Hygroscopicity of Nucleated Nanoparticles in CLOUD 7 Experiments

We investigated hygroscopicity of nucleated nanoparticles derived from dimethylamine and α-pinene with sulfuric acid during CLOUD 7 (Cosmic Leaving OUtdoor Droplets) campaign at CERN. The hygroscopicity of nucleated nanoparticles from 10 to 20 nm in mobility diameter was measured with a nano tandem differential mobility analyzer (nano-TDMA). Here, we present preliminary results from the CLOUD 7 experiments

Comparing secondary organic aerosol (SOA) volatility distributions derived from isothermal SOA particle evaporation data and FIGAERO-CIMS measurements

The volatility distribution of the organic compounds present in secondary organic aerosol (SOA) at different conditions is a key quantity that has to be captured in order to describe SOA dynamics accurately. The development of the Filter Inlet for Gases and AEROsols (FIGAERO) and its coupling to a chemical ionization mass spectrometer (CIMS; collectively FIGAERO-CIMS) has enabled near-simultaneous sampling of the gas and particle phases of SOA through thermal desorption of the particles. The thermal desorption data have been recently shown to be interpretable as a volatility distribution with the use of the positive matrix factorization (PMF) method. Similarly, volatility distributions can be inferred from isothermal particle evaporation experiments when the particle size change measurements are analyzed with process-modeling techniques. In this study, we compare the volatility distributions that are retrieved from FIGAERO-CIMS and particle size change measurements during isothermal particle evaporation with process-modeling techniques. We compare the volatility distributions at two different relative humidities (RHs) and two oxidation conditions. In high-RH conditions, where particles are in a liquid state, we show that the volatility distributions derived via the two ways are similar within a reasonable assumption of uncertainty in the effective saturation mass concentrations that are derived from FIGAERO-CIMS data. In dry conditions, we demonstrate that the volatility distributions are comparable in one oxidation condition, and in the other oxidation condition, the volatility distribution derived from the PMF analysis shows considerably more high-volatility matter than the volatility distribution inferred from particle size change measurements. We also show that the Vogel-Tammann-Fulcher equation together with a recent glass transition temperature parametrization for organic compounds and PMF-derived volatility distribution estimates are consistent with the observed isothermal evaporation under dry conditions within the reported uncertainties. We conclude that the FIGAERO-CIMS measurements analyzed with the PMF method are a promising method for inferring the volatility distribution of organic compounds, but care has to be taken when the PMF factors are analyzed. Future process-modeling studies about SOA dynamics and properties could benefit from simultaneous FIGAERO-CIMS measurements.Peer reviewe

Secondary Organic Aerosol Formation from Healthy and Aphid-Stressed Scots Pine Emissions.

One barrier to predicting biogenic secondary organic aerosol (SOA) formation in a changing climate can be attributed to the complex nature of plant volatile emissions. Plant volatile emissions are dynamic over space and time, and change in response to environmental stressors. This study investigated SOA production from emissions of healthy and aphid-stressed Scots pine saplings via dark ozonolysis and photooxidation chemistry. Laboratory experiments using a batch reaction chamber were used to investigate SOA production from different plant volatile mixtures. The volatile mixture from healthy plants included monoterpenes, aromatics, and a small amount of sesquiterpenes. The biggest change in the volatile mixture for aphid-stressed plants was a large increase (from 1.4 to 7.9 ppb) in sesquiterpenes-particularly acyclic sesquiterpenes, such as the farnesene isomers. Acyclic sesquiterpenes had different effects on SOA production depending on the chemical mechanism. Farnesenes suppressed SOA formation from ozonolysis with a 9.7-14.6% SOA mass yield from healthy plant emissions and a 6.9-10.4% SOA mass yield from aphid-stressed plant emissions. Ozonolysis of volatile mixtures containing more farnesenes promoted fragmentation reactions, which produced higher volatility oxidation products. In contrast, plant volatile mixtures containing more farnesenes did not appreciably change SOA production from photooxidation. SOA mass yields ranged from 10.8 to 23.2% from healthy plant emissions and 17.8-26.8% for aphid-stressed plant emissions. This study highlights the potential importance of acyclic terpene chemistry in a future climate regime with an increased presence of plant stress volatiles

The effect of cloudiness on new-particle formation : investigation of radiation levels

Peer reviewe

α-Pinene secondary organic aerosol at low temperature: chemical composition and implications for particle viscosity

Chemical composition, size distributions, and degree of oligomerization of secondary organic aerosol (SOA) from α-pinene (C10H16) ozonolysis were investigated for low-temperature conditions (223 K). Two types of experiments were performed using two simulation chambers at the Karlsruhe Institute of Technology: the Aerosol Preparation and Characterization (APC) chamber, and the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) chamber. Experiment type 1 simulated SOA formation at upper tropospheric conditions: SOA was generated in the AIDA chamber directly at 223 K at 61 % relative humidity (RH; experiment termed “cold humid”, CH) and for comparison at 6 % RH (experiment termed “cold dry”, CD) conditions. Experiment type 2 simulated SOA uplifting: SOA was formed in the APC chamber at room temperature (296 K) and < 1 % RH (experiment termed “warm dry”, WD) or 21 % RH (experiment termed “warm humid”, WH) conditions, and then partially transferred to the AIDA chamber kept at 223 K, and 61 % RH (WDtoCH) or 30 % RH (WHtoCH), respectively. Precursor concentrations varied between 0.7 and 2.2 ppm α-pinene, and between 2.3 and 1.8 ppm ozone for type 1 and type 2 experiments, respectively. Among other instrumentation, a chemical ionization mass spectrometer (CIMS) coupled to a filter inlet for gases and aerosols (FIGAERO), deploying I− as reagent ion, was used for SOA chemical composition analysis. For type 1 experiments with lower α-pinene concentrations and cold SOA formation temperature (223 K), smaller particles of 100–300 nm vacuum aerodynamic diameter (dva) and higher mass fractions (> 40 %) of adducts (molecules with more than 10 carbon atoms) of α-pinene oxidation products were observed. For type 2 experiments with higher α-pinene concentrations and warm SOA formation temperature (296 K), larger particles ( ∼  500 nm dva) with smaller mass fractions of adducts (< 35 %) were produced. We also observed differences (up to 20 °C) in maximum desorption temperature (Tmax) of individual compounds desorbing from the particles deposited on the FIGAERO Teflon filter for different experiments, indicating that Tmax is not purely a function of a compound\u27s vapor pressure or volatility, but is also influenced by diffusion limitations within the particles (particle viscosity), interactions between particles deposited on the filter (particle matrix), and/or particle mass on the filter. Highest Tmax were observed for SOA under dry conditions and with higher adduct mass fraction; lowest Tmax were observed for SOA under humid conditions and with lower adduct mass fraction. The observations indicate that particle viscosity may be influenced by intra- and inter-molecular hydrogen bonding between oligomers, and particle water uptake, even under such low-temperature conditions. Our results suggest that particle physicochemical properties such as viscosity and oligomer content mutually influence each other, and that variation in Tmax of particle desorptions may have implications for particle viscosity and particle matrix effects. The differences in particle physicochemical properties observed between our different experiments demonstrate the importance of taking experimental conditions into consideration when interpreting data from laboratory studies or using them as input in climate models

Emissions of biogenic volatile organic compounds from adjacent boreal fen and bog as impacted by vegetation composition

Peatland ecosystems emit biogenic volatile organic compounds (BVOC), which have a net cooling impact on the climate. However, the quality and quantity of BVOC emissions, and how they are regulated by vegetation and peatland type remain poorly understood. Here we measured BVOC emissions with dynamic enclosures from two major boreal peatland types, a minerotrophic fen and an ombrotrophic bog situated in Siikaneva, southern Finland and experimentally assessed the role of vegetation by removing vascular vegetation with or without the moss layer. Our measurements from four campaigns during growing seasons in 2017 and 2018 identified emissions of 59 compounds from nine different chemical groups. Isoprene accounted for 81 % of BVOC emissions. Measurements also revealed uptake of dichloromethane. Total BVOC emissions and the emissions of isoprene, monoterpenoids, sesquiterpenes, homoterpenes, and green leaf volatiles were tightly con-nected to vascular plants. Isoprene and sesquiterpene emissions were associated with sedges, whereas monoterpenoids and homoterpenes were associated with shrubs. Additionally, isoprene and alkane emissions were higher in the fen than in the bog and they significantly contributed to the higher BVOC emissions from intact vegetation in the fen. During an ex-treme drought event in 2018, emissions of organic halides were absent. Our results indicate that climate change with an increase in shrub cover and increased frequency of extreme weather events may have a negative impact on total BVOC emissions that otherwise are predicted to increase in warmer temperatures. However, these changes also accompanied a change in BVOC emission quality. As different compounds differ in their capacity to form secondary organic aerosols, the ultimate climate impact of peatland BVOC emissions may be altered.Peer reviewe

The effect of clouds and precipitation on the aerosol concentrations and composition in a boreal forest environment

Atmospheric aerosol particle concentrations are strongly affected by various wet processes, including below and in-cloud wet scavenging and in-cloud aqueous-phase oxidation. We studied how wet scavenging and cloud processes affect particle concentrations and composition during transport to a rural boreal forest site in northern Europe. For this investigation, we employed air mass history analysis and observational data. Long-term particle number size distribution (similar to 15 years) and composition measurements (similar to 8 years) were combined with air mass trajectories with relevant variables from reanalysis data. Some such variables were rainfall rate, relative humidity, and mixing layer height. Additional observational datasets, such as temperature and trace gases, helped further evaluate wet processes along trajectories with mixed effects models. All chemical species investigated (sulfate, black carbon, and organics) exponentially decreased in particle mass concentration as a function of accumulated precipitation along the air mass route. In sulfate (SO4) aerosols, clear seasonal differences in wet removal emerged, whereas organics (Org) and equivalent black carbon (eBC) exhibited only minor differences. The removal efficiency varied slightly among the different reanalysis datasets (ERA-Interim and Global Data Assimilation System; GDAS) used for the trajectory calculations due to the difference in the average occurrence of precipitation events along the air mass trajectories between the reanalysis datasets. Aqueous-phase processes were investigated by using a proxy for air masses travelling inside clouds. We compared air masses with no experience of approximated in-cloud conditions or precipitation during the past 24 h to air masses recently inside non-precipitating clouds before they entered SMEAR II (Station for Measuring Ecosystem-Atmosphere Relations). Significant increases in SO4 mass concentration were observed for the latter air masses (recently experienced non-precipitating clouds). Our mixed effects model considered other contributing factors affecting particle mass concentrations in SMEAR II: examples were trace gases, local meteorology, and diurnal variation. This model also indicated in-cloud SO4 production. Despite the reanalysis dataset used in the trajectory calculations, aqueous-phase SO4 formation was observed. Particle number size distribution measurements revealed that most of the in-cloud SO4 formed can be attributed to particle sizes larger than 200 nm (electrical mobility diameter). Aqueous-phase secondary organic aerosol (aqSOA) formation was non-significant.Peer reviewe