Real-time in situ measurements of trace gases from agriculturally cultivated soils by means of laser spectroscopic techniques

摘要

Two devices to study the exchange of climate relevant trace gases between arable cultivated soils and the atmosphere in the North China Plain are presented in this thesis. They are based on Tunable Diode Laser Photoacoustic Spectroscopy (TDL-PAS). These devices are capable of real-time in situ detection of trace gases. For methane a detection limit of 85 ppb and for ammonia of 111 ppb was achieved, respectively. For the field campaign at the experimental field Dongbeiwang (DBW) in Beijing it was necessary to optimize the instruments due to the harsh conditions in China, e.g. high variation in temperature, high humidity and particulate matter emissions. This included accurate thermally stabilization of the system as well as long-term stability of the laser diode and the possibility of unattended operation over a period of several days. These prerequisites were fulfilled and evaluated in Germany before the devices were brought to China for the field campaign in the years 2006 and 2007. Additionally, mobile closed chambers for the trace gas exchange measurements were designed in Germany. They consisted of two parts: One frame installed permanently in the soil, therein agricultural crops could be planted, and a hood placed on it during the measurement and removed afterwards again. Altogether seven frames made from stainless steel were constructed by a company located in Beijing. Three hoods of different heights (250, 500 and 1000 mm) were made from 8 mm colorless Plexiglas and were built by a German company. The innovation of this design was the possibility to insert up to eight cooling packs that cooled down the enclosed air in the chambers by mixing it via two fans. By comparing measurements with and without applying cooling packs it was shown that the temperature difference between both situations was increasing up to 10 K. According to ambient air temperature measurements the test also showed that by applying cooling packs the temperature of the enclosed air could be adapted close to ambient conditions. After installation of the closed chambers in DBW a test checking the gas tightness had to be performed. With this test leakages of the frames, hoods and tubes should be discovered. This was done by injection of 2 ml ethane into the closed chambers and studying the concentration decrease within one hour of closure time. For this test the permanently installed gas chromatograph in the measurement container in DBW was used, connected by Teflon tubes to the closed chambers. All closed chambers showed leakages lower than 10% and therefore could be considered as tight.For methane measurements the chambers were operated in the dynamic mode, so the air inside of the chamber was circulated through the TDL-PA system and pumped back into the chamber. The increase or decrease in methane concentration with time was determined and flux rates were calculated. The obtained data confirmed that the soil in DBW, a Calcaric Cambisol according to FAO classification, could be considered as a methane sink. The exchange rate ranged from ?0.17 to ?3.33 mg CH4-C m-² d-¹ for winter wheat and from ?0.68 to ?2.07 mg CH4-C m-²; d-¹ for bare soil. For summer maize the exchange rate was slightly lower and ranged from ?0.51 to ?1.0 mg CH4-C m-² d-¹ and from ?0.53 to ?1.14 mg CH4-C m-² d-¹ for the control plot.Due to the fact that elevated methane concentrations at daybreak were detected during the exchange measurements at the plots planted with winter wheat as well as at the control plot a diurnal variation in methane concentration was assumed. To verify and quantify this diurnal variation in methane concentration at DBW, one plot was selected for a 24 hour measurement campaign. During this measurement campaign ambient air methane concentrations of up to 22 ppm were observed during nighttime, which was elevenfold the normal concentration. Because the previous exchange measurements revealed that methane was not emitted by the soil it must originated from somewhere else. After the 24 hour measurement campaign the ambient air methane concentrations in DBW as well as at other places in the vicinity of DBW were studied to detect the source of the methane emissions. For that purpose an ultrasonic anemometer for wind direction and wind speed measurement was combined with the TDL-PA system. A diurnal variation with maximum methane concentrations of about 40 ppm during nighttime and early morning and minimum concentrations of about 1.4 ppm during the afternoon were detected in DBW. Research conducted at the campus of the CAU, 3.2 km south of DBW, showed a similar pattern. These results confirmed the urban heat island effect where stable atmospheric layering dominates during the night and a mixing layer dominates during daytime. According to literature the height of this atmospheric boundary layer in Beijing in autumn was of 1 km thickness during daytime and of 200 ? 400 m during nighttime. Moreover the high methane concentrations in the night verified the assumption of a methane emission source in the vicinity of DBW and the CAU. The search for a potential emission source revealed a landfill approximately 6 km north-west of the CAU as well as 5.5 km west of DBW. Measurements conducted at the landfill site itself showed a diurnal methane emission pattern as well, with maximum concentrations up to 450 ppm during nighttime and minimum concentrations of about 10 ppm during daytime.