1Particle Chemistry Dept., Max Planck Institute for Chemistry, Mainz, Germany
2Institute for Atmospheric Physics, Johannes Gutenberg University, Mainz, Germany
3Atmospheric Chemistry Dept., Max Planck Institute for Chemistry, Mainz, Germany
4Institute of Hydrochemistry, Technical University of Munich, Germany
5German National Meteorological Service (DWD), Observatory Hohenpeissenberg, Germany
*now at: Institute for Inorganic and Analytical Chemistry, Justus Liebig University Giessen, Germany
**now at Biogeochemistry Dept., Max Planck Institute for Chemistry, Mainz, Germany
***now at: Dept. of Physics, National University of Ireland, Galway, Ireland
Abstract. Detailed investigations of the chemical and microphysical properties of rural continental aerosols were performed during the HAZE2002 experiment, which was conducted in May 2002 at the Meteorological Observatory Hohenpeissenberg (DWD) in Southern Germany.
The online measurement data and techniques included: size-resolved chemical composition of submicron particles by aerosol mass spectrometry (AMS); total particle number concentrations and size distributions over the diameter range of 3 nm to 9 μm (CPC, SMPS, OPC); monoterpenes determined by gas chromatography- ion trap mass spectrometry; OH and H2SO4 determined by atmospheric pressure chemical ionization mass spectrometry (CIMS). Filter sampling and offline analytical techniques were used to determine: fine particle mass (PM2.5), organic, elemental and total carbon in PM2.5 (OC2.5, EC2.5, TC2.5), and selected organic compounds (dicarboxylic acids, polycyclic aromatic hydrocarbons, proteins).
Overall, the non-refractory components of submicron particles detected by aerosol mass spectrometry (PM1, 6.6±5.4 μg m−3, arithmetic mean and standard deviation) accounted for ~62% of PM2.5 determined by filter gravimetry (10.6±4.7 μg m−3). The relative proportions of non-refractory submicron particle components were: 11% ammonium, 19% nitrate, 20% sulfate, and 50% organics (OM1). In spite of strongly changing meteorological conditions and absolute concentration levels of particulate matter (3–13 μg m−3 PM1), OM1 was closely correlated with PM1 (r2=0.9) indicating a near-constant ratio of non-refractory organics and inorganics. In contrast, the ratio of nitrate to sulfate was highly dependent on temperature (14–32°C) and relative humidity (20–100%), which could be explained by thermodynamic model calculations of NH3/HNO3/NH4NO3 gas-particle partitioning. From the combination of optical and other sizing techniques (OPC, AMS, SMPS), an average refractive index of 1.40–1.45 was inferred for the measured rural aerosol particles.
The average ratio of OM1 to OC2.5 was 2, indicating a high proportion of heteroelements in the organic fraction of the sampled rural aerosol. This is consistent with the high ratio of oxygenated organic aerosol (OOA) over hydrocarbon-like organic aerosol (HOA) inferred from the AMS results (4:1), and also with the high abundance of proteins (~3%) indicating a high proportion of primary biological material (~30%) in PM2.5. Moreover, the low abundance of PAHs (<1 ng m−3) and EC (<1 μg m−3) in PM2.5 confirm a low contribution of combustion emissions, which are usually also major sources for HOA. Slightly enhanced HOA concentrations indicating fresh anthropogenic emissions were observed during a period when air masses were advected from the densely populated Po Valley, Italy.
Detection of several secondary organic aerosol compounds (dicarboxylic acids) and their precursors (monoterpenes) confirmed the finding that secondary aerosol from natural sources was an important aerosol constituent. A sharp decrease of the short lived monoterpenes indicated that during night-time the measurement station was isolated from ground emission sources by a stable inversion layer. Nighttime values can therefore be regarded to represent regional or long range transport.
New particle formation was observed almost every day with particle number concentrations exceeding 104 cm−3 (nighttime background level 1000–2000 cm−3). Closer inspection of two major events indicated that ternary H2SO4/H2O/NH3 nucleation triggered particle formation and that condensation of both organic and inorganic species contributed to particle growth.