W. Jaeschke

The Kleiner Feldberg Cloud Experiment 1990. An overview

An overview is given of the Kleiner Feldberg cloud experiment performed from 27 October until 13 November 1990. The experiment was carried out by numerous European research groups as a joint effort within the EUROTRAC-GCE project in order to study the interaction of cloud droplets with atmospheric trace constituents. After a description of the observational site and the measurements which were performed, the general cloud formation mechanisms encountered during the experiment are discussed. Special attention is given here to the process of moist adiabatic lifting. Furthermore, an overview is given regarding the pollutant levels in the gas phase, the particulate and the liquid phase, and some major findings are presented with respect to the experimental objectives. Finally, a first comparison attempts to put the results obtained during this campaign into perspective with the previous GCE field campaign in the Po Valley.

The Detection of Low Atmospheric SO2 Concentrations with a Chemiluminescence Technique

Abstract A chemiluminescence effect was found during oxidation of disulfitomercurate complex in aqueous solutions with KMnO4 under acid conditions. By employing a filter technique for air sampling the chemiluminescence method is applied to the detection of atmospheric sulfur dioxide. The quality of the complete procedure is demonstrated by comparative calibrations from the liquid and gas phase and comparative measurements with several other SO2 sensitive methods. The detection limit is shown to be (10±1) pptv SO2. Some measurements of atmospheric SO2 background concentrations are shown in order to demonstrate the potential of the whole procedure in its application to atmospheric SO2 measurements.

Cloud processing of soluble gases

Abstract Experimental data from the Great Dun Fell Cloud Experiment 1993 were used to investigate interactions between soluble gases and cloud droplets. Concentrations of H 2 O 2 , SO 2 , CH 3 COOOH, HCOOH, and HCHO were monitored at different sites within and downwind of a hill cap cloud and their temporal and spatial evolution during several cloud events was investigated. Significant differences were found between in-cloud and out-of-cloud concentrations, most of which could not be explained by simple dissolution into cloud droplets. Concentration patterns were analysed in relation to the chemistry of cloud droplets and the gas/liquid equilibrium. Soluble gases do not undergo similar behaviour: CH 3 COOH simply dissolves in the aqueous phase and is outgassed upon cloud dissipation; instead, SO 2 is consumed by its reaction with H 2 O 2 . The behaviour of HCOOH is more complex because there is evidence for in-cloud chemical production. The formation of HCOOH interferes with the odd hydrogen cycle by enhancing the liquid-phase production of H 2 O 2 . The H 2 O 2 concentration in cloud therefore results from the balance of consumption by oxidation of SO 2 in-cloud production, and the rate by which it is supplied to the system by entrainment of new air into the clouds.

The size-dependent chemical composition of cloud droplets

Abstract Size-dependent cloud droplet solute concentrations were measured using a two-stage fog water impactor at the summit station of Great Dun Fell (GDF) in the north of England. The measurements showed mostly higher concentrations in the small-droplet fraction. During one cloud event, however, higher solute concentrations were found in the larger-droplet fraction. In order to identify the factors governing the size dependence of cloud droplet solute concentrations, sensitivity studies by means of a diffusional growth model were performed. The time available for the droplets to grow was identified to be of great importance for the size dependence of solute concentrations. In cases when higher solute concentrations were found in the fraction containing the bigger droplets, the cloud droplets were relatively young having been formed by orographic lifting of the air at the GDF summit. For the other events the evidence indicates that the cloud was already formed far upwind from the summit site. Our experimental and model results imply that, after an initially strong decrease of solute concentrations with droplet size we would observe: • ⊎|increasing solute concentrations with increasing diameters during the initial stage of a cloud, e.g. near cloud base where the droplets have just been formed. The primary factors contributing to this behaviour are high peak supersaturations, large numbers of coarse aerosol particles, and high solubility of the aerosol particles. • ⊎|decreasing solute concentrations with increasing diameters in aged cloud parcels, such as those which can be observed high above the cloud base in cumuliform clouds or are advected to the observation point in the case of stratiform clouds. The primary factors contributing to this behaviour are low peak supersaturations, low numbers of coarse particles, and low solubility of the aerosol particles.

Measurements of H2S and SO2 over the Atlantic Ocean

Concentrations of sulfur gases H2S and SO2 have been measured in the marine atmosphere over the Atlantic Ocean at various sites. Mean values of 40 ng H2S m-3 STP and 209 ng SO2 m-3 STP are the results of the measurements. A diurnal variation of H2S concentration was detected on the west coast of Ireland with nighttime concentrations of up to 200 ng H2S m-3 STP and values below detection limit (15 ng H2S m-3 STP) during daytime.

NEW METHODS FOR THE ANALYSIS OF SO2 AND H2S IN REMOTE AREAS AND THEIR APPLICATION TO THE ATMOSPHERE

Abstract New techniques have been developed and examined for measuring H 2 S and SO 2 in the atmosphere. The calibration curves of the methods are reported and the detection limits are discussed by considering the deviation of the blank values. The atmospheric detection limits are demonstrated to be 0.01 μg H 2 S m −3 and 0.03μg SO 2 m −3 . Results of test measurements dealing with the reproducibility of the measured values and the sampling efficiency are reported. A short summary of some results which have been obtained by applying the methods to the atmosphere is given.

Contributions of H2S to the atmospheric sulfur cycle

H2S is a most important biogenic sulfur compound with regard to the atmospheric sulfur cycle. Our present knowledge of the spatial and temporal distribution of this trace gas is rather incomplete owing to unreliable analytical methods. Therefore, a new method for the analysis of H2S in the μg-range was applied. This paper deals with the results of ground- and aircraft measurements of H2S in unpolluted air over swamps and tidal flats. Based on the measured vertical distributions a removal coefficient of 2.3×10−5 sec−1 and an average lifetime of 12 hours were calculated. Some conclusions of the contribution of H2S to the atmospheric sulfur budget are added.

Ground-Based and Airborne Measurements of Nonmethane Hydrocarbons in BERLIOZ: Analysis and Selected Results

During the Berlin Ozone Experiment BERLIOZ in July–August 1998 quasi-continuous measurements ofC2–C12 nonmethane hydrocarbons (NMHCs) were carried out at 10 sites in and around the city of Berlin using on-line gas-chromatographic systems (GCs) with a temporal resolution of 20–120 minutes. Additional airborne NMHCmeasurements were made using canister sampling on three aircraft and an on-line GC system on a fourth aircraft. The ground based data are analyzed to characterize the different sites and to identify the influence of emissions from Berlin on its surroundings. Benzene mixing ratios at the 4 rural sites were rather low (<0.5 ppbv). Berlin (and the surrounding highway ring) was identified as the main source of anthropogenic NMHCs at Eichstädt and Blossin, whilst other sources were important at the furthermost site Menz. The median toluene/benzene concentration ratio in Berlin was 2.3 ppbv/ppbv, agreeing well with measurements in other German cities. As expected, the ratios at the background sites decreased with increasing distance to Berlin and were usually around one or below. On 20 and 21 July, the three northwesterly sites were situated downwind of Berlin and thus were influenced by its emissions. Considering the distance between the sites and the windspeed, the city plume was observed at reasonable time scales, showing decreasing toluene/benzene ratios of 2.3, 1.6 and 1.3 with increasing distance from Berlin. Isoprene was the only biogenic NMHC measured at BERLIOZ. It was themost abundant compound at the background sites on the hotter days, dominating the local NMHC reactivity with averaged contributions to the total OH loss rate of 51% and 70% at Pabstthum and Blossin, respectively. Emissionratios (relative to CO and to the sum of analysed NMHCs) were derived from airborne measurements. The comparison with an emission inventory suggests traffic-related emissions to be the predominating source of the considered hydrocarbon species. Problems were identified with the emission inventory for propane, ethene and pentanes.

Variations of uptake rates in benzene diffusive sampling as a function of ambient conditions

Abstract Diffusive samplers have found widespread use as a cost-effective technique in measuring ambient benzene concentrations. In a long-term field study the applicability of thermal desorbable Perkin Elmer (PE) diffusive samplers with Serdolit® AD-4 sorbent was tested for weekly integrated benzene measurements. Measuring was carried out under highly differing pollution levels and meteorological conditions. The mean uncertainty range for the benzene concentration interval of 0–18 μg/m 3 was calculated as 0.3 μg/m 3 . The coefficient of variation was 13%. Including the uncertainty of both the active and the passive technique, it can be interpreted as an upper limit. The detection limit was determined as 0.3 μg/m 3 , providing a technique for monitoring benzene concentrations under rural conditions. The mean experimentally determined uptake rate was 0.34±0.04 cm 3 /min for shielded sampling in a protective chamber (Sigma-2). The uptake rate had no relationship with air humidity and benzene level. In contrast, a correlation with air temperature was detected. On a weekly basis the seasonal effect of an annual temperature cycle amounted to ±10% in benzene concentration. A corresponding temperature correction by employing weekly averages reduced the deviation of weekly passive values from active measurement. No influence of ambient air velocity on the uptake rate was found up to a weekly average of 3.5 m/s if an appropriate wind shielding was employed. This was achieved by the original PE-end cap as well as by the Sigma-2 device.

Study of metal aerosol systems as a sink for atmospheric SO2

The chemical removal of SO2 in the presence of different aerosol systems has been investigated in laboratory experiments using a dynamic flow reactor. The aerosols consisted of wetted particles containing one of the following substances: MnCl2, Mn(NO3)2, MnSO4, CuCl2, Cu(NO3)2, CuSO4, FeCl3, NaCl. The SO2 removal rate R was measured as a function of the SO2 gas phase concentration (SO2)g, the spatial metal concentration CMe, and the relative humidity rH in the reactor. A first-order dependence with regard to (SO2)g was observed for each type of aerosol. For the Mn(II) and Cu(II) aerosols R was found to be a non-linear function of CMe except for MnSO4 and Cu(NO3)2 particles. The removal rate showed a significant increase with the relative humidity particularly when rH was close to the deliquescence point of the wetted particles. Among the Mn(II) and Cu(II) aerosols investigated Mn(NO3)2 was found to be most efficient for the chemical removal of SO2 at atmospheric background conditions, especially in haze and fog droplets. The results further indicate that the catalytic oxidation of S(IV) in such aerosol systems may be as efficient as its oxidation by H2O2 in cloud water.