Ambient and laboratory observations of organic ammonium salts in PM1.

Ambient measurements of PM1 aerosol chemical composition at Cabauw, the Netherlands, implicate higher ammonium concentrations than explained by the formation of inorganic ammonium salts. This additional particulate ammonium is called excess ammonium (eNH4). Height profiles over the Cabauw Experimental Site for Atmospheric Research (CESAR) tower, of combined ground based and airborne aerosol mass spectrometric (AMS) measurements on a Zeppelin airship show higher concentrations of eNH4 at higher altitudes compared to the ground. Through flights across the Netherlands, the Zeppelin based measurements furthermore substantiate eNH4 as a regional phenomenon in the planetary boundary layer. The excess ammonium correlates with mass spectral signatures of (di-)carboxylic acids, making a heterogeneous acid-base reaction the likely process of NH3 uptake. We show that this excess ammonium was neutralized by the organic fraction forming particulate organic ammonium salts. We discuss the significance of such organic ammonium salts for atmospheric aerosols and suggest that NH3 emission control will have benefits for particulate matter control beyond the reduction of inorganic ammonium salts.

Altered Th17/Treg balance and dysregulated IL-1ß response influence susceptibility/resistance to experimental autoimmune arthritis.

This study was aimed at gaining an insight into immune mechanisms of differential susceptibility to autoimmunity of individuals sharing the same major histocompatibility complex by studying arthritis-susceptible Lewis (LEW) and arthritis-resistant Wistar Kyoto (WKY) rats (both RT.1(l)) using the adjuvant arthritis (AA) model of rheumatoid arthritis (RA). Lymph node cells (LNC) and synovium-infiltrating cells (SIC) of LEW and WKY rat subjected to an arthritogenic challenge were tested. The frequency of T helper 17 (Th17) and T regulatory (Treg) cells was determined by flow cytometry, whereas serum and spleen adherent cell (SAC)-derived supernatant were analyzed for specific cytokines and chemokines. We observed that WKY rats are not deficient in generating a Th17 response to the arthritogenic challenge in LNC (periphery); however, the Th17/Treg ratio is markedly reduced in the joint (target organ) of WKY versus LEW rats because of reduced Th17 levels therein in WKY rats. These results suggest differential and selective decrease in Th17 cell migration into the joints of WKY rats. Interestingly, serum levels of chemokines RANTES and MCP-1 were reduced in WKY rats. Furthermore, WKY rats showed reduced serum IL-1ß level in vivo but no defect in IL-1ß production by SAC in vitro, suggesting an effective in vivo regulation of IL-1ß response. We also unraveled the role of interferon-γ (IFNγ), which we have previously reported to be increased in WKY versus LEW rats, in regulation of IL-1ß. Thus, reduced Th17/Treg ratio in the target organ (joints) and decreased systemic IL-1ß might contribute to the AA-resistance of WKY rats; whereas the converse factors render LEW more vulnerable to AA.

Population structure in relation to host-plant ecology and Wolbachia infestation in the comma butterfly.

Experimental work on Polygonia c-album, a temperate polyphagous butterfly species, has shown that Swedish, Belgian, Norwegian and Estonian females are generalists with respect to host-plant preference, whereas females from UK and Spain are specialized on Urticaceae. Female preference is known to have a strong genetic component. We test whether the specialist and generalist populations form respective genetic clusters using data from mitochondrial sequences and 10 microsatellite loci. Results do not support this hypothesis, suggesting that the specialist and generalist traits have evolved more than once independently. Mitochondrial DNA variation suggests a rapid expansion scenario, with a single widespread haplotype occurring in high frequency, whereas microsatellite data indicate strong differentiation of the Moroccan population. Based on a comparison of polymorphism in the mitochondrial data and sequences from a nuclear gene, we show that the diversity in the former is significantly less than that expected under neutral evolution. Furthermore, we found that almost all butterfly samples were infected with a single strain of Wolbachia, a maternally inherited bacterium. We reason that indirect selection on the mitochondrial genome mediated by a recent sweep of Wolbachia infection has depleted variability in the mitochondrial sequences. We also surmise that P. c-album could have expanded out of a single glacial refugium and colonized Morocco recently.

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

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.

Physical properties, chemical composition, and cloud forming potential of particulate emissions from a marine diesel engine at various load conditions.

Particulate matter (PM) emissions from one serial 4-stroke medium-speed marine diesel engine were measured for load conditions from 10% to 110% in test rig studies using heavy fuel oil (HFO). Testing the engine across its entire load range permitted the scaling of exhaust PM properties with load. Emission factors for particle number, particle mass, and chemical compounds were determined. The potential of particles to form cloud droplets (cloud condensation nuclei, CCN) was calculated from chemical composition and particle size. Number emission factors are (3.43 +/- 1.26) x 10(16) (kg fuel)(-1) at 85-110% load and (1.06 +/- 0.10) x 10(16) (kg fuel)(-1) at 10% load. CCN emission factors of 1-6 x 10(14) (kg fuel)(-1) are at the lower bound of data reported in the literature. From combined thermal and optical methods, black carbon (BC) emission factors of 40-60 mg/(kg fuel) were determined for 85-100% load and 370 mg/(kg fuel) for 10% load. The engine load dependence of the conversion efficiency for fuel sulfur into sulfate of (1.08 +/- 0.15)% at engine idle to (3.85 +/- 0.41)% at cruise may serve as input to global emission calculations for various load conditions.

The influence of small aerosol particles on the properties of water and ice clouds.

In this paper, results are presented of the influence of small organic- and soot-containing particles on the formation of water and ice clouds. There is strong evidence that these particles have grown from nano particle seeds produced by the combustion of oil products. Two series of field experiments are selected to represent the observations made. The first is the CLoud-Aerosol Characterisation Experiment (CLACE) series of experiments performed at a high Alpine site (Jungfraujoch), where cloud was in contact with the ground and the measuring station. Both water and ice clouds were examined at different times of the year. The second series of experiments is the CLOud Processing of regional Air Pollution advecting over land and sea (CLOPAP) series, where ageing pollution aerosol from UK cities was observed, from an airborne platform, to interact with warm stratocumulus cloud in a cloud-capped atmospheric boundary layer. Combining the results it is shown that aged pollution aerosol consists of an internal mixture of organics, sulfate, nitrate and ammonium, the organic component is dominated by highly oxidized secondary material. The relative contributions and absolute loadings of the components vary with location and season. However, these aerosols act as Cloud Condensation Nuclei (CCN) and much of the organic material, along with the other species, is incorporated into cloud droplets. In ice and mixed phase cloud, it is observed that very sharp transitions (extending over just a few metres) are present between highly glaciated regions and regions consisting of supercooled water. This is a unique finding; however, aircraft observations in cumulus suggest that this kind of structure may be found in these cloud types too. It is suggested that this sharp transition is caused by ice nucleation initiated by oxidised organic aerosol coated with sulfate in more polluted regions of cloud, sometimes enhanced by secondary ice particle production in these regions.

Dynamics of host plant use and species diversity in Polygonia butterflies (Nymphalidae).

The ability of insects to utilize different host plants has been suggested to be a dynamic and transient phase. During or after this phase, species can shift to novel host plants or respecialize on ancestral ones. Expanding the range of host plants might also be a factor leading to higher levels of net speciation rates. In this paper, we have studied the possible importance of host plant range for diversification in the genus Polygonia (Nymphalidae, Nymphalini). We have compared species richness between sistergroups in order to find out if there are any differences in number of species between clades including species that utilize only the ancestral host plants ('urticalean rosids') and their sisterclades with a broader (or in some cases potentially broader) host plant repertoire. Four comparisons could be made, and although these are not all phylogenetically or statistically independent, all showed clades including butterfly species using other or additional host plants than the urticalean rosids to be more species-rich than their sisterclade restricted to the ancestral host plants. These results are consistent with the theory that expansions in host plant range are involved in the process of diversification in butterflies and other phytophagous insects, in line with the general theory that plasticity may drive speciation.

Secondary organic aerosols from anthropogenic and biogenic precursors.

Secondary organic aerosol (SOA) formation from the photooxidation of an anthropogenic (1,3,5-trimethylbenzene) and a biogenic (alpha-pinene) precursor was investigated at the new PSI smog chamber. The chemistry of the gas phase was followed by proton transfer reaction mass spectrometry, while the aerosol chemistry was investigated with aerosol mass spectrometry, ion chromatography, laser desorption ionization mass spectrometry, and infrared spectroscopy, along with volatility and hygroscopicity studies. Evidence for oligomer formation for SOA from both precursors was given by an increasing abundance of compounds with a high molecular weight (up to 1000 Da) and by an increasing thermal stability with increasing aging time. The results were compared to data obtained from ambient aerosol samples, revealing a number of similar features.

[A chance finding during the sterilization of a cat: a mummified fetus in the abdominal cavity]. / Zufallsbefund bei der Sterilisation einer Katze: Mumifizierter Fetus in der Bauchhöhle.

While sterilizing a cat, a mummified pup is found in her abdominal cavity. Further examinations suggest that a primary abdominal pregnancy can be excluded, although no perforation or scar of the uterine wall is noticed during operation.

Hygroscopicity of aerosol particles at low temperatures. 1. New low-temperature H-TDMA instrument: setup and first applications.

A hygroscopicity tandem differential mobility analyzer (H-TDMA) is described that allows a fast and accurate determination of the water uptake by submicrometer aerosol particles at temperatures below 0 degrees C. To avoid volatilization of semivolatile particles, the humidification works without heating the gas stream, and the gas-phase composition is not changed during the analysis. The applied scanning mobility analysis allows a fast and accurate measurement of the humidogram, but care has to be taken with too high scanning velocities leading to artifacts in the particle size measurement. During a field campaign at a high-alpine site (Jungfraujoch, 3580 m above sea level), humidograms of free tropospheric particles were measured at T= -10 degrees C. The hygroscopic growth of these particles was characterized by monomodal growth distributions, which means that in the observed size range (dry particle diameters (Do) = 50-250 nm) the free tropospheric aerosol was to a large extent internally mixed. No distinct deliquescence was observed, indicating that the multicomponent aerosol particles are present in a liquid state even at a low relative humidity (RH) <10%. At RH 85%, average hygroscopic growth factors of 1.44, 1.49, and 1.53 were measured for Do = 50, 100, and 250 nm. The estimated soluble volume fraction of the particles in the observed size range was found to be 0.79, 0.86, and 0.91, respectively.

Hygroscopicity of aerosol particles at low temperatures. 2. Theoretical and experimental hygroscopic properties of laboratory generated aerosols.

A Hygroscopicity Tandem Differential Mobility Analyzer (H-TDMA) system has been used to measure hygroscopic growth curves and deliquescence relative humidities (DRH) of laboratory generated (NH4)2SO4, NaCl, and NaNO3 particles at temperatures T= 20 degrees C and -10 degrees C. Good agreement (better than 3.5%) between measured growth curves and Köhler theory was found using empirical temperature and concentration dependent values for water activity, solution density, and surface tension. The measured growth curves only experience a small temperature dependence in the observed temperature range. Therefore, to a first approximation, it is possible to neglect the temperature dependence of the water activity for theoretical calculations in the temperature range -10 degrees C < T < 25 degrees C. The small differences between experiment and theory, which were predominantly observed for NaCl particles, are probably caused by a small amount of water adsorbed on the "dry" crystals. It was also observed that these particles experience a significant restructuring at relative humidity RH < DRH, which was also taken into account for a comparison with theoretical curves. If salt particles are used for instrument calibration, precautions regarding the dry particle diameter have to be taken.

Identification of organic acids in secondary organic aerosol and the corresponding gas phase from chamber experiments.

Organic acids in the gas and aerosol phase from photooxidation of 1,3,5-trimethylbenzene in the presence of 300 ppb propene and 300 ppb NOx in smog chamber experiments were determined using a wet effluent diffusion denuder/aerosol collector coupled to ion chromatography (IC) with conductivity detection. Behind the IC, the samples were collected using a fraction collector, for identification of unresolved/unidentified organic acids with IC-mass spectrometry (MS). In total, 20 organic acids were found with MS of which 10 were identified. The organic acids identified offline by IC-MS were then further quantified based on the online IC data. The identification was additionally confirmed with gas chromatography-mass spectrometry. At the maximum aerosol concentration, organic acids comprised 20-45% of the total aerosol mass. The method has a detection limit of 10-100 ng/m3 for the identified carboxylic acids.

Identification of polymers as major components of atmospheric organic aerosols.

Results from photooxidation of aromatic compounds in a reaction chamber show that a substantial fraction of the organic aerosol mass is composed of polymers. This polymerization results from reactions of carbonyls and their hydrates. After aging for more than 20 hours, about 50% of the particle mass consists of polymers with a molecular mass up to 1000 daltons. This results in a lower volatility of this secondary organic aerosol and a higher aerosol yield than a model using vapor pressures of individual organic species would predict.