Development of the Jungfraujoch UV DIAL Lidar to Observe the Vertical Ozone Distribution in the Context of Stratosphere Troposphere Exchange and Long Range Transport

Tropospheric ozone is a climate relevant greenhouse gas, as well as an atmospheric pollutant. Its abundance in the troposphere is mainly governed by the influx of stratospheric air masses and the photochemical production due to anthropogenic and biogenic ozone precursors. Precise model simulations and measurements are needed to assess the exact impact of these sources onto the total tropospheric ozone content. In the latter case, vertical tropospheric ozone profiles are commonly obtained from in-situ balloon-borne soundings. These routine observations are performed with a maximum frequency of several measurements per week. Therefore, they are not suited to resolve the rather fast changes in the tropospheric ozone concentration. However, accurate vertical ozone profiles with temporal and spatial resolutions suitable for studying those changes have been produced for decades using remote sensing by means of the ozone UV differential absorption lidar (DIAL) technique. The main goals of this thesis aimed to address some of the unresolved problems of the ozone origin and evolution in the upper troposphere and lower stratosphere and were: to develop an UV DIAL for the observation of the vertical ozone distribution in the free troposphere and at the tropopause region. to perform experimental measurements of vertical ozone profiles in the free troposphere and the tropopause in order to assess the ability of the ozone UV DIAL to observe fast variations in vertical ozone distribution caused by stratosphere-troposphere exchange (STE), long range transport, and advection from the boundary layer. to assess the feasibility of systematic ozone profile retrieval by the ozone UV DIAL technique from the High Altitude Research Station Jungfraujoch (HARSJ, 3580 m ASL, 7°59'2''E, 46°32'53''N). The HARSJ was chosen for the experiment because of its location, which allows ozone UV DIAL measurements of the tropopause region without perturbation of the lower troposphere. Furthermore, previous atmospheric studies have shown that because of the station's location, the upper tropospheric data taken at the HARSJ can be regarded as representative for central and western Europe. During the first two and a half years of the thesis project the ozone UV DIAL was designed and built. The ozone UV DIAL transmitter is based on a commercial, fourth harmonic Nd:YAG laser. The on- (284 nm) and off- (304 nm) ozone UV DIAL wavelengths are produced by stimulated Raman scattering in high-pressure nitrogen. The receiver uses the existing astronomical Cassegrain telescope (76 cm in diameter) at the HARSJ. Spectral separation of the backscattered ozone UV DIAL wavelengths is carried out by a polychromator based on an concave imaging diffraction grating. The entire ozone UV DIAL detection unit is integrated into the existing long-range multi-wavelength polychromator box optically coupled at the Cassegrain telescope's rear end. With the current design, the ozone UV DIAL system provides hourly averaged ozone profiles reaching from 6 km to 12 km ASL with a vertical resolution better than 400 m at 6 km ASL and 1000 m at 12 km ASL. The relative statistical error of the profiles is 10% at 12 km ASL. The experimental measurements started in the spring of 2008 but were interrupted several times because of serious laser failures. As a first step of the experiment, the ozone UV DIAL profiles were compared to balloon borne ozone profiles taken by electrochemical concentration cell (ECC) sondes. The sondes were launched by the Swiss Meteorological Institute – Payerne (SMI, 46°49'N, 6°56'E, 491 m ASL) situated 80 km in northwestern direction of the HARSJ. The ozone UV DIAL and the sonde measurements were taken quasi simultaneously. The relative differences between the ozone UV DIAL and the sonde profiles were found to be below ±25% in a horizontally homogeneous atmosphere. The intercomparison has shown that the ozone UV DIAL is capable to accurately reproduce the vertical ozone distribution. Intercomparison with vertical ozone profiles taken in the vicinity of the HARSJ by an airplane-borne UV-photometer confirmed the performance of the ozone UV DIAL. Time series with duration of up to 21 hours were taken in order to study the time evolution of tropospheric events characterized by elevated ozone concentrations. As a result of these measurements three events, demonstrating different processes have been identified. In the first case an air layer with elevated ozone concentration was observed in the altitude range between 6 and 7 km ASL. The lower than 10% relative humidity and the time evolution of this layer allowed to determine its stratospheric origin. The observations are in a good agreement with the EURopean Air Pollution Dispersion (EURAD) model. The model predictions also agree with the elevated ozone concentration measured by the UV-photometer of the National Air Pollution Monitoring Network (NABEL) operated at the HARSJ. The evolution of an ozone-enriched layer in the tropopause region was followed for 21 hours during the second case study. The time evolution, the ECC data, and the EURAD model predictions suggest the possibility of a short filamentation process developing at the tropopause region. The measurements of the third event were made according to a prediction of STE forecasted by a dynamical model developed at the ETHZ. A short living enhancement of the ozone concentration has been observed at an altitude of about 9.5 km ASL. There are two possible explanations for this event. The first one could be a short living reversible STE event. A second explanation is a possible long-range transport of ozone and ozone precursor rich air from the forest fires in the Athens region suggested by the Hybrid Single Particle Lagrangian Integrated Trajectory Model (HYSPLIT) backward trajectories. However, the available information does not allow to make a definite conclusion. The ozone UV DIAL has been built successfully and has shown its ability to observe fast variation in vertical ozone distribution with high accuracy and precision. In combination with additional water vapor and temperature lidar observations and supported by model forecasting, this system could become a powerful tool for the improving of the understanding of upper troposphere and lower stratosphere ozone related processes. However, to allow future systematic observations the ozone UV DIAL will need an essential upgrade to resolve the problems related to the long preparation time, and the limited by technical reasons time of observation.

Estimation of the total VOC reactivity with OH by pump-and-probe OH lidar to determine a new indicator for ozone production

Many of our most severe problems of environmental pollution involve the Earth's atmosphere. The adverse effects of atmospheric pollution are particularly evident in the low troposphere, especially in urban/suburban areas where many sources contribute to the atmospheric burden. Ozone (O3) is one of the major constituents of the air pollution over cities commonly called photochemical smog. It is a secondary pollutant, produced by the reaction of primary pollutants, nitrogen oxides (NOx) and hydrocarbons (VOC), in the presence of sunlight. Although hydrocarbons and NOx have long been identified as the two key precursors to photochemical O3, the development of an effective strategy for reducing ozone production in photochemical smog by controlling the anthropogenic emissions of these precursors has proved to be problematic. The objective of the present study is to present and demonstrate the robustness of a new observable "indicator" for determining the sensitivity of ozone formation to VOC and NOx (VOC- and NOx-limited regime). This indicator is based on the reactivity of VOC and NOx with respect to OH. Simulation tests of the ability of this new indicator Θ = τOHVOC/τOHNOx to distinguish between a NOx and a VOC-limited regime were performed with a box model and a 3D model applied to a specific episode of photochemical smog (Athens) and of a less polluted area (the Swiss plateau). Whereas the NOx reactivity 1/τOHNOx can easily be measured by standard methods, the total VOC reactivity 1/τOHVOC will be estimated by measuring the inverse lifetime of OH with a new Pump-and-Probe Lidar instrument. The method consists of producing high OH concentrations by the flash photolysis of ozone and the subsequent O(1D) reaction with H2O and by following the OH relaxation by laser-induced fluorescence (LIF). Numerical simulation of the experiment will show that the total VOC reactivity with OH can be obtained by measuring the inverse lifetime of the OH and its absolute initial concentration with the Pump-and-Probe experiment as well as the NOx, CO and O3 concentrations with standard trace-gas detectors. This total in-situ VOC reactivity will be used to determine the new indicator Θ but will also help to test the accuracy of the VOC-lumped chemical mechanism in the numerical atmospheric simulation. In order to demonstrate the feasibility of the Pump-and-Probe experiment, laboratory investigations have been performed in controlled atmosphere: OH absorption and fluorescence emission spectra allowed the OH transition bands and the non-resonant fluorescence wavelength to be identified. High-resolution OH absorption spectra allowed the OH effective absorption cross section to be determined for assessing the experimental sensitivity and retrieving the OH concentration. The experimental retrieval of the rate constant for the OH+CH4 and OH+NO2 reactions reveals the ability of the pump-and-probe experiment to monitor the chemical kinetics of OH at atmospheric pressure and room temperature. OH relaxation measured in different VOC/NOx/O3 gas mixtures confirm the relevance of the model predictions of the OH relaxation approximated by a first-order chemical decay and the validity of the total VOC reactivity with respect to OH estimated by such an approximation. A first in-situ OH relaxation measurement realized directly in the air of the laboratory showed that the pump-and-probe method could be performed under typical PBL conditions. Preliminary range-resolved measurements yielding vertical profiles of the OH concentrations produced by flash photolysis of ambient ozone suggest a promising future for the Lidar pump-and-probe technique. The perspectives for the Pump-and-Probe Lidar experiment are expressed in the concluding section.

EPFL2000

Ozone and water-vapor measurements by Raman lidar in the planetary boundary layer: Error sources and field measurements

Bertrand Calpini, Gilles Larchevêque, Valentin Mitev, Valentin Simeonov, Hubert van den Bergh

A new lidar instrument was developed to measure tropospheric ozone and water vapor at low altitude. The lidar uses Raman scattering of an UV beam from atm. nitrogen, oxygen, and water vapor to retrieve ozone and water-vapor vertical profiles. By numerical simulation the authors study the sensitivity of the method to both atm. and device perturbations. The aerosol optical effect in the planetary boundary layer, ozone interference in water-vapor retrieval, statistical error, optical cross talk between Raman-shifted channels, and optical cross talk between an elastically backscattered signal in Raman-shifted signals and an after pulse effect are studied. In support of the main conclusions of this model study, time series of ozone and water vapor obtained at the Swiss Federal Institute of Technol. in Lausanne and during a field campaign in Crete are presented. They are compared with point monitor and balloon sounding measurements for daytime and nighttime conditions.

2001

Une première mesure lidar combinée d'ozone et de vent, à partir d'une instrumentation et d'une méthodologie coup par coup

During these last decades, air pollution has drawn the attention of scientists because of the deterioration of the human environment that it has caused. Unfortunately, the study of this dynamic phenomenon is very complex and requires the use of models that compute the evolution of the physico-chemical parameters of the atmosphere. Moreover, the predictions of the numerical simulations have to be validated by range- and time-resolved measurements, carried out continuously up to the top of the planetary boundary layer. Only the optical radar or lidar satisfies these specifications: for this reason the Laboratory for Air and Soil Pollution (LPAS) of the Swiss Federal Institute of Technology (EPFL) has developed such a system in order to provide the modellers with information complementary to that given by the ground measurements. This instrument, after mounting on a mobile platform, has determined the concentration of the key molecule ozone during several field campaigns, demonstrating its reliability and precision. Moreover, the EPFL system is a shot per shot lidar, able to record each detected signal and not only its average in a time interval. This feature is innovative to lidar determinations of tropospheric ozone and allows one to measure accurately the statistical error, to correct for the effect of systematic biases and to observe the dynamic behaviour of the atmosphere: the measurement of the statistical error has been used to build a model of the signal and of its noise, useful in the design of future lidar systems and for the comparison of the various data processing algorithms. the correction of the bias caused by the artificial deformation of the statistical distribution of the signal at long distance has led to a considerable increase of the range of the retrieved ozone profiles, the observation of the dynamic behaviour of the atmosphere has resulted in the first simultaneous measurement of a pollutant concentration and of the wind velocity with the same data set recorded by a lidar.

EPFL1996

Estimation of the total VOC reactivity with OH by pump-and-probe OH lidar to determine a new indicator for ozone production

EPFL2000

Une première mesure lidar combinée d'ozone et de vent, à partir d'une instrumentation et d'une méthodologie coup par coup

EPFL1996