We describe a fully computer-controlled differential optical absorption spectroscopy system for atmospheric air pollution monitoring. A receiving optical telescope can sequentially tune in to light beams from a number of distant high-pressure Xe lamp light sources to cover the area of a medium-sized city. A beam-finding servosystem and automatic gain control permit unattended long-time monitoring. Using an astronomical code, we can also search and track celestial sources. Selected wavelength regions are rapidly and repetitively swept by a monochromator to sensitively record the atmospheric absorption spectrum while avoiding the detrimental effects of atmospheric turbulence. By computer fitting to stored laboratory spectra, we can evaluate the path-averaged concentration of a number of important pollutants such as NO 2 , SO 2 , and 03. A measurement of NH 3 and NO close to the UV limit is also demonstrated.

The total flux of sulfur dioxide from the Italian volcanoes Etna, Stromboli, and Vulcano was determined using the differential absorption lidar technique. The measurements were performed from an oceanographic research ship making traverses under the volcanic plumes with the lidar system sounding vertically. By combining the integrated gas concentration over the plume cross section with wind velocity data, it was possible to determine the total fluxes of SO2 from the three volcanoes, all measured within a 3‐day period in September 1992. We found total fluxes of about 25, 180, and 1300 t/d for Vulcano, Stromboli, and Etna, respectively. These data, collected with an active remote‐sensing technique, were compared with simultaneous recording with passive differential optical absorption spectroscopy (DOAS) using the sky radiation as the light source. Since the geometry of the light paths crossing the volcanic plume is not well defined in the passive measurements, a correction to the DOAS data is required. The SO2 results are also compared with previously available data from correlation spectroscopy measurements. Lidar measurements on atomic mercury were also made for the plumes from Stromboli and Vulcano, but the system sensitivity and range only allowed estimates of upper limits for the Hg fluxes.

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SUMMARYThe LIDAR technique is an efficient tool in monitoring the distribution of atmospheric species of importance. We study the concentration of atmospheric atomic mercury in an Italian geothermal field and discuss the possibility of using recent results from local polynomial kernel regression theory for the evaluation ofthe derivative of the DIAL curve. A MISE-optimal bandwidth selector, which takes account of the heteroscedasticity in the regression is suggested. Further, we estimate the integrated amount of mercury in a certain area.K E Y woms locally weighted least squares regression; LIDAR measurements; air pollution; atmospheric atomic mercury; geothermal field

Abstract. Knowledge of the natural emissions of mercury in the Mediterranean basin, which has large cinnabar anomalies, has particular weight as these deposits could be an important source of atmospheric mercury. Data on the degassing rate of mercury from soils sampled both in mineralized areas (Mt. Amiata, Italy and Almaden, Spain) and rural areas are reported. Measurements were carried out "in situ' using a transparent flux chamber and collecting the gaseous mercury on gold collectors. The highest values were observed in Almaden over the roasted cinnabar banks (up to 100 l,g/m'~h) fiom past and present mining activity. In Italian rural areas the values of the volatilization rate of mercury are on the order of few ng/m2h. The degassing rate was observed to be strongly dependent on the ambient temperature and not only seasonal but also daily variations were measured in all the studied areas.

The differential absorption structure of the ozone spectrum between 250 and 330 nm has been investigated in order to determine the optimal wavelength region to be utilized for active differential optical absorption spectroscopy (DOAS) measurements. Considering aspects of atmospheric attenuation and interference from other species as well as the magnitude of the differential absorption cross section, an interval around 283 nm was found to be a good candidate for this application. This result was also verified during 12 months of continuous ozone monitoring in an urban environment.

Long-path DOAS (differential optical absorption spectroscopy) in the ultraviolet spectral region has been shown to be applicable for lowconcentration measurements of light aromatic hydrocarbons. However, because of spectral interferences among different aromatics as well as with oxygen, ozone, and sulfur dioxide, the application of the DOAS technique for this group of components is not without problems. This project includes a study of the differential absorption characteristics, between 250 and 280 nm, of twelve light aromatic hydrocarbons representing major constituents in technical solvents used in the automobile industry. Spectral overlapping between the different species, including oxygen, ozone, and sulfur dioxide, has been investigated and related to the chemical structure of the different aromatics. Interference effects in the DOAS application due to spectral overlapping have been investigated both in quantitative and in qualitative terms, with data from a field campaign at a major automobile manufacturing plant,

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