Refine
Year of publication
Document Type
- Preprint (541)
- Article (321)
- Conference Proceeding (1)
- Working Paper (1)
Language
- English (864)
Has Fulltext
- yes (864)
Is part of the Bibliography
- no (864)
Keywords
- Heavy Ion Experiments (20)
- Hadron-Hadron scattering (experiments) (11)
- Hadron-Hadron Scattering (8)
- Heavy-ion collision (5)
- Atmospheric chemistry (4)
- Collective Flow (4)
- Quark-Gluon Plasma (4)
- Jets (3)
- Jets and Jet Substructure (3)
- Atmospheric science (2)
Institute
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.
Under certain conditions, secondary organic aerosol (SOA) particles can exist in the atmosphere in an amorphous solid or semi-solid state. To determine their relevance to processes such as ice nucleation or chemistry occurring within particles requires knowledge of the temperature and relative humidity (RH) range for SOA to exist in these states. In the CLOUD experiment at CERN, we deployed a new in-situ optical method to detect the viscosity of α-pinene SOA particles and measured their transition from the amorphous viscous to liquid state. The method is based on the depolarising properties of laboratory-produced non-spherical SOA particles and their transformation to non-depolarising spherical liquid particles during deliquescence. We found that particles formed and grown in the chamber developed an asymmetric shape through coagulation. A transition to spherical shape was observed as the RH was increased to between 35 % at −10 ◦C and 80 % at −38 ◦C, confirming previous calculations of the viscosity transition conditions. Consequently, α-pinene SOA particles exist in a viscous state over a wide range of ambient conditions, including the cirrus region of the free troposphere. This has implications for the physical, chemical and ice-nucleation properties of SOA and SOA-coated particles in the atmosphere.
New particle formation driven by acid-base chemistry was initiated in the CLOUD chamber at CERN by introducing atmospherically relevant levels of gas phase sulfuric acid and dimethylamine (DMA). Ammonia was also present in the chamber as a gas-phase contaminant from earlier experiments. The composition of particles with volume median diameters (VMDs) as small as 10 nm was measured by the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS). Particulate ammonium-to-dimethylaminium ratios were higher than the gas phase ammonia-to-DMA ratios, suggesting preferential uptake of ammonia over DMA for the collected 10-30 nm VMD particles. This behavior is not consistent with present nanoparticle physico-chemical models, which predict a higher dimethylaminium fraction when NH3 and DMA are present at similar gas phase concentrations. Despite the presence in the gas phase of at least 100 times higher base concentrations than sulfuric acid, the recently formed particles always had measured base:acid ratios lower than 1:1. The lowest base fractions were found in particles below 15 nm VMD, with a strong size-dependent composition gradient that suggests a change to a mixed-phase state as the particles grew beyond this size. The reasons for the very acidic composition remain uncertain, but a possible explanation is that the particles did not reach thermodynamic equilibrium with respect to the bases due to rapid heterogeneous conversion of SO2 to sulfate. These results indicate that sulfuric acid does not require stabilization by ammonium or dimethylaminium as acid-base pairs in particles as small as 10 nm.
Hygroscopicity of nanoparticles produced from homogeneous nucleation in the CLOUD experiments
(2015)
Sulfuric acid, amines and oxidized organics have been found to be important compounds in the nucleation and initial growth of atmospheric particles. Because of the challenges involved in determining the chemical composition of objects with very small mass, however, the properties of the freshly nucleated particles and the detailed pathways of their formation processes are still not clear. In this study, we focus on a challenging size range, i.e. particles that have grown to diameters of 10 and 15nm following nucleation, and measure their water uptake. Water uptake constrains their chemical composition. We use a nanometer-hygroscopicity tandem differential mobility analyzer (nano-HTDMA) at subsaturated conditions (ca. 90% relative humidity at 293 K) to measure the hygroscopicity of particles during the seventh Cosmics Leaving OUtdoor Droplets (CLOUD7) experiments performed at CERN in 2012. In CLOUD7, the hygroscopicity of nucleated nanoparticles was measured in the presence of sulfuric acid, sulfuric acid-dimethylamine, and sulfuric acid-organics derived from α-pinene oxidation. The hygroscopicity parameter Κ decreased with increasing particle size indicating decreasing acidity of particles. No clear effect of the sulfuric acid monomer concentrations on the hygroscopicities of 10nm particles produced from sulfuric acid and dimethylamine was observed, whereas the hygroscopicity of 15nm particles sharply decreased with decreasing sulfuric acid monomer concentrations. In 20 particular, when the concentrations of sulfuric acid was 5.1 x 106 molecules cm exp -3 in the gas phase, and the dimethylamine mixing ratio was 11.8 ppt, the measured Κ of 15nm particles was 0.3 ± 0.01 close to the value reported for dimethylamine sulfate (DMAS) (Κ DMAS ~ 0.28). Furthermore, the difference in Κ between sulfuric acid and sulfuric acid-dimethylamine experiments increased with increasing particle size. The Κ values of particles in the presence of sulfuric acid and organics were much smaller than those of particles in the presence of sulfuric acid and dimethylamine. This suggests that the organics produced from α-pinene ozonolysis play a significant role in particle growth already at 10nm sizes.
New particle formation driven by acid–base chemistry was initiated in the CLOUD chamber at CERN by introducing atmospherically relevant levels of gas-phase sulfuric acid and dimethylamine (DMA). Ammonia was also present in the chamber as a gas-phase contaminant from earlier experiments. The composition of particles with volume median diameters (VMDs) as small as 10 nm was measured by the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS). Particulate ammonium-to-dimethylaminium ratios were higher than the gas-phase ammonia-to-DMA ratios, suggesting preferential uptake of ammonia over DMA for the collected 10–30 nm VMD particles. This behavior is not consistent with present nanoparticle physicochemical models, which predict a higher dimethylaminium fraction when NH3 and DMA are present at similar gas-phase concentrations. Despite the presence in the gas phase of at least 100 times higher base concentrations than sulfuric acid, the recently formed particles always had measured base : acid ratios lower than 1 : 1. The lowest base fractions were found in particles below 15 nm VMD, with a strong size-dependent composition gradient. The reasons for the very acidic composition remain uncertain, but a plausible explanation is that the particles did not reach thermodynamic equilibrium with respect to the bases due to rapid heterogeneous conversion of SO2 to sulfate. These results indicate that sulfuric acid does not require stabilization by ammonium or dimethylaminium as acid–base pairs in particles as small as 10 nm.
We report the first measurement of low-energy proton-capture cross sections of 124Xe in a heavy-ion storage ring. 124Xe54+ ions of five different beam energies between 5.5 and 8 AMeV were stored to collide with a windowless hydrogen target. The 125Cs reaction products were directly detected. The interaction energies are located on the high energy tail of the Gamow window for hot, explosive scenarios such as supernovae and x-ray binaries. The results serve as an important test of predicted astrophysical reaction rates in this mass range. Good agreement in the prediction of the astrophysically important proton width at low energy is found, with only a 30% difference between measurement and theory. Larger deviations are found above the neutron emission threshold, where also neutron and γ widths significantly impact the cross sections. The newly established experimental method is a very powerful tool to investigate nuclear reactions on rare ion beams at low center-of-mass energies.
The 124Xe(p,γ) reaction has been measured for the first time at energies around the Gamow window by using stored ions at the ESR facility. The desired beam energies below 10 MeV/u introduce new experimental challenges like windowless ions detection under UHV conditions, extremely short beam lifetimes and efficient beam deceleration and cooling, all of which have been successfully met.
Under certain conditions, secondary organic aerosol (SOA) particles can exist in the atmosphere in an amorphous solid or semi-solid state. To determine their relevance to processes such as ice nucleation or chemistry occurring within particles requires knowledge of the temperature and relative humidity (RH) range for SOA to exist in these states. In the Cosmics Leaving Outdoor Droplets (CLOUD) experiment at The European Organisation for Nuclear Research (CERN), we deployed a new in situ optical method to detect the viscous state of α-pinene SOA particles and measured their transition from the amorphous highly viscous state to states of lower viscosity. The method is based on the depolarising properties of laboratory-produced non-spherical SOA particles and their transformation to non-depolarising spherical particles at relative humidities near the deliquescence point. We found that particles formed and grown in the chamber developed an asymmetric shape through coagulation. A transition to a spherical shape was observed as the RH was increased to between 35 % at −10 °C and 80 % at −38 °C, confirming previous calculations of the viscosity-transition conditions. Consequently, α-pinene SOA particles exist in a viscous state over a wide range of ambient conditions, including the cirrus region of the free troposphere. This has implications for the physical, chemical, and ice-nucleation properties of SOA and SOA-coated particles in the atmosphere.
Particulate matter (PM) largely consists of secondary organic aerosol (SOA) that is formed via oxidation of biogenic and anthropogenic volatile organic compounds (VOCs). Unambiguous identification of SOA molecules and their assignment to their precursor vapors are challenges that have so far only succeeded for a few SOA marker compounds, which are now well characterized and (partly) available as authentic standards. In this work, we resolve the complex composition of SOA by means of a top-down approach based on the newly created Aerosolomics database, which is fed by non-target analysis results of filter samples from oxidation flow reactor experiments. We investigated the oxidation products from the five biogenic VOCs α-pinene, β-pinene, limonene, 3-carene, and trans-caryophyllene and from the four anthropogenic VOCs toluene, o-xylene, 1,2,4-trimethylbenzene, and naphthalene. Using ultrahigh-performance liquid chromatography coupled to a high-resolution (Orbitrap) mass spectrometer, we determine the molecular formula of 596 chromatographically separated compounds based on exact mass and isotopic pattern. We utilize retention time and fragmentation mass spectra as a basis for unambiguous attribution of the oxidation products to their parent VOCs. Based on the molecular-resolved application of the database, we are able to assign roughly half of the total signal of oxygenated hydrocarbons in ambient suburban PM2.5 to one of the nine studied VOCs. The application of the database enabled us to interpret the appearance of diurnal compound clusters that are formed by different oxidation processes. Furthermore, by performing a hierarchical cluster analysis (HCA) on the same set of filter samples, we identified compound clusters that depend on sulfur dioxide mixing ratio and temperature. This study demonstrates how Aerosolomics tools (database and HCA) applied to PM filter samples can improve our understanding of SOA sources, their formation pathways, and temperature-driven partitioning of SOA compounds.
Particulate matter (PM) largely consists of secondary organic aerosol (SOA) that is formed via oxidation of biogenic and anthropogenic volatile organic compounds (VOCs). Unambiguous identification of SOA molecules and their assignment to their precursor vapors is a challenge that has so far only succeeded for a few SOA marker compounds, which are now well characterized and (partly) available as authentic standards. In this work, we resolve the complex composition of SOA by a top-down approach based on a newly created aerosolomics database, which is fed by non-target analysis results of filter samples from oxidation flow reactor experiments. We investigated the oxidation products from the five biogenic VOCs α-pinene, β-pinene, limonene, 3-carene, and trans-caryophyllene and from the four anthropogenic VOCs toluene, o-xylene, 1,2,4-trimethylbenzene, and naphthalene. Using ultra-high performance liquid chromatography coupled to a high-resolution (Orbitrap) mass spectrometer, we determine the molecular formula of 596 chromatographically separated compounds based on exact mass and isotopic pattern. We utilize retention time and fragmentation mass spectra as a basis for unambiguous attribution of the oxidation products to their parent VOCs. Based on the molecular-resolved application of the database, we are able to assign roughly half of the total signal of oxygenated hydrocarbons in ambient suburban PM2.5 to one of the nine studied VOCs. The application of the database enabled us to interpret the appearance of diurnal compound clusters that are formed by different oxidation processes. Furthermore, the application of a hierarchical cluster analysis (HCA) on the same set of filter samples enabled us to identify compound clusters that depend on sulfur dioxide mixing ratio and temperature. This study demonstrates how aerosolomics tools (database and HCA) applied on PM filter samples can improve our understanding of SOA sources, their formation pathways, and temperature-driven partitioning of SOA compounds.