Nicolas Bukowiecki

Separation of volatile and non-volatile aerosol fractions by thermodesorption : instrumental development and applications

Abstract An instrument to remove volatile material from aerosol particles by thermal desorption is presented. The thermodesorber consists of a heated tube, where volatile material is desorbed from the particles, and a water- or air-cooled tube, consisting of activated charcoal. This last tube removes desorbed material and thus prevents it from re-adsorbing onto particles. Although designed for measuring particulate emissions from combustion processes it can also be applied to atmospheric aerosols. After theoretical and experimental determination of thermodesorber operating characteristics (temperature profile, losses, removal of desorbed material), examples of applications in several fields are given. Examples of atmospheric measurements at several remote and urban sites are presented. In combustion technology, the thermodesorber is applied to remove all volatile materials, allowing separation of volatile species and the non-volatile core (mainly elemental carbon) of combustion particles. Finally, the thermodesorber is used to study adsorption and desorption processes of polycyclic aromatic hydrocarbons on particles.

Diesel Aerosol Sampling in the Atmosphere

The University of Minnesota Center for Diesel Research along with a research team including Caterpillar, Cummins, Carnegie Mellon University, West Virginia University (WVU), Paul Scherrer Institute in Switzerland, and Tampere University in Finland have performed measurements of Diesel exhaust particle size distributions under real-world dilution conditions. A mobile aerosol emission laboratory (MEL) equipped to measure particle size distributions, number concentrations, surface area concentrations, particle bound PAHs, as well as CO 2 and NO x concentrations in real time was built and will be described. The MEL was used to follow two different Cummins powered tractors, one with an older engine (L10) and one with a state-of-the-art engine (ISM), on rural highways and measure particles in their exhaust plumes. This paper will describe the goals and objectives of the study and will describe representative particle size distributions observed in roadway experiments with the truck powered by the ISM engine.

New particle formation in the free troposphere: A question of chemistry and timing

From neutral to new Many of the particles in the troposphere are formed in situ, but what fraction of all tropospheric particles do they constitute and how exactly are they made? Bianchi et al. report results from a high-altitude research station. Roughly half of the particles were newly formed by the condensation of highly oxygenated multifunctional compounds. A combination of laboratory results, field measurements, and model calculations revealed that neutral nucleation is more than 10 times faster than ion-induced nucleation, that particle growth rates are size-dependent, and that new particle formation occurs during a limited time window. Science, this issue p. 1109 New particles form in the free troposphere mainly through condensation of highly oxygenated compounds. New particle formation (NPF) is the source of over half of the atmosphere’s cloud condensation nuclei, thus influencing cloud properties and Earth’s energy balance. Unlike in the planetary boundary layer, few observations of NPF in the free troposphere exist. We provide observational evidence that at high altitudes, NPF occurs mainly through condensation of highly oxygenated molecules (HOMs), in addition to taking place through sulfuric acid–ammonia nucleation. Neutral nucleation is more than 10 times faster than ion-induced nucleation, and growth rates are size-dependent. NPF is restricted to a time window of 1 to 2 days after contact of the air masses with the planetary boundary layer; this is related to the time needed for oxidation of organic compounds to form HOMs. These findings require improved NPF parameterization in atmospheric models.

Real-time characterization of ultrafine and accumulation mode particles in ambient combustion aerosols

Abstract The diffusion charging sensor (DC), photoelectric aerosol sensor (PAS) and condensation particle counter (CPC) are real-time particle instruments that have time resolutions s and are suitable for field use. This paper shows how the relative fraction of nuclei mode particles (D⩽50 nm ) in ambient combustion aerosols can be determined, along with the coverage degree of the respective accumulation mode particles with a modal diameter of ∼100 nm . Main tools for interpretation are the diameter of average surface D Ave, S (obtained from CPC and DC measurements) and PAS/DC versus D Ave, S scatter plots. Compared to the scanning mobility particle sizer (SMPS), which is a standard instrument for aerosol particle size distribution measurements, the presented method has a limited accuracy, but is substantially faster. Additionally, it is experimentally less demanding than SMPS measurements, especially for field applications.

Real-World Emission Factors for Antimony and Other Brake Wear Related Trace Elements: Size-Segregated Values for Light and Heavy Duty Vehicles

Hourly trace element measurements were performed in an urban street canyon and next to an interurban freeway in Switzerland during more than one month each, deploying a rotating drum impactor (RDI) and subsequent sample analysis by synchrotron radiation X-ray fluorescence spectrometry (SR-XRF). Antimony and other brake wear associated elements were detected in three particle size ranges (2.5-10, 1-2.5, and 0.1-1 microm). The hourly measurements revealed that the effect of resuspended road dust has to be taken into account for the calculation of vehicle emission factors. Individual values for light and heavy duty vehicles were obtained for stop-and-go traffic in the urban street canyon. Mass based brake wear emissions were predominantly found in the coarse particle fraction. For antimony, determined emission factors were 11 +/- 7 and 86 +/- 42 microg km(-1) vehicle(-1) for light and heavy duty vehicles, respectively. Antimony emissions along the interurban freeway with free-flowing traffic were significantly lower. Relative patterns for brake wear related elements were very similar for both considered locations. Beside vehicle type specific brake wear emissions, road dust resuspension was found to be a dominant contributor of antimony in the street canyon.

Analysis of long-term aerosol size distribution data from Jungfraujoch with emphasis on free tropospheric conditions, cloud influence, and air mass transport

Six years of aerosol size distribution measurements between 20 and 600 nm diameters and total aerosol concentration above 10 nm from March 2008 to February 2014 at the high-alpine site Jungfraujoch are presented. The size distribution was found to be typically bimodal with mode diameters and widths relatively stable throughout the year and the observation period. New particle formation was observed on 14.5% of all days without a seasonal preference. Particles typically grew only into the Aitken mode and did not reach cloud condensation nucleus (CCN) sizes on the time scale of several days. Growth of preexisting particles in the Aitken mode, on average, contributed very few CCN. We concluded that the dominant fraction of CCN at Jungfraujoch originated in the boundary layer. A number of approaches were used to distinguish free tropospheric (FT) conditions and episodes with planetary boundary layer (PBL) influence. In the absence of PBL injections, the concentration of particles larger than 90 nm (N90, roughly corresponding to the CCN concentration) reached a value ~40 cm−3 while PBL influence caused N90 concentrations of several hundred or even 1000 cm−3. Comparing three criteria for free tropospheric conditions, we found FT prevalence for 39% of the time with over 60% during winter and below 20% during summer. It is noteworthy that a simple criterion based on standard trace gas measurements appeared to outperform alternative approaches.

Atmospheric ice nuclei at the high-altitude observatory Jungfraujoch, Switzerland

Abstract The state of a slightly supercooled ephemeral cloud can be changed by the presence of a few particles capable of catalysing freezing, and potentially result in precipitation. We investigated the atmospheric abundance of particles active as ice nuclei at −8°C (IN−8) over the course of a year at the high-alpine station Jungfraujoch (3580 m.a.s.l., Switzerland) through the use of immersion freezing assays of particles collected on quartz micro-fibre filters. In addition, we determined IN−8 on a hill in the planetary boundary layer 95 km northwest of Jungfraujoch and in the dust laden Saharan Air Layer reaching Tenerife. Results indicate a strong seasonality of IN−8 at Jungfraujoch. Values were largest during summer (between 1 and 10 m−3) and about two orders of magnitude smaller during winter. Sahara dust events had a negligible influence on IN−8 at Jungfraujoch. Seasonality in the boundary layer was not observed in the upper, but in the lower bound of IN−8 values. Values<1 m−3 were only found on cold winter days, when IN−8 were more likely to have already been activated and deposited than on warmer days. A good correlation between IN−8 and maximum daily temperature at Jungfraujoch (R2=0.54) suggests IN−8 abundance at Jungfraujoch may be limited most of the year by microphysical processing related to IN activation in approaching air masses.

Ice nucleation active particles are efficiently removed by precipitating clouds

Ice nucleation in cold clouds is a decisive step in the formation of rain and snow. Observations and modelling suggest that variations in the concentrations of ice nucleating particles (INPs) affect timing, location and amount of precipitation. A quantitative description of the abundance and variability of INPs is crucial to assess and predict their influence on precipitation. Here we used the hydrological indicator δ18O to derive the fraction of water vapour lost from precipitating clouds and correlated it with the abundance of INPs in freshly fallen snow. Results show that the number of INPs active at temperatures ≥ −10 °C (INPs−10) halves for every 10% of vapour lost through precipitation. Particles of similar size (>0.5 μm) halve in number for only every 20% of vapour lost, suggesting effective microphysical processing of INPs during precipitation. We show that INPs active at moderate supercooling are rapidly depleted by precipitating clouds, limiting their impact on subsequent rainfall development in time and space.

Quantitative analysis of heavy metals in automotive brake linings: A comparison between wet-chemistry based analysis and in-situ screening with a handheld X-ray fluorescence spectrometer

Two extraction procedures for ecologically relevant elements present in automotive brake linings (Sb, Bi, Pb, Cd, Cr (total), Co, Cu, Mo, Ni, Sr, V, Zn, Sn) were developed and validated, applying a high pressure asher (HPA-S) and microwave extraction, respectively. Both of these methods allowed for the quantitative analysis of the extracted elements by inductively coupled plasma optical emission spectrometry (ICP-OES). The results were compared to measurements using a handheld energy-dispersive X-ray fluorescence spectrometer (ED-XRF), being in discussion by regulating agencies as in-situ screening tool for brake pads. The comparison indicates that the handheld ED-XRF analysis is basically an efficient screening tool for a reliable assessment of trace metal contents in automotive brake pads with respect to legal standards. While a quantitative determination of elements like Cd, Co, Cr, Mn, Mo, Ni, Pb and Sb was achievable, other elements (V, Cu, Bi, Zn, Sn and Sr) could only be determined qualitatively due to the special matrix characteristics of brake pads.

Simultaneous dry and ambient measurements of aerosol size distributions at the Jungfraujoch

In a field campaign at the high-alpine site Jungfraujoch (JFJ, 3580 m asl), in-situ aerosol size distributions were measured simultaneously outdoor at ambient conditions (temperature T < −5 °C) and indoor at dry conditions (T ≈ 25 °C and relative humidity RH < 10%) by means of two scanning mobility particle sizers (SMPS). In addition, measurements of hygroscopic growth factors were performed with a hygroscopicity tandem differential mobility analyzer (H-TDMA). The measured growth factors, being a monotonic function of the relative humidity (RH), were fitted with a modified Köhler model. A comparison between dry and ambient size distributions shows two main features: First, the dry total number concentration is often considerably smaller (on average 28%) than the ambient total number concentration, and is most likely due to the evaporation of volatile material at the higher temperature. These particle losses mainly concern small particles (dry diameter D ≲ 100 nm), and therefore have only a minimal affect on the surface and volume concentrations. A slight correlation between ambient RH and the magnitude of particle loss was observed, but it was not possible to establish an empirical model for a quantification. Second, the dry number size distribution is shifted towards smaller particles, reflecting the hygroscopic behavior of the aerosols. To link the ambient and the dry size distributions we modeled this shift using the H-TDMA measurements and a modified Köhler model. The corrected dry surface and volume concentrations are in good agreement with the ambient measurements for the whole RH range, but the correction works best for RH < 80%. The results indicate that size distribution data measured at indoor conditions (i.e. dry and warm) may be successfully corrected to reflect ambient conditions, which are relevant for determining the impact of aerosol on climate.