Experimental study on the influence of dimethylamine on the detection of gas phase sulfuric acid using chemical ionization mass spectrometry (CIMS)

Based on quantum chemistry calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H_2SO_4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment was set up at the CLOUD aerosol chamber to test the quantitative detection of H_2SO_4 by CIMS by directly comparing the measured H_2SO_4 with and without DMA being present in the sample air. It was found that the H_2SO_4 cluster distribution changes but the CIMS detection efficiency is not strongly influenced

Activation of sub-3 nm organic particles in the particle size magnifier using humid and dry conditions

The accurate measurement of aerosol particles and clusters smaller than 3 nm in diameter is crucial for the understanding of new particle formation processes. The particle counters used for measuring these particles are typically calibrated with metal or salt particles under dry conditions, which does not always represent the field conditions where these instruments are later used. In this study, we calibrated the All nano Condensation Nucleus Counter (nCNC), consisting of the PSM (Particle Size Magnifier) and a laminar flow butanol based CPC (Condensational Particle Counter), with well-defined biogenic oxidation products from beta-caryophyllene oxidation and compared it to a calibration with tungsten oxide under the same conditions. The organic particles were detected less efficiently than the inorganic ones. This resulted in a higher cut-off size for beta-caryophyllene oxidation products than for tungsten oxide. At the same PSM settings, the cut-off size for tungsten oxide was 1.2 nm and for beta-caryophyllene oxidation products 1.9 nm. However, repeating the calibration of the biogenic particles at 13% relative humidity at 31 degrees C, increased their detection efficiency in the PSM, increasing the cut-off diameter to 1.6 nm. Additionally, we present a comparison of the ion concentrations measured with the PSM and the NAIS (Neutral Cluster and Air Ion Spectrometer) during new particle formation experiments in the CLOUD (Cosmics Leaving Outdoors Droplets) chamber. In these experiments, we produced particles from different organic precursors, such as alpha-pinene, beta-caryophyllene and isoprene, as well as iodine. This way, we could determine the shift in cut-off diameter of the PSM for several different atmospherically relevant chemical compounds and compare it to the laboratory calibrations. We saw a diameter shift for the organic precursors of +0.3 nm in the PSM compared to the NAIS. These two approaches agreed well with each other and show that it is important to know the chemical composition of the measured particles to determine the exact size distribution using a supersaturation scanning method.Peer reviewe

Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI-APi-TOF (Chemical Ionization-Atmospheric Pressure interface-Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (Peer reviewe

Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI-APi-TOF (Chemical Ionization-Atmospheric Pressure interface-Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H2SO4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4-H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self-contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit

Renal function during rofecoxib therapy in patients with metastatic cancer: retrospective analysis of a prospective phase II trial

German Clinical Trials Register DRKS: DRKS0000011

The role of low-volatility organic compounds in initial particle growth in the atmosphere

About half of present-day cloud condensation nuclei originate from atmospheric nucleation, frequently appearing as a burst of new particles near midday1. Atmospheric observations show that the growth rate of new particles often accelerates when the diameter of the particles is between one and ten nanometres2, 3. In this critical size range, new particles are most likely to be lost by coagulation with pre-existing particles4, thereby failing to form new cloud condensation nuclei that are typically 50 to 100 nanometres across. Sulfuric acid vapour is often involved in nucleation but is too scarce to explain most subsequent growth5, 6, leaving organic vapours as the most plausible alternative, at least in the planetary boundary layer7, 8, 9, 10. Although recent studies11, 12, 13 predict that low-volatility organic vapours contribute during initial growth, direct evidence has been lacking. The accelerating growth may result from increased photolytic production of condensable organic species in the afternoon2, and the presence of a possible Kelvin (curvature) effect, which inhibits organic vapour condensation on the smallest particles (the nano-Köhler theory)2, 14, has so far remained ambiguous. Here we present experiments performed in a large chamber under atmospheric conditions that investigate the role of organic vapours in the initial growth of nucleated organic particles in the absence of inorganic acids and bases such as sulfuric acid or ammonia and amines, respectively. Using data from the same set of experiments, it has been shown15 that organic vapours alone can drive nucleation. We focus on the growth of nucleated particles and find that the organic vapours that drive initial growth have extremely low volatilities (saturation concentration less than 10−4.5 micrograms per cubic metre). As the particles increase in size and the Kelvin barrier falls, subsequent growth is primarily due to more abundant organic vapours of slightly higher volatility (saturation concentrations of 10−4.5 to 10−0.5 micrograms per cubic metre). We present a particle growth model that quantitatively reproduces our measurements. Furthermore, we implement a parameterization of the first steps of growth in a global aerosol model and find that concentrations of atmospheric cloud concentration nuclei can change substantially in response, that is, by up to 50 per cent in comparison with previously assumed growth rate parameterizations

Experimental particle formation rates spanning tropospheric sulfuric acid and ammonia abundances, ion production rates, and temperatures

Binary nucleation of sulfuric acid and water as well as ternary nucleation involving ammonia are thought to be the dominant processes responsible for new particle formation (NPF) in the cold temperatures of the middle and upper troposphere. Ions are also thought to be important for particle nucleation in these regions. However, global models presently lack experimentally measured NPF rates under controlled laboratory conditions and so at present must rely on theoretical or empirical parameterizations. Here with data obtained in the European Organization for Nuclear Research CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we present the first experimental survey of NPF rates spanning free tropospheric conditions. The conditions during nucleation cover a temperature range from 208 to 298K, sulfuric acid concentrations between 5x10(5) and 1x10(9)cm(-3), and ammonia mixing ratios from zero added ammonia, i.e., nominally pure binary, to a maximum of -1400 parts per trillion by volume (pptv). We performed nucleation studies under pure neutral conditions with zero ions being present in the chamber and at ionization rates of up to 75ion pairs cm(-3)s(-1) to study neutral and ion-induced nucleation. We found that the contribution from ion-induced nucleation is small at temperatures between 208 and 248K when ammonia is present at several pptv or higher. However, the presence of charges significantly enhances the nucleation rates, especially at 248K with zero added ammonia, and for higher temperatures independent of NH3 levels. We compare these experimental data with calculated cluster formation rates from the Atmospheric Cluster Dynamics Code with cluster evaporation rates obtained from quantum chemistry.Peer reviewe

Neutral molecular cluster formation of sulfuric acid-dimethylamine observed in real time under atmospheric conditions

Peer reviewe

Influence of temperature on the molecular composition of ions and charged clusters during pure biogenic nucleation

It was recently shown by the CERN CLOUD experiment that biogenic highly oxygenated molecules (HOMs) form particles under atmospheric conditions in the absence of sulfuric acid, where ions enhance the nucleation rate by 1-2 orders of magnitude. The biogenic HOMs were produced from ozonolysis of alpha-pinene at 5 degrees C. Here we extend this study to compare the molecular composition of positive and negative HOM clusters measured with atmospheric pressure interface time-of-flight mass spectrometers (APi-TOFs), at three different temperatures (25, 5 and -25 degrees C). Most negative HOM clusters include a nitrate (NO3-) ion, and the spectra are similar to those seen in the nighttime boreal forest. On the other hand, most positive HOM clusters include an ammonium (NH4+) 4) ion, and the spectra are characterized by mass bands that differ in their molecular weight by similar to 20 C atoms, corresponding to HOM dimers. At lower temperatures the average oxygen to carbon (O : C) ratio of the HOM clusters decreases for both polarities, reflecting an overall reduction of HOM formation with decreasing temperature. This indicates a decrease in the rate of autoxidation with temperature due to a rather high activation energy as has previously been determined by quantum chemical calculations. Furthermore, at the lowest temperature (-25 degrees C), the presence of C-30 clusters shows that HOM monomers start to contribute to the nucleation of positive clusters. These experimental findings are supported by quantum chemical calculations of the binding energies of representative neutral and charged clusters.Peer reviewe