Comparisons of continuous atmospheric CH4, CO2 and N2O measurements - results from a travelling instrument campaign at Mace Head

A 2-month measurement campaign with a Fourier transform infrared analyser as a travelling comparison instrument (TCI) was performed at the Advanced Global Atmospheric Gases Experiment (AGAGE) and World Meteorological Organization (WMO) Global Atmosphere Watch (GAW) station at Mace Head, Ireland. The aim was to evaluate the compatibility of atmospheric methane (CH4), carbon dioxide (CO2) and nitrous oxide (N2O) measurements of the routine station instrumentation, consisting of a gas chromatograph (GC) for CH4 and N2O as well as a cavity ring-down spectroscopy (CRDS) system for CH4 and CO2. The advantage of a TCI approach for quality control is that the comparison covers the entire ambient air measurement system, including the sample intake system and the data evaluation process. For initial quality and performance control, the TCI was run in parallel with the Heidelberg GC before and after the measurement campaign at Mace Head. Median differences between the Heidelberg GC and the TCI were well within the WMO inter-laboratory compatibility target for all three greenhouse gases. At Mace Head, the median difference between the station GC and the TCI were −0.04 nmol mol−1 for CH4 and −0.37 nmol mol−1 for N2O (GC-TCI). For N2O, a similar difference (−0.40 nmol mol−1) was found when measuring surveillance or working gas cylinders with both instruments. This suggests that the difference observed in ambient air originates from a calibration offset that could partly be due to a difference between the WMO N2O X2006a reference scale used for the TCI and the Scripps Institution of Oceanography (SIO-1998) scale used at Mace Head and in the whole AGAGE network. Median differences between the CRDS G1301 and the TCI at Mace Head were 0.12 nmol mol−1 for CH4 and 0.14 μmol mol−1 for CO2 (CRDS G1301 – TCI). The difference between both instruments for CO2 could not be explained, as direct measurements of calibration gases show no such difference. The CH4 differences between the TCI, the GC and the CRDS G1301 at Mace Head are much smaller than the WMO inter-laboratory compatibility target, while this is not the case for CO2 and N2O

Comparisons of continuous atmospheric CH4, CO2 and N2O measurements – results from a travelling instrument campaign at Mace Head

A 2-month measurement campaign with a Fourier transform infrared analyser as a travelling comparison instrument (TCI) was performed at the Advanced Global Atmospheric Gases Experiment (AGAGE) and World Meteorological Organization (WMO) Global Atmosphere Watch (GAW) station at Mace Head, Ireland. The aim was to evaluate the compatibility of atmospheric methane (CH4), carbon dioxide (CO2) and nitrous oxide (N2O) measurements of the routine station instrumentation, consisting of a gas chromatograph (GC) for CH4 and N2O as well as a cavity ring-down spectroscopy (CRDS) system for CH4 and CO2. The advantage of a TCI approach for quality control is that the comparison covers the entire ambient air measurement system, including the sample intake system and the data evaluation process. For initial quality and performance control, the TCI was run in parallel with the Heidelberg GC before and after the measurement campaign at Mace Head. Median differences between the Heidelberg GC and the TCI were well within the WMO inter-laboratory compatibility target for all three greenhouse gases. At Mace Head, the median difference between the station GC and the TCI were -0.04 nmol mol(-1) for CH4 and -0.37 nmol mol(-1) for N2O (GC-TCI). For N2O, a similar difference (-0.40 nmol mol(-1)) was found when measuring surveillance or working gas cylinders with both instruments. This suggests that the difference observed in ambient air originates from a calibration offset that could partly be due to a difference between the WMO N2O X2006a reference scale used for the TCI and the Scripps Institution of Oceanography (SIO-1998) scale used at Mace Head and in the whole AGAGE network. Median differences between the CRDS G1301 and the TCI at Mace Head were 0.12 nmol mol(-1) for CH4 and 0.14 mu mol mol(-1) for CO2 (CRDS G1301 - TCI). The difference between both instruments for CO2 could not be explained, as direct measurements of calibration gases show no such difference. The CH4 differences between the TCI, the GC and the CRDS G1301 at Mace Head are much smaller than the WMO inter-laboratory compatibility target, while this is not the case for CO2 and N2O

High-precision quasi-continuous atmospheric greenhouse gas measurements at Trainou tower (Orléans forest, France)

International audienceResults from the Trainou tall tower measurement station installed in 2006 are presented for atmospheric measurements of CO 2 , CH 4 , N 2 O, SF 6 , CO, H 2 mole fractions and radon-222 activity. Air is sampled from four sampling heights (180, 100, 50 and 5 m) of the Trainou 200 m television tower in the Orléans forest in France (47 • 57 53 N, 2 • 06 45 E, 131 m a.s.l.). The station is equipped with a custom-built CO 2 analyser (CARIBOU), which is based on a commercial non-dispersive, infrared (NDIR) analyser (Licor 6252), and a coupled gas chromatography (GC) system equipped with an electron capture detector (ECD) and a flame ionization detector (FID) (HP6890N, Agilent) and a reduction gas detector (PP1, Peak Performer). Air intakes , pumping and air drying system are shared between the CARIBOU and the GC systems. The ultimately achieved short-term repeatability (1 sigma, over several days) for the GC system is 0.05 ppm for CO 2 , 1.4 ppb for CH 4 , 0.25 ppb for N 2 O, 0.08 ppb for SF 6 , 0.88 ppb for CO and 3.8 for H 2. The repeatability of the CARIBOU CO 2 analyser is 0.06 ppm. In addition to the in situ measurements, weekly flask sampling is performed, and flask air samples are analysed at the Laboratoire des Sciences du Climat et de l'Environnement (LSCE) central laboratory for the same species as well for stable isotopes of CO 2. The comparison between in situ measurements and the flask sampling showed averaged differences of 0.08 ± 1.40 ppm for CO 2 , 0.7±7.3 ppb for CH 4 , 0.6±0.6 ppb for N 2 O, 0.01±0.10 ppt for SF 6 , 1.5±5.3 ppb for CO and 4.8±6.9 ppb for H 2 for the years 2008-2012. At Trainou station, the mean annual increase rates from 2007 to 2011 at the 180 m sampling height were 2.2 ppm yr −1 for CO 2 , 4 ppb yr −1 for CH 4 , 0.78 ppb yr −1 for N 2 O and 0.29 ppt yr −1 for SF 6. For all species, the 180 m sampling level showed the smallest diurnal variation. Mean diurnal gradients between the 50 m and the 180 m sampling level reached up to 30 ppm CO 2 , 15 ppm CH 4 or 0.5 ppb N 2 O during nighttime whereas the mean gradients are smaller than 0.5 ppm for CO 2 and 1.5 ppb for CH 4 during afternoon

Evaluation of Mixing-Height Retrievals from Automatic Profiling Lidars and Ceilometers in View of Future Integrated Networks in Europe

International audienceThe determination of the depth of daytime and nighttime mixing layers must be known very accurately to relate boundary-layer concentrations of gases or particles to upstream fluxes. The mixing-height is parametrized in numerical weather prediction models, so improving the determination of the mixing height will improve the quality of the estimated gas and particle budgets. Datasets of mixing-height diurnal cycles with high temporal and spatial resolutions are sought by various end users. Lidars and ceilometers provide vertical profiles of backscatter from aerosol particles. As aerosols are predominantly concentrated in the mixing layer, lidar backscatter profiles can be used to trace the depth of the mixing layer. Large numbers of automatic profiling lidars and ceilometers are deployed by meteorological services and other agencies in several European countries providing systems to monitor the mixing height on temporal and spatial scales of unprecedented density. We investigate limitations and capabilities of existing mixing height retrieval algorithms by applying five different retrieval techniques to three different lidars and ceilometers deployed during two 1-month campaigns. We studied three important steps in the mixing height retrieval process, namely the lidar/ceilometer pre-processing to reach sufficient signal-to-noise ratio, gradient detection techniques to find the significant aerosol gradients, and finally quality control and layer attribution to identify the actual mixing height from multiple possible layer detections. We found that layer attribution is by far the most uncertain step. We tested different gradient detection techniques, and found no evidence that the first derivative, wavelet transform, and two-dimensional derivative techniques have different skills to detect one or multiple significant aerosol gradients from lidar and ceilometer attenuated backscatter. However, our study shows that, when mixing height retrievals from a ultraviolet lidar and a near-infrared ceilometer agreed, they were 25-40% more likely to agree with an independent radiosonde mixing height retrieval than when each lidar or ceilometer was used alone. Furthermore, we point to directions that may assist the layer attribution step, for instance using commonly available surface measurements of radiation and temperature to derive surface sensible heat fluxes as a proxy for the intensity of convective mixing. It is a worthwhile effort to pursue such studies so that within a few years automatic profiling lidar and ceilometer networks can be utilized efficiently to monitor mixing heights at the European scale. © 2011 Springer Science+Business Media B.V

Comprehensive laboratory and field testing of cavity ring-down spectroscopy analyzers measuring H₂O, CO₂, CH₄ and CO

International audienceTo develop an accurate measurement network of greenhouse gases, instruments in the field need to be stable and precise and thus require infrequent calibrations and a low consumption of consumables. For about 10 years, cavity ring-down spectroscopy (CRDS) analyzers have been available that meet these stringent requirements for precision and stability. Here, we present the results of tests of CRDS instruments in the laboratory (47 instruments) and in the field (15 instruments). The precision and stability of the measurements are studied. We demonstrate that, thanks to rigorous testing, newer models generally perform better than older models, especially in terms of reproducibility between instruments. In the field, we see the importance of individual diagnostics during the installation phase, and we show the value of calibration and target gases that assess the quality of the data. Finally, we formulate recommendations for use of these analyzers in the field

High accuracy measurements of dry mole fractions of carbon dioxide and methane in humid air

Traditional techniques for measuring the mole fractions of greenhouse gases in the well-mixed atmosphere have required dry sample gas streams (dew point < −25 °C) to achieve the inter-laboratory compatibility goals set forth by the Global Atmosphere Watch programme of the World Meteorological Organisation (WMO/GAW) for carbon dioxide (±0.1 ppm in the Northern Hemisphere and ±0.05 ppm in the Southern Hemisphere) and methane (±2 ppb). Drying the sample gas to low levels of water vapour can be expensive, time-consuming, and/or problematic, especially at remote sites where access is difficult. Recent advances in optical measurement techniques, in particular cavity ring down spectroscopy, have led to the development of greenhouse gas analysers capable of simultaneous measurements of carbon dioxide, methane and water vapour. Unlike many older technologies, which can suffer from significant uncorrected interference from water vapour, these instruments permit accurate and precise greenhouse gas measurements that can meet the WMO/GAW <i>inter-laboratory compatibility goals</i> (WMO, 2011a) without drying the sample gas. In this paper, we present laboratory methodology for empirically deriving the water vapour correction factors, and we summarise a series of in-situ validation experiments comparing the measurements in humid gas streams to well-characterised dry-gas measurements. By using the manufacturer-supplied correction factors, the dry-mole fraction measurements have been demonstrated to be well within the GAW compatibility goals up to a water vapour concentration of at least 1%. By determining the correction factors for individual instruments once at the start of life, this water vapour concentration range can be extended to at least 2% over the life of the instrument, and if the correction factors are determined periodically over time, the evidence suggests that this range can be extended up to and even above 4% water vapour concentrations