Total sulfate vs. sulfuric acid monomer concenterations in nucleation studies

Sulfuric acid is known to be a key component for atmospheric nucleation. Precise determination of sulfuric-acid concentration is a crucial factor for prediction of nucleation rates and subsequent growth. In our study, we have noticed a substantial discrepancy between sulfuric-acid monomer concentrations and total-sulfate concentrations measured from the same source of sulfuric-acid vapor. The discrepancy of about 1-2 orders of magnitude was found with similar particle-formation rates. To investigate this discrepancy, and its effect on nucleation, a method of thermally controlled saturator filled with pure sulfuric acid (97% wt.) for production of sulfuric-acid vapor is applied and rigorously tested. The saturator provided an independent vapor-production method, compared to our previous method of the furnace (Brus et al., 2010, 2011), to find out if the discrepancy is caused by the production method itself. The saturator was used in a H2SO4-H2O nucleation experiment, using a laminar flow tube to check reproducibility of the nucleation results with the saturator method, compared to the furnace. Two independent methods of mass spectrometry and online ion chromatography were used for detecting sulfuric-acid or sulfate concentrations. Measured sulfuric-acid or total-sulfate concentrations are compared to theoretical predictions calculated using vapor pressure and a mixing law. The calculated prediction of sulfuric-acid concentrations agrees very well with the measured values when total sulfate is considered. Sulfuric-acid monomer concentration was found to be about 2 orders of magnitude lower than theoretical predictions, but with a temperature dependency similar to the predictions and the results obtained with the ion-chromatograph method. Formation rates are reproducible when compared to our previous results with both sulfuric-acid or total-sulfate detection and sulfuric-acid production methods separately, removing any doubts that the vapor-production method would cause the discrepancy. Possible reasons for the discrepancy are discussed and some suggestions include that the missing sulfuric acid is in clusters, formed with contaminants found in most laboratory experiments. One-to-two-order-of-magnitude higher sulfuric-acid concentrations (measured as total sulfate in this study) would contribute to a higher fraction of particle growth rate than assumed from the measurements by mass spectrometers (i.e. sulfuric-acid monomer). However, the observed growth rates by sulfate-containing vapor in this study does not directly imply a similar situation in the field, where sources of sulfate are much more diverse.Peer reviewe

Závislost velikosti částic na koncentraci kyseliny sírové při binární nukleaci systému H2SO4-H2O

In the experiment we studied water-sulphuric acid binary homogeneous nucleation in laminar flow chamber. Nucleation rates and mean diameter were determined as a function of sulphuric acid concentration in three different relative humidities. Number of sulphuric acid molecules in critical cluster was determined from the experimental data and the results are in fair agreement with previous experiments

New particle formation infrequently observed in Himalayan foothills – why?

A fraction of the Himalayan aerosols originate from secondary sources, which are currently poorly quantified. To clarify the climatic importance of regional secondary particle formation in the Himalayas, data from 2005 to 2010 of continuous aerosol measurements at a high-altitude (2180 m) Indian Himalayan site, Mukteshwar, were analyzed. For this period, the days were classified, and the particle formation and growth rates were calculated for clear new particle formation (NPF) event days. The NPF events showed a pronounced seasonal cycle. The frequency of the events peaked in spring, when the ratio between event and non-event days was 53 %, whereas the events were truly sporadic on any other seasons. The annual mean particle formation and growth rates were 0.40 cm<sup>−3</sup> s<sup>−1</sup> and 2.43 nm h<sup>−1</sup>, respectively. The clear annual cycle was found to be mainly controlled by the seasonal evolution of the Planetary Boundary Layer (PBL) height together with local meteorological conditions. Spring NPF events were connected with increased PBL height, and therefore characterised as boundary layer events, while the rare events in other seasons represented lower free tropospheric particle formation. This provides insight on the vertical extent of NPF in the atmosphere

Results of the first air ion spectrometer calibration and intercomparison workshop

The Air Ion Spectrometer (AIS) measures mobility and size distributions of atmospheric ions. The Neutral cluster and Air Ion Spectrometer (NAIS) can additionally measure neutral particles. The number of the (N)AIS instruments in the world is only 11. Nevertheless, they are already widely used in atmospheric ion studies, particularly related to the initial steps of new particle formation. There is no standard method applicable for calibrating the ion spectrometers in the sub-3 nm ion range. However, recent development of high resolution DMAs has enabled the size separation of small ions with good mobility resolution. For the first time, the ion spectrometers were intercompared and calibrated in a workshop, held in January–February 2008 in Helsinki, Finland. The overall goal was to experimentally determine the (N)AIS transfer functions. Monomobile mobility standards, 241-Am charger ions and silver particles were generated and used as calibration aerosols. High resolution DMAs were used to size-separate the smaller (1–10 nm) ions, while at bigger diameters (4–40 nm) the size was selected with a HAUKE-type DMA. Negative ion mobilities were detected by (N)AISs with slightly better accuracy than positive, nonetheless, both were somewhat overestimated. A linear fit of slope of one to the whole dataset of mobilities suggested that (N)AISs measured the negative mobilities 1.36±0.16 times larger compared with the reference instruments. Similarly, positive mobilities were measured 1.39±0.15 times larger compared with the reference instruments. The completely monomobile mobility standards were measured with the best accuracy. The (N)AIS concentrations were compared with an aerosol electrometer (AE) and a condensation particle counter (CPC). At sizes below 1.5 nm (positive) and 3 nm (negative) the ion spectrometers detected higher concentrations while at bigger sizes they showed similar concentrations as the reference instruments. The total particle concentrations measured by the NAISs were within ±50% of the reference CPC concentration at 4–40 nm sizes. The lowest cut-off size of the NAIS in neutral particle measurements was determined to be between 1.5 and 3 nm, depending on the measurement conditions and the polarity

Soot on snow experiments: light-absorbing impurities effect on the natural snowpack

Abstract. Light-absorbing impurities affect snow and ice via a decrease in albedo and a consequent disturbance to the radiative energy balance. Experimentally, these matters have only been examined in a few studies. Here we present results from a series of experiments in which we deposited different soot concentrations onto natural snow in different regions of Finland, and thereafter monitored the changes of the snowpack through the melting season. Measurements of the particulates in the snow indicated concentrations in the range of thousands of ppb to have clear effects on the snow properties, including the albedo, the physical snow characteristics, and an increased melt rate. For soot concentrations in the hundreds of ppb range, the effects were not as clearly visible, and it was more difficult to attribute the effects solely to the soot on the snow. Comparisons between our experimental data and the widely used Snow, Ice and Aerosol Radiation (SNICAR) model showed a general agreement when the model was specifically tuned to our measurements. This study highlights the importance of additional experimental studies, to further articulate and quantify the effects of light-absorbing impurities on snow. </jats:p

The Unmanned Systems Research Laboratory (USRL): A New Facility for UAV-Based Atmospheric Observations

The Unmanned Systems Research Laboratory (USRL) of the Cyprus Institute is a new mobile exploratory platform of the EU Research Infrastructure Aerosol, Clouds and Trace Gases Research InfraStructure (ACTRIS). USRL offers exclusive Unmanned Aerial Vehicle (UAV)-sensor solutions that can be deployed anywhere in Europe and beyond, e.g., during intensive field campaigns through a transnational access scheme in compliance with the drone regulation set by the European Union Aviation Safety Agency (EASA) for the research, innovation, and training. UAV sensor systems play a growing role in the portfolio of Earth observation systems. They can provide cost-effective, spatial in-situ atmospheric observations which are complementary to stationary observation networks. They also have strong potential for calibrating and validating remote-sensing sensors and retrieval algorithms, mapping close-to-the-ground emission point sources and dispersion plumes, and evaluating the performance of atmospheric models. They can provide unique information relevant to the short- and long-range transport of gas and aerosol pollutants, radiative forcing, cloud properties, emission factors and a variety of atmospheric parameters. Since its establishment in 2015, USRL is participating in major international research projects dedicated to (1) the better understanding of aerosol-cloud interactions, (2) the profiling of aerosol optical properties in different atmospheric environments, (3) the vertical distribution of air pollutants in and above the planetary boundary layer, (4) the validation of Aeolus satellite dust products by utilizing novel UAV-balloon-sensor systems, and (5) the chemical characterization of ship and stack emissions. A comprehensive overview of the new UAV-sensor systems developed by USRL and their field deployments is presented here. This paper aims to illustrate the strong scientific potential of UAV-borne measurements in the atmospheric sciences and the need for their integration in Earth observation networks