Automated System for Monitoring Trace C2H2in Ambient Air by Cavity Ring-Down Spectroscopy Combined with Sample Preconcentration

2008 ◽  
Vol 42 (19) ◽  
pp. 7354-7359 ◽  
Author(s):  
Manik Pradhan ◽  
M. S. I. Aziz ◽  
Roberto Grilli ◽  
Andrew J. Orr-Ewing
2007 ◽  
Vol 90 (1) ◽  
pp. 1-9 ◽  
Author(s):  
M. Pradhan ◽  
R.E. Lindley ◽  
R. Grilli ◽  
I.R. White ◽  
D. Martin ◽  
...  

2012 ◽  
Vol 5 (6) ◽  
pp. 8995-9020
Author(s):  
A. Pierce ◽  
D. Obrist ◽  
H. Moosmüller ◽  
X. Faïn ◽  
C. Moore

Abstract. The ability to make high time resolution measurements of gaseous elemental mercury (GEM) concentrations in air is imperative for the understanding of mercury cycling. Here we describe further development and field implementation of a laboratory prototype pulsed cavity ring-down spectroscopy (CRDS) system for high time resolution, continuous and automated measurement of GEM concentrations in ambient air. In particular, we present use of an external, isotopically enriched Hg cell for automated wavelength locking and wavelength stabilization to maintain laser wavelength on the peak of GEM absorption line in ambient air. We further describe implementation of differential absorption measurements using a piezoelectric tuning element that allows for continuous accounting of system baseline extinction losses needed to calculate GEM absorption coefficients. Data acquisition systems and software programs were modified to acquire high-speed ring-down data at 50 Hz repetition rate as well as process and analyze data in real time. The system was installed in a mobile trailer, and inlet systems and temperature controls were designed to minimize effects of changes in ambient air temperature and ozone (O3) concentration. Data that identify technical challenges and interferences that occurred during measurements, including temperature fluctuations, interferences by ambient O3 and drifts in frequency conversion efficiencies are discussed. Successful development of a CRDS system capable of measuring ambient air GEM concentrations with high time resolution is based on minimizing these interferences.


2010 ◽  
Vol 3 (2) ◽  
pp. 375-386 ◽  
Author(s):  
H. Chen ◽  
J. Winderlich ◽  
C. Gerbig ◽  
A. Hoefer ◽  
C. W. Rella ◽  
...  

Abstract. High-accuracy continuous measurements of greenhouse gases (CO2 and CH4) during the BARCA (Balanço Atmosférico Regional de Carbono na Amazônia) phase B campaign in Brazil in May 2009 were accomplished using a newly available analyzer based on the cavity ring-down spectroscopy (CRDS) technique. This analyzer was flown without a drying system or any in-flight calibration gases. Water vapor corrections associated with dilution and pressure-broadening effects for CO2 and CH4 were derived from laboratory experiments employing measurements of water vapor by the CRDS analyzer. Before the campaign, the stability of the analyzer was assessed by laboratory tests under simulated flight conditions. During the campaign, a comparison of CO2 measurements between the CRDS analyzer and a nondispersive infrared (NDIR) analyzer on board the same aircraft showed a mean difference of 0.22±0.09 ppm for all flights over the Amazon rain forest. At the end of the campaign, CO2 concentrations of the synthetic calibration gases used by the NDIR analyzer were determined by the CRDS analyzer. After correcting for the isotope and the pressure-broadening effects that resulted from changes of the composition of synthetic vs. ambient air, and applying those concentrations as calibrated values of the calibration gases to reprocess the CO2 measurements made by the NDIR, the mean difference between the CRDS and the NDIR during BARCA was reduced to 0.05±0.09 ppm, with the mean standard deviation of 0.23±0.05 ppm. The results clearly show that the CRDS is sufficiently stable to be used in flight without drying the air or calibrating in flight and the water corrections are fully adequate for high-accuracy continuous airborne measurements of CO2 and CH4.


2016 ◽  
Vol 24 (5) ◽  
pp. 5523 ◽  
Author(s):  
Laura E. McHale ◽  
Arsineh Hecobian ◽  
Azer P. Yalin

2010 ◽  
Vol 10 (6) ◽  
pp. 2879-2892 ◽  
Author(s):  
X. Faïn ◽  
H. Moosmüller ◽  
D. Obrist

Abstract. Cavity ring-down spectroscopy (CRDS) is a direct absorption technique that utilizes path lengths up to multiple kilometers in a compact absorption cell and has a significantly higher sensitivity than conventional absorption spectroscopy. This tool opens new prospects for study of gaseous elemental mercury (Hg0) because of its high temporal resolution and reduced sample volume requirements (<0.5 l of sample air). We developed a new sensor based on CRDS for measurement of (Hg0) mass concentration. Sensor characteristics include sub-ng m−3 detection limit and high temporal resolution using a frequency-doubled, tuneable dye laser emitting pulses at ~253.65 nm with a pulse repetition frequency of 50 Hz. The dye laser incorporates a unique piezo element attached to its tuning grating allowing it to tune the laser on and off the Hg0 absorption line on a pulse-to-pulse basis to facilitate differential absorption measurements. Hg0 absorption measurements with this CRDS laboratory prototype are highly linearly related to Hg0 concentrations determined by a Tekran 2537B analyzer over an Hg0 concentration range from 0.2 ng m−3 to 573 ng m−3, implying excellent linearity of both instruments. The current CRDS instrument has a sensitivity of 0.10 ng Hg0 m−3 at 10-s time resolution. Ambient-air tests showed that background Hg0 levels can be detected at low temporal resolution (i.e., 1 s), but also highlight a need for high-frequency (i.e., pulse-to-pulse) differential on/off-line tuning of the laser wavelength to account for instabilities of the CRDS system and variable background absorption interferences. Future applications may include ambient Hg0 flux measurements with eddy covariance techniques, which require measurements of Hg0 concentrations with sub-ng m−3 sensitivity and sub-second time resolution.


2020 ◽  
Vol 13 (5) ◽  
pp. 2577-2600 ◽  
Author(s):  
Midhun George ◽  
Maria Dolores Andrés Hernández ◽  
Vladyslav Nenakhov ◽  
Yangzhuoran Liu ◽  
John Philip Burrows

Abstract. Hydroperoxyl (HO2) and organic peroxy (RO2) radicals have an unpaired spin and are highly reactive free radicals. Measurements of the sum of HO2 and RO2 provide unique information about the chemical processing in an air mass. This paper describes the experimental features and capabilities of the Peroxy Radical Chemical Enhancement and Absorption Spectrometer (PeRCEAS). This is an instrument designed to make measurements on aircraft from the boundary layer to the lower stratosphere. PeRCEAS combines the amplified conversion of peroxy radicals to nitrogen dioxide (NO2) with the sensitive detection of NO2 using cavity ring-down spectroscopy (CRDS) at 408 nm. PeRCEAS is a dual-channel instrument, with two identical reactor–detector lines working out of phase with one another at a constant and defined pressure lower than ambient at the aircraft altitude. The suitability of PeRCEAS for airborne measurements in the free troposphere was evaluated by extensive characterisation and calibration under atmospherically representative conditions in the laboratory. The use of alternating modes of the two instrumental channels successfully captures short-term variations in the sum of peroxy radicals, defined as RO2∗ (RO2∗=HO2+∑RO2+OH+∑RO, with R being an organic chain) in ambient air. For a 60 s measurement, the RO2∗ detection limit is < 2 pptv for a minimum (2σ) NO2 detectable mixing ratio < 60 pptv, under laboratory conditions in the range of atmospheric pressures and temperatures expected in the free troposphere. PeRCEAS has been successfully deployed within the OMO (Oxidation Mechanism Observations) and EMeRGe (Effect of Megacities on the transport and transformation of pollutants on the Regional and Global scales) missions in different airborne campaigns aboard the High Altitude LOng range research aircraft (HALO) for the study of the composition of the free troposphere.


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