Atmospheric peroxy radicals: ROXMAS, a new mass-spectrometric methodology for speciated measurements of HO2 and ∑RO2 and first results

Hanke, M.; Uecker, J.; Reiner, Thomas; Arnold, Frank

doi:10.1016/s1387-3806(01)00548-6

Cited by 83 publications

(91 citation statements)

References 40 publications

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“…The sulphuric acid concentration was measured by a chemical ionization mass spectrometer (CIMS) built by the MPI-K Heidelberg (see Hanke et al, 2002). The time resolution of the spectrometer was less than 1 s, but the data was averaged over 60 s in order to reduce statistical error.…”

Section: Measurementsmentioning

confidence: 99%

Atmospheric sulphuric acid and aerosol formation: implications from atmospheric measurements for nucleation and early growth mechanisms

Sihto

Kulmala²,

Kerminen³

et al. 2006

Atmos. Chem. Phys.

462

560

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Abstract.We have investigated the formation and early growth of atmospheric secondary aerosol particles building on atmospheric measurements. The measurements were part of the QUEST 2 campaign which took place in spring 2003 in Hyytiälä (Finland). During the campaign numerous aerosol particle formation events occurred of which 15 were accompanied by gaseous sulphuric acid measurements. Our detailed analysis of these 15 events is focussed on nucleation and early growth (to a diameter of 3 nm) of fresh particles. It revealed that new particle formation seems to be a function of the gaseous sulphuric acid concentration to the power from one to two when the time delay between the sulphuric acid and particle number concentration is taken into account. From the time delay the growth rates of freshly nucleated particles from 1 nm to 3 nm were determined. The mean growth rate was 1.2 nm/h and it was clearly correlated with the gaseous sulphuric acid concentration. We tested two nucleation mechanisms -recently proposed cluster activation and kinetic type nucleation -as possible candidates to explain the observed dependences, and determined experimental nucleation coefficients. We found that some events are dominated by the activation mechanism and some by the kinetic mechanism. Inferred coefficients for the two nucleation mechanisms are the same order of magnitude as chemical re-action coefficients in the gas phase and they correlate with the product of gaseous sulphuric acid and ammonia concentrations. This indicates that besides gaseous sulphuric acid also ammonia has a role in nucleation.

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Section: Measurementsmentioning

confidence: 99%

Atmospheric sulphuric acid and aerosol formation: implications from atmospheric measurements for nucleation and early growth mechanisms

Sihto

Kulmala²,

Kerminen³

et al. 2006

Atmos. Chem. Phys.

462

560

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“…The used data included particle size distributions measured with Twin-DMPS systems, sulphuric acid concentration measured with chemical ionization mass spectrometers (CIMS, see e.g. Hanke et al, 2002) and meteorological data, such as temperature and relative humidity. The time resolution was 10-15 min for the DMPS measurements and less than 1 s for the sulphuric acid data.…”

Section: The Utilised Data Setsmentioning

confidence: 99%

Connections between atmospheric sulphuric acid and new particle formation during QUEST III–IV campaigns in Heidelberg and Hyytiälä

et al. 2007

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Abstract. This study investigates the connections between atmospheric sulphuric acid and new particle formation during QUEST III and BACCI/QUEST IV campaigns. The campaigns have been conducted in Heidelberg (2004) and Hyytiälä (2005), the first representing a polluted site surrounded by deciduous forest, and the second a rural site in a boreal forest environment. We have studied the role of sulphuric acid in particle formation and growth by determining 1) the power-law dependencies between sulphuric acid ([H 2 SO 4 ]), and particle concentrations (N 3−6 ) or formation rates at 1 nm and 3 nm (J 1 and J 3 ); 2) the time delays between [H 2 SO 4 ] and N 3−6 or J 3 , and the growth rates for 1-3 nm particles; 3) the empirical nucleation coefficients A and K in relations J 1 =A[H 2 SO 4 ] and J 1 =K[H 2 SO 4 ] 2 , respectively; 4) theoretical predictions for J 1 and J 3 for the days when no significant particle formation is observed, based on the observed sulphuric acid concentrations and condensation sinks. In both environments, N 3−6 or J 3 and [H 2 SO 4 ] were linked via a power-law relation with exponents typically ranging from 1 to 2. The result suggests that the cluster activation theory and kinetic nucleation have the potential to explain the observed particle formation. However, some differences between the sites existed: The nucleation coefficients were about an order of magnitude greater in Heidelberg than in Hyytiälä conditions. The time lags between J 3 and [H 2 SO 4 ] were consistently lower than the corresponding Correspondence to: I. Riipinen (ilona.riipinen@helsinki.fi) delays between N 3−6 and [H 2 SO 4 ]. The exponents in the J 3 ∝[H 2 SO 4 ] n J 3 -connection were consistently higher than or equal to the exponents in the relation N 3−6 ∝[H 2 SO 4 ] n N36 . In the J 1 values, no significant differences were found between the observed rates on particle formation event days and the predictions on non-event days. The J 3 values predicted by the cluster activation or kinetic nucleation hypotheses, on the other hand, were considerably lower on non-event days than the rates observed on particle formation event days. This study provides clear evidence implying that the main process limiting the observable particle formation is the competition between the growth of the freshly formed particles and their loss by scavenging, rather than the initial particle production by nucleation of sulphuric acid. In general, it can be concluded that the simple models based on sulphuric acid concentrations and particle formation by cluster activation or kinetic nucleation can predict the occurence of atmospheric particle formation and growth well, if the particle scavenging is accurately accounted for.

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“…Gaseous sulphuric acid was measured at both sites by a chemical ionization mass spectrometer (CIMS) built by the MPI-K Heidelberg Arnold, 1993, 1994;Hanke et al, 2002). The principle of this measurement method is to convert the hardly detectable trace gas into more easily detectable product ions through a highly efficient ion-molecule reaction (IMR).…”

Section: Measurements Of Gaseous Sulphuric Acidmentioning

confidence: 99%

The contribution of sulphuric acid to atmospheric particle formation and growth: a comparison between boundary layers in Northern and Central Europe

et al. 2005

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Abstract. Atmospheric gaseous sulphuric acid was measured and its influence on particle formation and growth was investigated building on aerosol data. The measurements were part of the EU-project QUEST and took place at two different measurement sites in Northern and Central Europe (Hyytiälä, Finland, March-April 2003 and Heidelberg, Germany, March-April 2004). From a comprehensive data set including sulphuric acid, particle number size distributions and meteorological data, particle growth rates, particle formation rates and source rates of condensable vapors were inferred. Growth rates were determined in two different ways, from particle size distributions as well as from a so-called timeshift analysis. Moreover, correlations between sulphuric acid and particle number concentration between 3 and 6 nm were examined and the influence of air masses of different origin was investigated. Measured maximum concentrations of sulphuric acid were in the range from 1×10 6 to 16×10 6 cm −3 . The gaseous sulphuric acid lifetime with respect to condensation on aerosol particles ranged from 2 to 33 min in Hyytiälä and from 0.5 to 8 min in Heidelberg. Most calculated values (growth rates, formation rates, vapor source rates) were considerably higher in Central Europe (Heidelberg), due to the more polluted air and higher preexistent aerosol concentrations. Close correlations between H 2 SO 4 and nucleation mode particles (size range: 3-6 nm) were found on most days at both sites. The percentage contribution of sulphuric acid to particle growth was below 10% at both places and to initial growth below 20%. An air mass analysis indicated that at Heidelberg new particles were formed predominantly in air advected from southwesterly directions.

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Atmospheric peroxy radicals: ROXMAS, a new mass-spectrometric methodology for speciated measurements of HO2 and ∑RO2 and first results

Cited by 83 publications

References 40 publications

Atmospheric sulphuric acid and aerosol formation: implications from atmospheric measurements for nucleation and early growth mechanisms

Atmospheric sulphuric acid and aerosol formation: implications from atmospheric measurements for nucleation and early growth mechanisms

Connections between atmospheric sulphuric acid and new particle formation during QUEST III–IV campaigns in Heidelberg and Hyytiälä

The contribution of sulphuric acid to atmospheric particle formation and growth: a comparison between boundary layers in Northern and Central Europe

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