Torsten Tritscher

Aging of biogenic secondary organic aerosol via gas-phase OH radical reactions

The Multiple Chamber Aerosol Chemical Aging Study (MUCHACHAS) tested the hypothesis that hydroxyl radical (OH) aging significantly increases the concentration of first-generation biogenic secondary organic aerosol (SOA). OH is the dominant atmospheric oxidant, and MUCHACHAS employed environmental chambers of very different designs, using multiple OH sources to explore a range of chemical conditions and potential sources of systematic error. We isolated the effect of OH aging, confirming our hypothesis while observing corresponding changes in SOA properties. The mass increases are consistent with an existing gap between global SOA sources and those predicted in models, and can be described by a mechanism suitable for implementation in those models.

Changes of hygroscopicity and morphology during ageing of diesel soot

Soot particles are an important component of atmospheric aerosol and their interaction with water is important for their climate effects. The hygroscopicity of fresh and photochemically aged soot and secondary organic aerosol (SOA) from diesel passenger car emissions was studied under atmospherically relevant conditions in a smog chamber at sub-and supersaturation of water vapor. Fresh soot particles show no significant hygroscopic growth nor cloud condensation nucleus (CCN) activity. Ageing by condensation of SOA formed by photooxidation of the volatile organic carbon (VOC) emission leads to increased water uptake and CCN activity as well as to a compaction of the initially non-spherical soot particles when exposed to high relative humidity (RH). It is important to consider the latter effect for the interpretation of mobility based measurements. The vehicle with oxidation catalyst (EURO3) emits much fewer VOCs than the vehicle without after-treatment (EURO2). Consequently, more SOA is formed for the latter, resulting in more pronounced effects on particle hygroscopicity and CCN activity. Nevertheless, the aged soot particles did not reach the hygroscopicity of pure SOA particles formed from diesel VOC emissions, which are similarly hygroscopic (0.06 < κH − TDMA < 0.12 and 0.09 < κCCN < 0.14) as SOA from other precursor gases investigated in previous studies.

Water uptake of clay and desert dust aerosol particles at sub- and supersaturated water vapor conditions

Airborne mineral dust particles serve as cloud condensation nuclei (CCN), thereby influencing the formation and properties of warm clouds. It is therefore of atmospheric interest how dust aerosols with different mineralogy behave when exposed to high relative humidity (RH) or supersaturation (SS) with respect to liquid water. In this study the subsaturated hygroscopic growth and the supersaturated cloud condensation nucleus activity of pure clays and real desert dust aerosols were determined using a hygroscopicity tandem differential mobility analyzer (HTDMA) and a cloud condensation nuclei counter (CCNC), respectively. Five different illite, montmorillonite and kaolinite clay samples as well as three desert dust samples (Saharan dust (SD), Chinese dust (CD) and Arizona test dust (ATD)) were investigated. Aerosols were generated both with a wet and a dry disperser. The water uptake was parameterized via the hygroscopicity parameter kappa. The hygroscopicity of dry generated dust aerosols was found to be negligible when compared to processed atmospheric aerosols, with CCNC derived kappa values between 0.00 and 0.02 (the latter corresponds to a particle consisting of 96.7% by volume insoluble material and approximately 3.3% ammonium sulfate). Pure clay aerosols were generally found to be less hygroscopic than natural desert dust particles. The illite and montmorillonite samples had kappa approximately 0.003. The kaolinite samples were less hygroscopic and had kappa=0.001. SD (kappa=0.023) was found to be the most hygroscopic dry-generated desert dust followed by CD (kappa=0.007) and ATD (kappa=0.003). Wet-generated dust showed an increased water uptake when compared to dry-generated samples. This is considered to be an artifact introduced by redistribution of soluble material between the particles. Thus, the generation method is critically important when presenting such data. These results indicate any atmospheric processing of a fresh mineral dust particle which leads to the addition of more than approximately 3% soluble material will significantly enhance its hygroscopicity and CCN activity.

NanoScan SMPS – A Novel, Portable Nanoparticle Sizing and Counting Instrument

A novel instrument, the NanoScan SMPS (TSI 3910), is introduced here that provides the capability of employing well-established Scanning Mobility Particle Sizing (SMPS) technology in a format that can be easily utilized in the field. The use of a non-radioactive unipolar charger, radial Differential Mobility Analyzer (rDMA) and isopropanol-based Condensation Particle Counter (CPC) removes transport and application restrictions on occasion encountered with current SMPS technology. The NanoScan SMPS was compared initially to a TSI component SMPS reference system using several sizes of monodisperse silver particles. A further comparison was completed with polydisperse NaCl and Emery Oil particles. A linearity test for the instrument was performed by comparison to the ultra-fine butanol CPC (TSI 3776) as concentration reference. Subsequently, in-vehicle measurements during a freeway journey between two German cities were made to provide an example of everyday exposure to nanoparticles while driving. Coupling continuous in-vehicle measurements with GPS technology enabled an easy on-route characterization of particle size distributions, allowing source appointment of measurements, identification of evident hotspots as well as a variety of other sources of interest. Finally, the NanoScan SMPS was applied to different processes within a production test facility. Here direct comparisons between ventilation (background) and in the breathing zone were made. These measurements demonstrated the variation between the nature of the nanoparticles in the ventilation system from those within the breathing zone. During all tests the NanoScan SMPS was found to provide data that compares very well with that of the reference SMPS. It also showed a clear linearity with the CPC measurement up to concentrations as high as 106 particles/cm3. In conclusion, the NanoScan SMPS was found to be a reliable tool for nanoparticle sizing and counting in applications where current SMPS instruments would prove to be challenging.

Predicting hygroscopic growth using single particle chemical composition estimates

Single particle mass spectral data, collected in Paris, France, have been used to predict hygroscopic growth at the single particle level. The mass fractions of black carbon, organic aerosol, ammonium, nitrate, and sulphate present in each particle were estimated using a combination of single particle mass spectrometer and bulk aerosol chemical composition measurements. The Zdanovskii-Stokes-Robinson (ZSR) approach was then applied to predict hygroscopic growth factors based on these mass fraction estimates. Smaller particles with high black carbon mass fractions and low inorganic ion mass fractions exhibited the lowest predicted growth factors, while larger particles with high inorganic ion mass fractions exhibited the highest growth factors. Growth factors were calculated for subsaturated relative humidity (90%) to enable comparison with hygroscopic tandem differential mobility analyzer measurements. Mean predicted and measured hygroscopic growth factors for 110, 165, and 265 nm particles were found to agree within 6%. Single particle-based ZSR hygroscopicity estimates offer an advantage over bulk aerosol composition-based hygroscopicity estimates by providing additional chemical mixing state information. External mixing can be determined for particles of a given diameter through examination of the predicted hygroscopic growth factor distributions. Using this approach, 110 nm and 265 nm particles were found to be predominantly internally mixed; however, external mixing of 165 nm particles was observed periodically when thinly coated and thickly coated black carbon particles were simultaneously detected. Single particle-resolved chemical information will be useful for modeling efforts aimed at constraining cloud condensation nuclei activity and hygroscopic growth.

Multi-Instrument Manager Tool for Data Acquisition and Merging of Optical and Electrical Mobility Size Distributions

Electrical mobility classification (EC) followed by Condensation Particle Counter (CPC) detection is the technique combined in Scanning Mobility Particle Sizers(SMPS) to retrieve nanoparticle size distributions in the range from 2.5 nm to 1 μm. The detectable size range of SMPS systems can be extended by the addition of an Optical Particle Sizer(OPS) that covers larger sizes from 300 nm to 10 μm. This optical sizing method reports an optical equivalent diameter, which is often different from the electrical mobility diameter measured by the standard SMPS technique. Multi-Instrument Manager (MIMTM) software developed by TSI incorporates algorithms that facilitate merging SMPS data sets with data based on optical equivalent diameter to compile single, wide-range size distributions. Here we present MIM 2.0, the next-generation of the data merging tool that offers many advanced features for data merging and post-processing. MIM 2.0 allows direct data acquisition with OPS and NanoScan SMPS instruments to retrieve real-time particle size distributions from 10 nm to 10 μm, which we show in a case study at a fireplace. The merged data can be adjusted using one of the merging options, which automatically determines an overall aerosol effective refractive index. As a result an indirect and average characterization of aerosol optical and shape properties is possible. The merging tool allows several pre-settings, data averaging and adjustments, as well as the export of data sets and fitted graphs. MIM 2.0 also features several post-processing options for SMPS data and differences can be visualized in a multi-peak sample over a narrow size range.