Showing papers by "Tuukka Petäjä published in 2011"

Role of sulphuric acid, ammonia and galactic cosmic rays in atmospheric aerosol nucleation

Abstract: Atmospheric aerosols exert an important influence on climate through their effects on stratiform cloud albedo and lifetime and the invigoration of convective storms. Model calculations suggest that almost half of the global cloud condensation nuclei in the atmospheric boundary layer may originate from the nucleation of aerosols from trace condensable vapours, although the sensitivity of the number of cloud condensation nuclei to changes of nucleation rate may be small. Despite extensive research, fundamental questions remain about the nucleation rate of sulphuric acid particles and the mechanisms responsible, including the roles of galactic cosmic rays and other chemical species such as ammonia. Here we present the first results from the CLOUD experiment at CERN. We find that atmospherically relevant ammonia mixing ratios of 100 parts per trillion by volume, or less, increase the nucleation rate of sulphuric acid particles more than 100–1,000-fold. Time-resolved molecular measurements reveal that nucleation proceeds by a base-stabilization mechanism involving the stepwise accretion of ammonia molecules. Ions increase the nucleation rate by an additional factor of between two and more than ten at ground-level galactic-cosmic-ray intensities, provided that the nucleation rate lies below the limiting ion-pair production rate. We find that ion-induced binary nucleation of H_(2)SO_(4)–H_(2)O can occur in the mid-troposphere but is negligible in the boundary layer. However, even with the large enhancements in rate due to ammonia and ions, atmospheric concentrations of ammonia and sulphuric acid are insufficient to account for observed boundary-layer nucleation.

Organic condensation: a vital link connecting aerosol formation to cloud condensation nuclei (CCN) concentrations

Abstract: Atmospheric aerosol particles influence global climate as well as impair air quality through their effects on atmospheric visibility and human health Ultrafine (

Particle Size Magnifier for Nano-CN Detection

Abstract: A new particle size magnifier (PSM) for detection of nano-CN as small as ∼1 nm in mobility diameter was developed, calibrated and tested in atmospheric measurements. The working principle of a PSM is to mix turbulently cooled sample flow with heated clean air flow saturated by the working fluid. This provides a high saturation ratio for the working fluid and activates the seed particles and grows them by condensation of the working fluid. In order to reach high saturation ratios, and thus to activate nano-CN without homogeneous nucleation, diethylene glycol was chosen as the working fluid. The PSM was able to grow nano-CN to mean diameter of 90 nm, after which an ordinary condensation particle counter was used to count the grown particles (TSI 3010). The stability of the PSM was found to be good making it suitable for stand-alone field measurements. Calibration results show that the detection efficiency of the prototype PSM + TSI 3010 for charged tetra-alkyl ammonium salt molecules having mobility equival...

A review of the anthropogenic influence on biogenic secondary organic aerosol

Abstract: . Because of the climate and air quality effects of organic aerosol, it is important to quantify the influence of anthropogenic emissions on the aerosol burden, both globally and regionally, and both in terms of mass and number. Methods exist with which the fractions of organic aerosol resulting directly from anthropogenic and biogenic processes can be estimated. However, anthropogenic emissions can also lead to an enhancement in secondary organic aerosol formation from naturally emitted precursors. We term this enhanced biogenic secondary organic aerosol (eBSOA). Here, we review the mechanisms through which such an effect may occur in the atmosphere and describe a work flow via which it may be quantified, using existing measurement techniques. An examination of published data reveals support for the existence of the enhancement effect.

Atmospheric ions and nucleation: a review of observations

Abstract: . This review is based on ca. 260 publications, 93 of which included data on the temporal and spatial variation of the concentration of small ions ( −3 . However, concentrations up to 5000 cm −3 have been observed. The results are in agreement with observations of ion production rates in the atmosphere. We also summarised observations on the conversion of small ions to intermediate ions, which can act as embryos for new atmospheric aerosol particles. Those observations include the formation rates ( J 2 [ion]) of 2-nm intermediate ions, growth rates (GR[ion]) of sub-3 nm ions, and information on the chemical composition of the ions. Unfortunately, there were only a few studies which presented J 2 [ion] and GR[ion]. Based on the publications, the formation rates of 2-nm ions were 0–1.1 cm −3 s −1 , while the total 2-nm particle formation rates varied between 0.001 and 60 cm −3 s −1 . Due to small changes in J 2 [ion], the relative importance of ions in 2-nm particle formation was determined by the large changes in J 2 [tot], and, accordingly the contribution of ions increased with decreasing J 2 [tot]. Furthermore, small ions were observed to activate for growth earlier than neutral nanometer-sized particles and at lower saturation ratio of condensing vapours.

Growth rates of nucleation mode particles in Hyytiälä during 2003−2009: variation with particle size, season, data analysis method and ambient conditions

Abstract: . The condensational growth rate of aerosol particles formed in atmospheric new particle formation events is one of the most important factors influencing the lifetime of these particles and their ability to become climatically relevant. Diameter growth rates (GR) of nucleation mode particles were studied based on almost 7 yr of data measured during the years 2003–2009 at a boreal forest measurement station SMEAR II in Hyytiala, Finland. The particle growth rates were estimated using particle size distributions measured with a Differential Mobility Particle Sizer (DMPS), a Balanced Scanning Mobility Analyzer (BSMA) and an Air Ion Spectrometer (AIS). Two GR analysis methods were tested. The particle growth rates were also compared to an extensive set of ambient meteorological parameters and trace gas concentrations to investigate the processes/constituents limiting the aerosol growth. The median growth rates of particles in the nucleation mode size ranges with diameters of 1.5–3 nm, 3–7 nm and 7–20 nm were 1.9 nm h−1, 3.8 nm h−1, and 4.3 nm h−1, respectively. The median relative uncertainties in the growth rates due to the size distribution instrumentation in these size ranges were 25%, 19%, and 8%, respectively. For the smallest particles (1.5–3 nm) the AIS data yielded on average higher growth rate values than the BSMA data, and higher growth rates were obtained from positively charged size distributions as compared with negatively charged particles. For particles larger than 3 nm in diameter no such systematic differences were found. For these particles the uncertainty in the growth rate related to the analysis method, with relative uncertainty of 16%, was similar to that related to the instruments. The growth rates of 7–20 nm particles showed positive correlation with monoterpene concentrations and their oxidation rate by ozone. The oxidation rate by OH did not show a connection with GR. Our results indicate that the growth of nucleation mode particles in Hyytiala is mainly limited by the concentrations of organic precursors.

Quantification of the volatility of secondary organic compounds in ultrafine particles during nucleation events

Abstract: . Condensation of secondary organic compounds onto ultrafine aerosols is important for growing these particles to sizes where they can act as cloud condensation nuclei. The organic flux to ultrafine particles depends strongly on the volatility of the condensing compounds. This paper presents quantitative estimates of the volatility of secondary organic aerosol (SOA) in freshly nucleated particles. We examine 13 nucleation/growth events in two remote continental locations, Hyytiala, Finland and Egbert, ON, Canada. Two independent methods are used to quantify the volatility of the growing nucleation mode: (1) modelling of the growing nucleation mode to determine which volatilities allow the model to reproduce observed growth, and (2) modelling of the evaporation of heated aerosols in a Volatility Differential Mobility Particle Sizer to determine which volatilities allow the model to reproduce the observed evaporation. We find that the average saturation vapor concentration (C*) in the freshly nucleated particles (once Dp > 3 nm) is likely less than 10−3–10−2 μg m−3 (this corresponds to 3 × 106−3 × 107 molecules cm−3 and a saturation vapor pressure of 10−8–10−7 Pa). This maximum volatility depends somewhat on other uncertain factors that affect the size-dependent condensation of secondary organic compounds such as the surface tension, mass accommodation coefficient and the volatility of the pre-existing aerosols. However, our tests suggest that under no reasonable assumptions can the SOA in the ultrafine particles contain a majority of compounds with C* > 10−2 μg m−3. We demonstrate that the growth could be driven by either gas-phase or particle-phase chemistry but cannot conclude which is responsible for the low-volatility SOA.

A statistical proxy for sulphuric acid concentration

Abstract: . Gaseous sulphuric acid is a key precursor for new particle formation in the atmosphere. Previous experimental studies have confirmed a strong correlation between the number concentrations of freshly formed particles and the ambient concentrations of sulphuric acid. This study evaluates a body of experimental gas phase sulphuric acid concentrations, as measured by Chemical Ionization Mass Spectrometry (CIMS) during six intensive measurement campaigns and one long-term observational period. The campaign datasets were measured in Hyytiala, Finland, in 2003 and 2007, in San Pietro Capofiume, Italy, in 2009, in Melpitz, Germany, in 2008, in Atlanta, Georgia, USA, in 2002, and in Niwot Ridge, Colorado, USA, in 2007. The long term data were obtained in Hohenpeissenberg, Germany, during 1998 to 2000. The measured time series were used to construct proximity measures ("proxies") for sulphuric acid concentration by using statistical analysis methods. The objective of this study is to find a proxy for sulfuric acid that is valid in as many different atmospheric environments as possible. Our most accurate and universal formulation of the sulphuric acid concentration proxy uses global solar radiation, SO2 concentration, condensation sink and relative humidity as predictor variables, yielding a correlation measure (R) of 0.87 between observed concentration and the proxy predictions. Interestingly, the role of the condensation sink in the proxy was only minor, since similarly accurate proxies could be constructed with global solar radiation and SO2 concentration alone. This could be attributed to SO2 being an indicator for anthropogenic pollution, including particulate and gaseous emissions which represent sinks for the OH radical that, in turn, is needed for the formation of sulphuric acid.

Comparison of ambient aerosol extinction coefficients obtained from in-situ, MAX-DOAS and LIDAR measurements at Cabauw

Abstract: In the field, aerosol in-situ measurements are often performed under dry conditions (relative humidity RH<30-40%). Since ambient aerosol particles experience hygroscopic growth at enhanced RH, their microphysical and optical properties especially the aerosol light scattering are also strongly dependent on RH. The knowledge of this RH effect is of crucial importance for climate forcing calculations or for the comparison of remote sensing with in-situ measurements. Here, we will present results from a four-month campaign which took place in summer 2009 in Cabauw, The Netherlands. The aerosol scattering coefficient σsp(λ) was measured dry and at various, predefined RH conditions between 20 and 95% with a humidified nephelometer. The scattering enhancement factor f(RH,I") is the key parameter to describe the effect of RH on σsp(λ) and is defined as σsp(RH,I") measured at a certain RH divided by the dry σsp(dry,I"). The measurement of f(RH,I") together with the dry absorption measurement (assumed not to change with RH) allows the determination of the actual extinction coefficient σep(RH,I") at ambient RH. In addition, a wide range of other aerosol properties were measured in parallel. The measurements were used to characterize the effects of RH on the aerosol optical properties. A closure study showed the consistency of the aerosol in-situ measurements. Due to the large variability of air mass origin (and thus aerosol composition) a simple parameterization of (RH,?) could not be established. If (RH,?) needs to be predicted, the chemical composition and size distribution need to be known. Measurements of four MAX-DOAS (multi-axis differential optical absorption spectroscopy) instruments were used to retrieve vertical profiles of σep("). The values of the lowest layer were compared to the in-situ values after conversion of the latter ones to ambient RH. The comparison showed a good correlation of R<2 Combining double low line 0.62-0.78, but the extinction coefficients from MAX-DOAS were a factor of 1.5-3.4 larger than the in-situ values. Best agreement is achieved for a few cases characterized by low aerosol optical depths and low planetary boundary layer heights. Differences were shown to be dependent on the applied MAX-DOAS retrieval algorithm. The comparison of the in-situ extinction data to a Raman LIDAR (light detection and ranging) showed a good correlation and higher values measured by the LIDAR (R2 Combining double low line 0.82−0.85, slope of 1.69-1.76) if the Raman retrieved profile was used to extrapolate the directly measured extinction coefficient to the ground. The comparison improved if only nighttime measurements were used in the comparison (R2 Combining double low line 0.96, slope of 1.12). © 2011 Author(s).

The role of relative humidity in continental new particle formation

Abstract: [1] Relative humidity (RH) has been observed to be anticorrelated with continental new particle formation. Several reasons have been proposed for this rather surprising finding, but no firm conclusions have been drawn so far. Here we study several of the proposed reasons: Enhanced coagulational scavenging of sub-3 nm clusters at high RH, diminished solar radiation at high RH leading to diminished gas phase oxidation chemistry, and increased condensation sink (CS) of condensable gases due to hygroscopic growth of the preexisting particles. Our theoretical calculations indicate that the increase of coagulational scavenging plays a relatively small role in the inhibition of nucleation at high RH. On the other hand, field data show that the maximum observed gas phase sulphuric acid concentrations are limited to RHs below 60%. The field data also indicate that this is likely due to low OH concentrations at high RH. This finding is also supported by aerosol dynamics model simulations. The model was used to find out whether this is mainly due to decreased source (solar radiation) or increased sink (CS) terms at the elevated RH. The simulation results show that the decreased source term at high RH limits H2SO4 levels in the air, and therefore high new particle formation rates (above ∼1 cm−3 s−1) rarely occur above 80% RH.

Seasonal variation of CCN concentrations and aerosol activation properties in boreal forest

Abstract: . As a part of EUCAARI activities, the annual cycle of cloud condensation nuclei (CCN) concentrations and critical diameter for cloud droplet activation as a function of supersaturation were measured using a CCN counter and a HTDMA (hygroscopicity tandem differential mobility analyzer) at SMEAR II station, Hyytiala, Finland. The critical diameters for CCN activation were estimated from (i) the measured CCN concentration and particle size distribution data, and (ii) the hygroscopic growth factors by applying κ-Kohler theory, in both cases assuming an internally mixed aerosol. The critical diameters derived by these two methods were in good agreement with each other. The effect of new particle formation on the diurnal variation of CCN concentration and critical diameters was studied. New particle formation was observed to increase the CCN concentrations by 70–110%, depending on the supersaturation level. The average value for the κ-parameter determined from hygroscopicity measurements was κ = 0.18 and it predicted well the CCN activation in boreal forest conditions in Hyytiala. The derived critical diameters and κ-parameter confirm earlier findings with other methods, that aerosol particles at CCN sizes in Hyytiala are mostly organic, but contain also more hygrosopic, probably inorganic salts like ammonium sulphate, making the particles more CCN active than pure secondary organic aerosol.

Aerosol hygroscopicity and CCN activation kinetics in a boreal forest environment during the 2007 EUCAARI campaign

Abstract: . Measurements of size-resolved cloud condensation nuclei (CCN) concentrations, subsaturated hygroscopic growth, size distribution, and chemical composition were collected from March through May, 2007, in the remote Boreal forests of Hyytiala, Finland, as part of the European Integrated project on Aerosol Cloud Climate and Air Quality Interactions (EUCAARI) campaign. Hygroscopicity parameter, κ, distributions were derived independently from Continuous Flow-Streamwise Thermal Gradient CCN Chamber (CFSTGC) and Hygroscopicity Tandem Differential Mobility Analyzer (HTDMA) measurements. CFSTGC-derived κ values for 40, 60, and 80 nm particles range mostly between 0.10 and 0.40 with an average characteristic of highly oxidized organics of 0.20 ± 0.10, indicating that organics play a dominant role for this environment. HTDMA-derived κ were generally 30% lower. Diurnal trends of κ show a minimum at sunrise and a maximum in the late afternoon; this trend covaries with inorganic mass fraction and the m/z 44 organic mass fraction given by a quadrupole aerosol mass spectrometer, further illustrating the importance of organics in aerosol hygroscopicity. The chemical dispersion inferred from the observed κ distributions indicates that while 60 and 80 nm dispersion increases around midday, 40 nm dispersion remains constant. Additionally, 80 nm particles show a markedly higher level of chemical dispersion than both 40 and 60 nm particles. An analysis of droplet activation kinetics for the sizes considered indicates that most of the CCN activate as rapidly as (NH4)2SO4 calibration aerosol.

The summertime Boreal forest field measurement intensive (HUMPPA-COPEC-2010): an overview of meteorological and chemical influences

Abstract: . This paper describes the background, instrumentation, goals, and the regional influences on the HUMPPA-COPEC intensive field measurement campaign, conducted at the Boreal forest research station SMEAR II (Station for Measuring Ecosystem-Atmosphere Relation) in Hyytiala, Finland from 12 July–12 August 2010. The prevailing meteorological conditions during the campaign are examined and contrasted with those of the past six years. Back trajectory analyses show that meteorological conditions at the site in 2010 were characterized by a higher proportion of southerly flow than in the other years studied. As a result the summer of 2010 was anomalously warm and high in ozone making the campaign relevant for the analysis of possible future climates. A comprehensive land use analysis, provided on both 5 and 50 km scales, shows that the main vegetation types surrounding the site on both the regional and local scales are: coniferous forest (Scots pine and/or Norway spruce); mixed forest (Birch and conifers); and woodland scrub (e.g. Willows, Aspen); indicating that the campaign results can be taken as representative of the Boreal forest ecosystem. In addition to the influence of biogenic emissions, the measurement site was occasionally impacted by sources other than vegetation. Specific tracers have been used here to identify the time periods when such sources have impacted the site namely: biomass burning (acetonitrile and CO), urban anthropogenic pollution (pentane and SO2) and the nearby Korkeakoski sawmill (enantiomeric ratio of chiral monoterpenes). None of these sources dominated the study period, allowing the Boreal forest summertime emissions to be assessed and contrasted with various other source signatures.

Experimental observation of strongly bound dimers of sulfuric acid: application to nucleation in the atmosphere.

Abstract: Sulfuric acid is a key compound in atmospheric nucleation. Here we report on the observation of a close-to-collision-limited sulfuric acid dimer formation in atmospherically relevant laboratory conditions in the absence of measurable quantities of ammonia or organics. The observed dimer formation rate was clearly higher than the measured new particle formation rate at ∼1.5 nm suggesting that the rate limiting step for the nucleation takes place after the dimerization step. The quantum chemical calculations suggested that even in the ultraclean conditions there exist (a) stabilizing compound(s) with (a) concentration(s) high enough to prevent the dimer evaporation. Such a stabilizing compound should be abundant enough in any natural environment and would therefore not limit the formation of sulfuric acid dimers in the atmosphere.

An Instrumental Comparison of Mobility and Mass Measurements of Atmospheric Small Ions

Abstract: Ambient, naturally charged small ions (<2000 Da) were measured in Hyytiala, Finland, with a mass spectrometer (atmospheric pressure interface time-of-flight, APi-TOF) and two mobility spectrometers (air ion spectrometer, AIS, and balanced scanning mobility analyzer, BSMA). To compare these different instrument types, a mass/mobility conversion and instrumental transfer functions are required to convert high-resolution mass spectra measured by the APi-TOF into low-resolution mobility spectra measured by the AIS and BSMA. A modified version of the Stokes-Millikan equation was used to convert between mass and mobility. Comparison of APi-TOF and BSMA results showed good agreement, especially for sizes above 200 Da (Pearson's R = 0.7–0.9). Below this size, agreement was fair, and broadening BSMA transfer functions improved the correlation. To achieve equally good agreement between APi-TOF and AIS, AIS results needed to be shifted by 1–1.5 mobility channels. The most likely cause was incorrect sizing in the AIS...

The effect of H 2 SO 4 – amine clustering on chemical ionization mass spectrometry (CIMS) measurements of gas-phase sulfuric acid

Abstract: . The state-of-the art method for measuring atmospheric gas-phase sulfuric acid is chemical ionization mass spectrometry (CIMS) based on nitrate reagent ions. We have assessed the possible effect of the sulfuric acid molecules clustering with base molecules on CIMS measurements using computational chemistry. From the computational data, three conclusions can be drawn. First, a significant fraction of the gas-phase sulfuric acid molecules are very likely clustered with amines if the amine concentration is around or above a few ppt. Second, some fraction of these acid-amine clusters may not be charged by the CIMS instrument, though the most reliable computational methods employed predict this fraction to be small; on the order of ten percent or less. Third, the amine molecules will evaporate practically immediately after charging, thus evading detection. These effects may need to be taken into account in the interpretation of atmospheric measurement data obtained using chemical ionization methods. The purpose of this study is not to criticize the CIMS method, but to help understand the implications of the measured results.

Characterisation of corona-generated ions used in a Neutral cluster and Air Ion Spectrometer (NAIS)

Abstract: . We characterized size and chemical composition of ions generated by a corona-needle charger of a Neutral cluster and Air Ion Spectrometer (NAIS) by using a high resolution differential mobility analyzer and a time-of-flight mass spectrometer. Our study is crucial to verify the role of corona-generated ions in the particle size spectra measured with the NAIS, in which a corona charger is used to charge aerosol particles down to the size range overlapping with the size of generated ions. The size and concentration of ions produced by the corona discharging process depend both on corona voltage and on properties and composition of carrier gas. Negative ions were

Observations of Nano-CN in the Nocturnal Boreal Forest

Abstract: New particle formation has been proposed to happen via activation of nanometer-sized condensation nuclei (nano-CN), which can be large molecules or molecular clusters. Electrically neutral nano-CN have mostly been outside the measurement range until recently. To address the concentrations and plausible chemical composition of the nano-CN, we measured the neutral particle size distribution down to mobility diameter ∼1.3 nm with a pulse-height CPC in Hyytiala, southern Finland during springs 2007–2009. We also performed laboratory experiments with variable concentrations of precursors and oxidants in order to reproduce the atmospheric observations. The atmospheric nano-CN data were compared to ion size distributions (∼0.8–7.5 nm) measured with a BSMA ion spectrometer, and the mass spectra of natural ions detected with an APi-TOF mass spectrometer. We detected elevated concentrations of nano-CN, especially in the nocturnal boundary layer. However, the night-time nano-CN did not grow to sizes larger than a fe...

Spatial and vertical extent of nucleation events in the Midwestern USA: insights from the Nucleation In ForesTs (NIFTy) experiment

Abstract: . Measurements of aerosol particle physical and chemical properties, gas phase concentrations and meteorological parameters were made along a transect in southern Indiana during the Nucleation In ForesTs (NIFTy) experiment conducted in May 2008. These measurements indicate nucleation was observed at all three measurement sites on almost half of all sampling days. The intensity of the nucleation events, as measured by the increase in ≥10 nm aerosol particle number concentrations of approximately 2×10 4 cm −3 over a layer of at least 300 m depth, is in good agreement with recent model results for the Midwestern USA derived using PMCAMx-UF. During the hour after termination of nucleation approximately half of the number concentration reduction is due to coagulation, while the remainder is due in equal parts to dry deposition and entrainment of relatively ultra-fine aerosol particle free troposphere air. Clear nucleation with continuous subsequent growth is only observed on days when the morning fractional cloud cover was less than 30%. It is associated with a clear transition from a strongly stratified atmosphere with low turbulence intensity and weak vertical velocities, to much a weaker vertical gradient of wind speed, increased turbulence intensity and stronger downwards vertical velocities, consistent with growth of the mixed layer and entrainment of air from the residual layer. Nucleation intensity is not very strongly determined by the prevailing condensational sink. However, there is a strong correlation between both a modified version of the Nucleation Parameter from Boy and Kulmala (2002) and ultrafine aerosol particle number concentrations, and mean morning H 2 SO 4 concentrations and ultrafine aerosol particle number concentrations. Five A-class event days during NIFTy were characterized by values of the dimensionless nucleation parameter of Kuang et al. (2010) that are below 0.3, further indicating the applicability of their postulate that nucleation is favored by L Γ values below 0.7. Based on aerosol particle composition measurements it appears that aerosol particle formation and initial growth to approximately 30 nm diameter is dominated by ammonium and sulfate. Conservative estimates of the percent contribution of H 2 SO 4 to aerosol particle growth (for sub-30 nm aerosol particles) on five A-class event days ranged from 23 to 85%.

Homogenous nucleation of sulfuric acid and water at close to atmospherically relevant conditions

Abstract: . In this study the homogeneous nucleation rates in the system of sulfuric acid and water were measured by using a flow tube technique. The goal was to directly compare particle formation rates obtained from atmospheric measurements with nucleation rates of freshly nucleated particles measured with particle size magnifier (PSM) which has detection efficiency of unity for particles having mobility diameter of 1.5 nm. The gas phase sulfuric acid concentration in this study was measured with the chemical ionization mass spectrometer (CIMS), commonly used in field measurements. The wall losses of sulfuric acid were estimated from measured concentration profiles along the flow tube. The initial concentrations of sulfuric acid estimated from loss measurements ranged from 108 to 3 × 109 molecules cm−3. The nucleation rates obtained in this study cover about three orders of magnitude from 10−1 to 102 cm−3 s−1 for commercial ultrafine condensation particle counter (UCPC) TSI model 3025A and from 101 to 104 cm−3 s−1 for PSM. The nucleation rates and the slopes (dlnJ/dln [H2SO4]) show satisfactory agreement when compared to empirical kinetic and activation models and the latest atmospheric nucleation data. To the best of our knowledge, this is the first experimental work providing temperature dependent nucleation rate measurements using a high efficiency particle counter with a cut-off-size of 1.5 nm together with direct measurements of gas phase sulfuric acid concentration.

Intercomparison of air ion spectrometers: an evaluation of results in varying conditions

Abstract: . We evaluated 11 air ion spectrometers from Airel Ltd. after they had spent one year in field measurements as a part of the EUCAARI project: 5 Air Ion Spectrometers (AIS), 5 Neutral cluster and Air Ion Spectrometers (NAIS) and one Airborne NAIS (ANAIS). This is the first time that an ANAIS is evaluated and compared so extensively. The ion spectrometers' mobility and concentration accuracy was evaluated. Their measurements of ambient air were compared between themselves and to reference instruments: a Differential Mobility Particle Sizer (DMPS), a Balanced Scanning Mobility Analyzer (BSMA), and an Ion-DMPS. We report on the simultaneous measurement of a new particle formation (NPF) event by all 11 instruments and the 3 reference instruments. To our knowledge, it is the first time that the size distribution of ions and particles is measured by so many ion spectrometers during a NPF event. The new particle formation rates (~0.2 cm−3 s−1 for ions and ~2 cm−3 s−1 for particles) and growth rates (~25 nm h−1 in the 3–7 nm size range) were calculated for all the instruments. The NAISs and the ANAIS gave higher concentrations and formation rates than the AISs. For example, the AISs agreed with the BSMA within 11 % and 28 % for negative and positive ion concentration respectively, whereas the NAISs agreed within 23 % and 29 %. Finally, based on the results presented here, we give guidelines for data evaluation, when data from different individual ion spectrometers are compared.

Soil Nitrites Influence Atmospheric Chemistry

Abstract: Public discussion of climate change typically revolves around greenhouse gases, aerosol particles, and the role of human actions ( 1 – 3 ), but it is just beginning to reflect an awareness of the important role played by the global nitrogen cycle ( 4 ). It has been difficult, however, to disentangle the nitrogen cycle's role in climate change owing to its complex interactions with other biogeochemical cycles, including the carbon and sulfur cycles ( 5 ), and with factors such as soil, vegetation, and water. These interactions can lead to unexpected, nonlinear responses in the Earth system as a whole. On page 1616 of this issue, Su et al. ( 6 ) illuminate one poorly understood set of interactions, showing that nitrite in soil can produce nitrous acid (HONO) emissions that are a source of hydroxyl (OH) radicals in the atmosphere. The finding helps identify one source of “missing” atmospheric HONO, and highlights how HONO emissions could rise with increasing temperatures and nitrogen fertilizer use.

Comparison of quartz and Teflon filters for simultaneous collection of size-separated ultrafine aerosol particles and gas-phase zero samples

Abstract: In this research, the two most common filter media, quartz and Teflon, were tested to obtain information about the possible adsorption of gas-phase compounds onto filters during long sample collection of atmospheric aerosols. Particles of nanometer-size for off-line chemical characterization were collected using a recently introduced differential mobility analyzer for size separation. Samples were collected at an urban site (Helsinki, SMEARIII station) during spring 2010. Sampling time was 4 to 10 days for particles 50, 40, or 30 nm in diameter. Sample air flow was 4 L/min. The sampling setup was arranged so that two samples were obtained for each sampling period almost simultaneously: one containing particles and adsorbed gas-phase compounds and one containing adsorbed gas-phase compounds only. Filters were extracted and analyzed for the presence of selected carboxylic acids, polyols, nitrogen-containing compounds, and aldehydes. The results showed that, in quartz filter samples, gas-phase adsorption may be responsible for as much as 100% of some compound masses. Whether quartz or Teflon, simultaneous collection of gas-phase zero samples is essential during the whole sampling period. The dependence of the adsorption of gas-phase compounds on vapor pressure and the effect of adsorption on the deposited aerosol layer are discussed.

Contrasting organic aerosol particles from boreal and tropical forests during HUMPPA-COPEC-2010 and AMAZE-08 using coherent vibrational spectroscopy

Abstract: . We present the vibrational sum frequency generation spectra of organic particles collected in a boreal forest in Finland and a tropical forest in Brazil. These spectra are compared to those of secondary organic material produced in the Harvard Environmental Chamber. By comparing coherent vibrational spectra of a variety of terpene and olefin reference compounds, along with the secondary organic material synthesized in the environmental chamber, we show that submicron aerosol particles sampled in Southern Finland during HUMPPA-COPEC-2010 are composed to a large degree of material similar in chemical composition to synthetic α-pinene-derived material. For material collected in Brazil as part of AMAZE-08, the organic component is found to be chemically complex in the coarse mode but highly uniform in the fine mode. When combined with histogram analyses of the isoprene and monoterpene abundance recorded during the HUMPPA-COPEC-2010 and AMAZE-08 campaigns, the findings presented here indicate that if air is rich in monoterpenes, submicron-sized secondary aerosol particles that form under normal OH and O3 concentration levels can be described in terms of their hydrocarbon content as being similar to α-pinene-derived model secondary organic aerosol particles. If the isoprene concentration dominates the chemical composition of organic compounds in forest air, then the hydrocarbon component of secondary organic material in the submicron size range is not simply well-represented by that of isoprene-derived model secondary organic aerosol particles but is more complex. Throughout the climate-relevant size range of the fine mode, however, we find that the chemical composition of the secondary organic particle material from such air is invariant with size, suggesting that the particle growth does not change the chemical composition of the hydrocarbon component of the particles in a significant way.

Local Air Pollution Versus Short-range Transported Dust Episodes: A Comparative Study for Submicron Particle Number Concentration

Abstract: We measured the submicron particle number concentrations in the urban/suburban atmosphere of Amman-Jordan during the spring of 2009. The main objective was to distinguish the differences in the submicron particle number concentrations with/without dust episodes. In the absence of dust episodes the concentrations showed distinguished daily patterns, which were similar at both the urban and the urban atmosphere with lower concentrations (at least 1:2) at the suburban site. The daily pattern during the first five working days (Saturday-Wednesday) was different than that that on either Thursday or Friday. During the morning rush hours the number concentrations were as high as 120×10^3 and 75×10^3 1/cm^3 at the urban and suburban sites during those workdays, respectively. These concentrations were about 21 and 14 times what was observed during the background conditions (5.5×10^3 1/cm^3 between midnight and early morning) at both sites. This suggests that traffic emissions are one of the main sources in the urban/suburban atmosphere of Amman. The number concentration of submicron aerosol particles, which originated from the nearby highway, at the urban site decreased exponentially with the wind speed. During a dust episode the total number concentration of submicron particles was about 1/5 of what is typically observed during workdays without dust episodes. The lower concentrations were attributed here for two reasons: increased wind speed and coagulation of locally emitted urban particles with the regional dust particles. These observations in the absence of dust episodes agree well with other studies for highly populated cities. The limitation of this study is the lack of information about the particle number size distribution that can reveal the modal structure of aerosol particles in Amman.

A complete methodology for the reliable collection, sample preparation, separation and determination of organic compounds in ultrafine 30 nm, 40 nm and 50 nm atmospheric aerosol particles

Abstract: A complete reliable methodology including several extraction and chromatographic techniques has been developed for the determination of selected organic compounds in atmospheric aerosol particles. Size separated ultrafine particles (Dp ≤ 50nm) and total suspended particles (TSP) were collected in a urban and forest environment. One third of the samples contained TS particles and the rest of the samples were size-separated (30, 40 or 50 nm particles) with a differential mobility analyzer (DMA). Gas chromatography-mass spectrometric and liquid chromatography-mass spectrometric methods were developed for the analysis of the target compounds and the sample pretreatment was shortened by exploiting ultrasonic energy. The investigated compounds included seven amines (average concentrations ranged between 0.1 and 10.9 ng m−3), eight aldehydes (0.1–11.9 ng m−3), two polyols (0.1–81.5 ng m−3) and sixteen acids (0.1–47.2 ng m−3). The whole methodology including sample preparation and analysis methods was carefully validated by comparison of the results obtained with those provided by a conventional extraction method, non-assisted by ultrasound and by standard addition methodology, respectively. There were clear differences, up to two orders of magnitude, in the concentrations of the target compounds in aerosol samples with different sizes collected from an urban and forest environment.

Comprehensive two-dimensional gas chromatography, a valuable technique for screening and semiquantitation of different chemical compounds in ultrafine 30 nm and 50 nm aerosol particles

Abstract: Comprehensive two dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-TOF-MS) was used for screening and semiquantitation of semivolatile organic compounds in aerosol particles. As the volatility was a prerequisite parameter for the analysis, some compounds were transformed viaderivatization such as silylation into more volatile ones. The identification of the analytes was made by comparing the GC retention indices and the TOF mass spectra with the NIST and the Golm metabolome database reference libraries. The data treatment was simplified by exploiting an additional classification of the identified compounds, namely the main functional group or specific element present in the molecule leading to different groups of compounds. This methodology was applied to identify compounds in 30 ± 4 nm, 50 ± 5 nm and total suspended particles (TSP) collected during spring and autumn of 2009 and summer of 2010 at the Station for Measuring Forest Ecosystem Atmosphere Relations (SMEAR II) at Hyytiala (Finland). The number of identified compounds was higher than 400, which were the most relevant compounds present in the samples, in terms of concentrations. The analysis of aerosol particles of different sizes, collected simultaneously, revealed that the number of compounds increased with the particle size whereas the normalized response factor decreased in most of the cases, aldehydes being an exception. This decrease could be associated with the formation or aggregation of new compounds onto the particles when they grow in the atmosphere.

Intercomparison of air ion spectrometers: a basis for data interpretation

Abstract: Specific Comments: Line 156: Assuming that the corona charger is not 100% efficient there should still remain electrically neutral particles; therefore, it seems inappropriate to state \"particle-free\" air. Also, it is not clear how the offset measurements are done. Is the classifying voltage applied during the offset measurements? Is the offset current affected by the presence of the classifying voltage?

Erratum: Relationship between aerosol oxidation level and hygroscopic properties of laboratory generated secondary organic aerosol (SOA) particles (Geophysical Research Letters (2010) 38 (L03805))

Abstract: Copyright (2011) American Geophysical Union. These materials are made available for use in research, teaching and private study, pursuant to U.S. Copyright Law. The user must assume full responsibility for any use of the materials, including but not limited to, infringement of copyright and publication rights of reproduced materials. Any materials used for academic research or otherwise should be fully credited with the source. Erratum: Relationship between aerosol oxidation level and hygroscopic properties of laboratory generated secondary organic aerosol (SOA) particles (Geophysical Research Letters (2010) 38 (L03805))

The variability of urban aerosol size distributions and optical properties in São Paulo – Brazil: new particle formation events occur at the site

Abstract: Introduction Conclusions References