Measurements of aerosol particles in the Skocjan Caves, Slovenia.

For the first time, continuous aerosol measurements were performed in the Skocjan Caves, one of the most important cave systems in the world, and listed by UNESCO as a natural and cultural world heritage site since 1986. Measurements of PM10 were performed during three different periods: (1) in December 2011, the average background concentration was found to be about 4 µg m(-3); (2) in June 2012, a higher concentration was measured (8 µg m(-3)); and (3) from 8 to 20 August 2012, the highest concentration of 15.3 µg m(-3) was measured. Based on the PM10 measurement results, and as compared to similar measurements outside the cave, it can be hypothesized that the increase in the cave's aerosol concentration during the summer was connected to both the higher number of visitors and the polluted atmospheric air entering the cave upon entering of the cave system. Additional measurement of nanoparticles with scanning mobility particle sizer spectrometer (size between 14.1 and 710.5 nm) confirmed these findings; during the summer period, a severe raise in the total aerosol concentration of 30-50 times was found when groups of visitors entered the cave. Our results on nanoparticles demonstrated that we were able to detect very small changes and variations in aerosol concentration inside the cave. To our knowledge, these are the first results on nanoaerosol measurements in a cave, and we believe that such measurements may lead to the implementation of better protection of delicate cave systems.

Chemical composition and hygroscopic properties of size-segregated aerosol particles collected at the Adriatic coast of Slovenia.

The chemical composition as well as the water uptake characteristics of aerosols was determined in size-segregated samples collected during November 2002 on the Slovenian coast. Major ions, water-soluble organic compounds (WSOC), short-chain carboxylic acids and trace elements were determined in the water-soluble fraction of the aerosol. Total aerosol black carbon (BC) was measured from filter samples. Our results showed that the origin of air masses is an important factor that controls the variation in the size distribution of the main components. Very high concentrations of WSOC as well as higher concentrations of BC were found under mostly continental influence. Besides the main ionic species (SO4(2-), NH4(+), K+) in the finest size fraction (0.17-0.53 microm), the concentration of NO3(-) was also high. The difference between the two different air mass origins is particularly expressed for Cl-, Na+, Mg2+ and Ca2+ determined in particles larger than 1.6 microm. As expected, a very good correlation was found between Na+ and Cl-. A good correlation was found between sea salt elements and elements of crustal origin (Na+, Cl-, Mg2+, Ca2+, Sr). A good relationship between typical anthropogenic tracers (K, V and Pb) was also observed. The mass growth factors, for all size fractions of aerosols collected under continental influence were very low (maximum 2.23 at 94%, 1.6-5.1 microm), while under marine influence the mass growth factors increased significantly with the particle size. At 97% humidity, the mass growth factors were 6.95 for the size fraction 0.53-1.6 microm and 9.78 for larger particles (1.6-5.1 microm).

Determination of sulfur oxides formed during the S(IV) oxidation in the presence of iron.

The reaction products (i.e., sulfate (SO4(2-)) and dithionate (S2O6(2-))) of S(IV) oxidation in the presence of iron(III) under different experimental conditions were investigated. Ion-interaction chromatography was used for the separation of sulfate and dithionate using tetrabutylammonium hydroxide (TBAOH) as an ion-pair reagent. The chromatographic method was optimized by varying the composition of the mobile phase (i.e., concentration of TBAOH, acetonitrile and Na2CO3) and by varying the flow rate of the mobile phase. The method was successfully applied to the determination of dithionate formed during the S(IV) oxidation in the presence of Fe(III). In air-saturated solutions sulfate was observed as the only product, while in N2-saturated solutions dithionate was also determined, but it is the minor reaction product and represents about 4% of the total amount of oxidized HSO3- under the studied conditions.