Carbon dioxide and methane observations from the continental mountain station Kasprowy Wierch in the Tatra Mountains, southern Poland, are presented. They cover a six‐year period from 1994 to 2000. Significant year‐to‐year variability of CO2 concentration was observed. The seasonal cycles 1996–1997 were similar, with a peak‐to‐peak amplitude of the selected and smoothed CO2 record of approximately 20 ppm and no significant increase of the annual mean values. For 1998 and 1999 large increases of the annual mean values by 3.3 and 4.0 ppm per year, respectively, were observed. This increase was accompanied by a reduction of the seasonal amplitude of the smoothed record to approximately 15 ppm in 1998 and 16 ppm in 1999. In 2000 the seasonal amplitude increased again to a value similar as in 1996/1997, whereas the mean annual value remained close to that recorded for 1999. Similar features can also be traced in the selected and smoothed CO2 record for Schauinsland station, Germany, located ca. 1000 km west of Kasprowy Wierch. These similarities strongly suggest that both stations are capturing the same large‐scale European phenomena, most probably related to a disturbance of the CO2 cycle by the recent El Niño event. The mean CH4 mixing ratio at Kasprowy Wierch for the period 1996–1999 was about 30 ppb higher than over the Atlantic Ocean, confirming previous observations that the European continent is a net source of methane throughout the year. No significant seasonal cycle of methane has been observed at Kasprowy Wierch. The short‐term changes of CO2 and CH4 are strongly correlated during winter months: the average monthly mean slope of the linear relationship between CH4 and CO2 was 10.7 ± 0.3 ppbCH4 per ppmCO2. During summer months this strong correlation breaks down. Diurnal changes of CO2 and CH4 mixing ratios observed at Kasprowy Wierch are typical for continental mountain sites, with a distinct minimum of CO2 during afternoon hours in summer and maximum during winter. For CH4, diurnal cycles have similar shape throughout the year, with a broad maximum during daytime. The mean peak‐to‐peak amplitudes for summer (July) were 4.5 ppm for CO2 and 30 ppb for CH4, whereas during winter (February) they diminished to 1.5 ppm and 10 ppb, respectively.
Carbon dioxide and methane observations from the continental mountain station Kasprowy Wierch in the Tatra Mountains, southern Poland, are presented. They cover a six-year period from 1994 to 2000. Significant year-to-year variability of CO 2 concentration was observed. The seasonal cycles 1996-1997 were similar, with a peak-to-peak amplitude of the selected and smoothed CO 2 record of approximately 20 ppm and no significant increase of the annual mean values. For 1998 and 1999 large increases of the annual mean values by 3.3 and 4.0 ppm per year, respectively, were observed. This increase was accompanied by a reduction of the seasonal amplitude of the smoothed record to approximately 15 ppm in 1998 and 16 ppm in 1999. In 2000 the seasonal amplitude increased again to a value similar as in 1996/1997, whereas the mean annual value remained close to that recorded for 1999. Similar features can also be traced in the selected and smoothed CO 2 record for Schauinsland station, Germany, located ca. 1000 km west of Kasprowy Wierch. These similarities strongly suggest that both stations are capturing the same large-scale European phenomena, most probably related to a disturbance of the CO 2 cycle by the recent El Niño event. The mean CH 4 mixing ratio at Kasprowy Wierch for the period 1996-1999 was about 30 ppb higher than over the Atlantic Ocean, confirming previous observations that the European continent is a net source of methane throughout the year. No significant seasonal cycle of methane has been observed at Kasprowy Wierch. The short-term changes of CO 2 and CH 4 are strongly correlated during winter months: the average monthly mean slope of the linear relationship between CH 4 and CO 2 was 10.7 ± 0.3 ppbCH 4 per ppmCO 2 . During summer months this strong correlation breaks down. Diurnal changes of CO 2 and CH 4 mixing ratios observed at Kasprowy Wierch are typical for continental mountain sites, with a distinct minimum of CO 2 during afternoon hours in summer and maximum during winter. For CH 4 , diurnal cycles have similar shape throughout the year, with a broad maximum during daytime. The mean peak-to-peak amplitudes for summer (July) were 4.5 ppm for CO 2 and 30 ppb for CH 4 , whereas during winter (February) they diminished to 1.5 ppm and 10 ppb, respectively.
A simplified model of the ECD is presented, which is based on the assumption that only a change in the concentration of electron is generating a signal. The model allows to determine four different time constants related to: the collection of electrons (tau(1)), the loss of electrons in the capture process by the impurity molecules (tau(2)), the loss of sample molecules by electron capture (tau(n)) and the removing rate of molecules from the detector volume by the carrier gas (tau(v)). The values of these time constants have been estimated to be in the range of micros for tau(1), ms for tau(2), a part of a second for tau(n) and a few seconds for tau(v). The electron capture efficiency coefficient (p) and the detection coefficient (S(d)) have been defined. These coefficients serve in the model for the coulometric calculation of the mass of analyzed compounds, if the detector works using the conditions described.
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