Ulla Makkonen

Direct Observations of Atmospheric Aerosol Nucleation

Aerosol Formation Most atmospheric aerosol particles result from a growth process that begins with atmospheric molecules and clusters, progressing to larger and larger sizes as they acquire other molecules, clusters, and particles. The initial steps of this process involve very small entities—with diameters of less than 2 nanometers—which have been difficult to observe. Kulmala et al. (p. 943; see the Perspective by Andreae) developed a sensitive observational protocol that allows these tiny seeds to be detected and counted, and they mapped out the process of aerosol formation in detail. Detailed aerosol measurements provide a consistent framework for the formation of particles from atmospheric gases. [Also see Perspective by Andreae] Atmospheric nucleation is the dominant source of aerosol particles in the global atmosphere and an important player in aerosol climatic effects. The key steps of this process occur in the sub–2-nanometer (nm) size range, in which direct size-segregated observations have not been possible until very recently. Here, we present detailed observations of atmospheric nanoparticles and clusters down to 1-nm mobility diameter. We identified three separate size regimes below 2-nm diameter that build up a physically, chemically, and dynamically consistent framework on atmospheric nucleation—more specifically, aerosol formation via neutral pathways. Our findings emphasize the important role of organic compounds in atmospheric aerosol formation, subsequent aerosol growth, radiative forcing and associated feedbacks between biogenic emissions, clouds, and climate.

Size distribution and chemical composition of airborne particles in south-eastern Finland during different seasons and wildfire episodes in 2006.

The inorganic main elements, trace elements and PAHs were determined from selected PM(1), PM(2.5) and PM(10) samples collected at the Nordic background station in Virolahti during different seasons and during the wildfire episodes in 2006. Submicron particles are those most harmful to human beings, as they are able to penetrate deep into the human respiratory system and may cause severe health effects. About 70-80%, of the toxic trace elements, like lead, cadmium, arsenic and nickel, as well as PAH compounds, were found in particles smaller than 1 microm. Furthermore, the main part of the copper, zinc, and vanadium was associated with submicron particles. In practice, all the PAHs found in PM(10) were actually in PM(2.5). For PAHs and trace elements, it is more beneficial to analyse the PM(2.5) or even the PM(1) fraction instead of PM(10), because exclusion of the large particles reduces the need for sample cleaning to minimize the matrix effects during the analysis. During the wildfire episodes, the concentrations of particles smaller than 2.5 microm, as well as those of submicron particles, increased, and also the ratio PM(1)/PM(10) increased to about 50%. On the fire days, the mean potassium concentration was higher in all particle fractions, but ammonium and nitrate concentrations rose only in particles smaller than 1.0 microm. PAH concentrations rose even to the same level as in winter.

Toxicological effects of emission particles from fossil- and biodiesel-fueled diesel engine with and without DOC/POC catalytic converter

There is increasing demand for renewable energy and the use of biodiesel in traffic is a major option when implying this increment. We investigated the toxicological activities of particulate emissions from a nonroad diesel engine, operated with conventional diesel fuel (EN590), and two biodiesels: rapeseed methyl ester (RME) and hydrotreated fresh vegetable oil (HVO). The engine was operated with all fuels either with or without catalyst (DOC/POC). The particulate matter (PM1) samples were collected from the dilution tunnel with a high-volume cascade impactor (HVCI). These samples were characterized for ions, elements, and polycyclic aromatic hydrocarbon (PAH) compounds. Mouse RAW264.7 macrophages were exposed to the PM samples for 24 h. Inflammatory mediators, (TNF-α and MIP-2), cytotoxicity, genotoxicity, and oxidative stress (reactive oxygen species [ROS]) were measured. All the samples displayed mostly dose-dependent toxicological activity. EN590 and HVO emission particles had larger inflammatory responses than RME-derived particles. The catalyst somewhat increased the responses per the same mass unit. There were no substantial differences in the cytotoxic responses between the fuels or catalyst use. Genotoxic responses by all the particulate samples were at same level, except weaker for the RME sample with catalyst. Unlike other samples, EN590-derived particles did not significantly increase ROS production. Catalyst increased the oxidative potential of the EN590 and HVO-derived particles, but decreased that with RME. Overall, the use of biodiesel fuels and catalyst decreased the particulate mass emissions compared with the EN590 fuel. Similar studies with different types of diesel engines are needed to assess the potential benefits from biofuel use in engines with modern technologies.

Ambient observations of dimers from terpene oxidation in the gas phase

We present ambient observations of dimeric monoterpene oxidation products (C16–20HyO6–9) in gas and particle phases in the boreal forest in Finland in spring 2013 and 2014, detected with a chemical ionization mass spectrometer with a filter inlet for gases and aerosols employing acetate and iodide as reagent ions. These are among the first online dual-phase observations of such dimers in the atmosphere. Estimated saturation concentrations of 10−15 to 10−6 µg m−3 (based on observed thermal desorptions and group-contribution methods) and measured gas-phase concentrations of 10−3 to 10−2 µg m−3 (~106–107 molecules cm−3) corroborate a gas-phase formation mechanism. Regular new particle formation (NPF) events allowed insights into the potential role dimers may play for atmospheric NPF and growth. The observationally constrained Model for Acid-Base chemistry in NAnoparticle Growth indicates a contribution of ~5% to early stage particle growth from the ~60 gaseous dimer compounds.

Ambient observations of dimers from terpene oxidation in the gas phase: Implications for new particle formation and growth: Ambient Observations of Gas-Phase Dimers

We present ambient observations of dimeric monoterpene oxidation products (C16–20HyO6–9) in gas and particle phases in the boreal forest in Finland in spring 2013 and 2014, detected with a chemical ionization mass spectrometer with a filter inlet for gases and aerosols employing acetate and iodide as reagent ions. These are among the first online dual-phase observations of such dimers in the atmosphere. Estimated saturation concentrations of 10−15 to 10−6 µg m−3 (based on observed thermal desorptions and group-contribution methods) and measured gas-phase concentrations of 10−3 to 10−2 µg m−3 (~106–107 molecules cm−3) corroborate a gas-phase formation mechanism. Regular new particle formation (NPF) events allowed insights into the potential role dimers may play for atmospheric NPF and growth. The observationally constrained Model for Acid-Base chemistry in NAnoparticle Growth indicates a contribution of ~5% to early stage particle growth from the ~60 gaseous dimer compounds.

Aerosol Chemistry Resolved by Mass Spectrometry: Linking Field Measurements of Cloud Condensation Nuclei Activity to Organic Aerosol Composition

Aerosol hygroscopic properties were linked to its chemical composition by using complementary online mass spectrometric techniques in a comprehensive chemical characterization study at a rural mountaintop station in central Germany in August 2012. In particular, atmospheric pressure chemical ionization mass spectrometry ((-)APCI-MS) provided measurements of organic acids, organosulfates, and nitrooxy-organosulfates in the particle phase at 1 min time resolution. Offline analysis of filter samples enabled us to determine the molecular composition of signals appearing in the online (-)APCI-MS spectra. Aerosol mass spectrometry (AMS) provided quantitative measurements of total submicrometer organics, nitrate, sulfate, and ammonium. Inorganic sulfate measurements were achieved by semionline ion chromatography and were compared to the AMS total sulfate mass. We found that up to 40% of the total sulfate mass fraction can be covalently bonded to organic molecules. This finding is supported by both on- and offline soft ionization techniques, which confirmed the presence of several organosulfates and nitrooxy-organosulfates in the particle phase. The chemical composition analysis was compared to hygroscopicity measurements derived from a cloud condensation nuclei counter. We observed that the hygroscopicity parameter (κ) that is derived from organic mass fractions determined by AMS measurements may overestimate the observed κ up to 0.2 if a high fraction of sulfate is bonded to organic molecules and little photochemical aging is exhibited.

Field comparison of measurement methods for sulphur dioxide and aerosol sulphate

Abstract Sampling methods for sulphur dioxide and particulate sulphate were compared at the Virolahti background station in southeastern Finland in 1993–1994. The methods compared included a monitor, two-stage and three-stage filter packs, an absorption solution and a passive sampler. No significant difference in the sulphur dioxide and sulphate results between the two filter pack methods was found ( n = 28). The sulphur dioxide results from the monitor were 6% lower than the results from the two-stage sampler ( n = 164). The average of sulphur dioxide results for six months from the daily absorption solution was only 4% higher than the results from the two-stage sampler, despite the significant absolute and relative bias between the two methods. The sulphate results from the prefilter of the low-volume absorption solution were considerably lower than the results of the two-stage sampler. The results from the two-week and the one-month passive samplers were in good agreement with the other methods, although their results were somewhat higher. The relative standard deviation for four parallel monthly passive samplers varied between 2% and 15%, with a median of 6%. The comparison showed that the passive sampler can be used to replace the absorption solution method, but at clean background stations the sampling time should not be shorter than one month. For measuring daily sulphur dioxide concentrations the sensitive monitor and the two- or three-stage filter pack methods are the viable alternatives.

Amines in boreal forest air at SMEAR II station in Finland

We measured amines in boreal forest air in Finland both in gas and particle phases with 1 h time resolution using an online ion chromatograph (instrument for Measuring AeRosols and Gases in Ambient Air – MARGA) connected to an electrospray ionization quadrupole mass spectrometer (MS). The developed MARGA-MS method was able to separate and detect seven different amines: monomethylamine (MMA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA), propylamine (PA), and butylamine (BA). The detection limits of the method for amines were low (0.2–3.1 ng m−3), the accuracy of ICMS analysis was 11–37 %, and the precision 10–15 %. The proper measurements in the boreal forest covered about 8 weeks between March and December 2015. The amines were found to be an inhomogeneous group of compounds, showing different seasonal and diurnal variability. Total MMA (MMA(tot)) peaked together with the sum of ammonia and ammonium ions already in March. In March, monthly means for MMA were< 2.4 and 6.8± 9.1 ng m−3 in gas and aerosol phases, respectively, and for NH3 and NH+4 these were 52± 16 and 425± 371 ng m−3, respectively. Monthly medians in March for MMA(tot), NH3, and NH+4 were < 2.4, 19 and 90 ng m−3, respectively. DMA(tot) and TMA(tot) had summer maxima indicating biogenic sources. We observed diurnal variation for DMA(tot) but not for TMA(tot). The highest concentrations of these compounds were measured in July. Then, monthly means for DMA were < 3.1 and 8.4± 3.1 ng m−3 in gas and aerosol phases, respectively, and for TMA these were 0.4± 0.1 and 1.8± 0.5 ng m−3. Monthly medians in July for DMA were below the detection limit (DL) and 4.9 ng m−3 in gas and aerosol phases, respectively, and for TMA these were 0.4 and 1.4 ng m−3. When relative humidity of air was > 90 %, gas-phase DMA correlated well with 1.1–2 nm particle number concentration (R2 = 0.63) suggesting that it participates in atmospheric clustering. EA concentrations were low all the time. Its July means were < 0.36 and 0.4± 0.4 ng m−3 in gas and aerosol phases, respectively, but individual concentration data correlated well with monoterpene concentrations in July. Monthly means of PA and BA were below detection limits at all times.

Effect of salt formation on condensation of organic compounds on atmospheric nanoparticles

Freshly formed atmospheric nanoparticles have been observed to contain also such organic compounds which have too high saturation vapor pressure to condense on nanoparticles reversibly. The condensation of these compounds on the particles may be facilitated by particle phase processes that transform the compounds into less-volatile form. Here we use particle growth model MABNAG to study the effect of particle phase acid-base chemistry on the condensation of organic acids and bases.