in terms of engines, exhaust after-treatment systems (e.g., diesel particulate filter, selective catalytic reduction, and three-way catalyst) and fuels (diesel, diesel-electric (hybrid), ethanol, and compressed natural gas). Regarding emission standards, the buses operated at EURO III, EURO IV, and EEV (enhanced environmentally friendly vehicle) emission levels. The chemical composition of exhaust particles was determined by using a soot particle aerosol mass spectrometer (SP-AMS). Based on the SP-AMS results, the bus emission particles were dominated by organics and refractory black carbon (rBC). The mass spectra of organics consisted mostly of hydrocarbon fragments (54–86% of total organics), the pattern of hydrocarbon fragments being rather similar regardless of the bus type. Regarding oxygenated organic fragments, ethanol-fueled buses had unique mass-to-charge ratios (m/z) of 45, 73, 87, and 89 (mass fragments of C2H5O+, C3H5O2+, C4H7O2+, and C4H9O2+, respectively) that were not detected for the other bus types at the same level. For rBC, there was a small difference in the ratio of C4+ and C5+ to C3+ for different bus types but also for the individual buses of the same type. In addition to organics and rBC, the presence of trace metals in the bus emission particles was investigated. Copyright

Wildfires as a Source of Aerosol Particles Transported to the Northern European Regions

Each year large areas of forested land in Europe are burned by more than 50,000 fires. Over the past few years, climatic anomalies in temperature and precipitation have resulted in an increase in fire events. The exceptional fire occurrences in the 2000s and their regional consequences on atmospheric air quality have been observed in the northern European regions. In the last 10 years almost annually the episodes of long-range transported (LRT) biomass smokes from Eastern European fires have been reported, exceptionally intense smoke plumes having been detected in 2002 and 2006. Typically, the smoke episodes occur in spring or/and late summer and they last for few days. As the particulate matter (PM) concentrations are generally quite low in Northern Europe, the LRT smoke plumes increase the PM concentrations in several folds even at the background sites with no local emissions. As a result, there are exceedances in the European Union PM daily limit values, which result in serious health problems. This chapter describes the episodes of wildfire particles observed in Northern Europe in the last 10 years. It discusses the chemical and physical properties of particles, the transformation during the transport as well as the methods to investigate the composition and source areas of smoke plumes.

Spatiotemporal Variation in Composition of Submicron Particles in Santiago Metropolitan Region, Chile

The chemical composition of submicron particles (aerodynamic diameter Da < 1.0 μm) was investigated at three locations in the Santiago Metropolitan Region (SMR), Chile. Measurements campaigns were conducted in winter and spring 2016, at representative sites of a rural, urban and urban receptor environment. Instrumentation consisted of an optical analyzer to determine Black Carbon (BC) and the Aerosol Chemical Speciation Monitor (ACSM) to measure concentrations of particulate chloride (Cl-), nitrate (NO3-), sulfate (SO42-), ammonium (NH4+) and non-refractory carbonaceous species (organics). Complementary data, such as ozone concentration and meteorological parameters were obtained from the public air quality network. Results showed that in both the winter and spring seasons the organics predominated in the mass of submicron particles. This fraction was followed in decreasing order by NO3-, NH4+, BC, SO42- and Cl-. The highest average organics concentrations were measured in winter at the urban (32.2 µg m–3) and urban receptor sites (20.1 µg m–3). In winter, average concentrations of both NO3- and NH4+ were higher at the urban receptor site (12.3 and 4.5 µg m–3, respectively) when compared to the urban site (6.4 and 3.1 µg m–3, respectively). In general, all the measured species were present in higher concentrations during winter, excepting SO42-, which was the only one that increased during spring. The transition towards spring was also associated with an acidification of the aerosol at the rural and urban receptor site, while at the urban site the aerosol was observed alkaline. The highest average ozone concentration during both the winter and spring seasons were recorded at the urban receptor site (7.2 and 24.0 ppb, respectively). The study reports data showing that the atmosphere in the SRM has a considerable load of particulate organic compounds, NO3- and NH4+, which are in higher concentrations at urban sites during the winter season. Based on wind patterns and the hourly profiles of chemical species, the study suggests that during daytime the polluted air masses from the urban center can move to the northeast part of the region (namely urban receptor site) leading to the formation of submicron particles as well as photochemical ozone.