Comparison of formaldehyde measurements by Hantzsch, CRDS and DOAS in the SAPHIR chamber

Glowania, Marvin; Rohrer, Franz; Dorn, Hans-Peter; Hofzumahaus, A.; Holland, F.; Kiendler‐Scharr, Astrid; Wahner, Andreas; Fuchs, Hendrik

doi:10.5194/amt-14-4239-2021

Cited by 24 publications

(29 citation statements)

References 55 publications

(73 reference statements)

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“…On a global scale, the emission of carbon from biogenic volatile organic compounds (BVOCs) exceeds 1000 Tg per year (Guenther et al, 2012). Among all BVOC emissions, monoterpenes are the second most important class of species, contributing up to 16 % to the total emissions.…”

Section: Introductionmentioning

confidence: 99%

Atmospheric photooxidation and ozonolysis of Δ<sup>3</sup>-carene and 3-caronaldehyde: rate constants and product yields

et al. 2021

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Abstract. The oxidation of Δ3-carene and one of its main oxidation products, caronaldehyde, by the OH radical and O3 was investigated in the atmospheric simulation chamber SAPHIR under atmospheric conditions for NOx mixing ratios below 2 ppbv. Within this study, the rate constants of the reaction of Δ3-carene with OH and O3 and of the reaction of caronaldehyde with OH were determined to be (8.0±0.5)×10-11 cm3 s−1 at 304 K, (4.4±0.2)×10-17 cm3 s−1 at 300 K and (4.6±1.6)×10-11 cm3 s−1 at 300 K, in agreement with previously published values. The yields of caronaldehyde from the reaction of OH and ozone with Δ3-carene were determined to be 0.30±0.05 and 0.06±0.02, respectively. Both values are in reasonably good agreement with reported literature values. An organic nitrate (RONO2) yield from the reaction of NO with RO2 derived from Δ3-carene of 0.25±0.04 was determined from the analysis of the reactive nitrogen species (NOy) in the SAPHIR chamber. The RONO2 yield of the reaction of NO with RO2 derived from the reaction of caronaldehyde with OH was found to be 0.10±0.02. The organic nitrate yields of Δ3-carene and caronaldehyde oxidation with OH are reported here for the first time in the gas phase. An OH yield of 0.65±0.10 was determined from the ozonolysis of Δ3-carene. Calculations of production and destruction rates of the sum of hydroxyl and peroxy radicals (ROx=OH+HO2+RO2) demonstrated that there were no unaccounted production or loss processes of radicals in the oxidation of Δ3-carene for conditions of the chamber experiments. In an OH-free experiment with added OH scavenger, the photolysis frequency of caronaldehyde was obtained from its photolytical decay. The experimental photolysis frequency was a factor of 7 higher than the value calculated from the measured solar actinic flux density, an absorption cross section from the literature and an assumed effective quantum yield of unity for photodissociation.

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Section: Introductionmentioning

confidence: 99%

Atmospheric photooxidation and ozonolysis of Δ<sup>3</sup>-carene and 3-caronaldehyde: rate constants and product yields

et al. 2021

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“…The operating principle of cavity ringdown spectroscopy as used by the G2307 is described fully in Glowania et al (2021), and briefly summarized here. Air is pulled through a temperature and pressure-controlled cavity at a rate of 120 0.4 standard liters per minute (SLPM).…”

Section: Picarro G2307 Description and Calibrationmentioning

confidence: 99%

“…In recent years, several 65 commercially available instruments have been developed towards that goal, including a cavity ring down spectroscopy (CRDS) instrument from Picarro, a photoacoustic gas analyser from Gasera, and Tunable Diode Laser Spectroscopy (TDLS) instruments from Aeris Technologies and Aerodyne Research, Inc. Here, we focus on the Aeris MIRA and Picarro CRDS G2307 instruments, which have been compared against other instruments in a small number of informal (Whitehill et al, 2018;Furdyna, 2020) and peer-reviewed (Shutter et al, 2019;Glowania et al, 2021) intercomparison efforts. Since those efforts, the Picarro G2307 instrument implemented updates to its spectral fitting algorithm, and the Aeris MIRA instrument has offered improved thermal stabilization.…”

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confidence: 99%

“…Whitehill et al (2018) found an inverse correlation between Picarro HCHO measurements and instrument-reported water mixing ratios at typical, ambient concentrations and, along with Furdyna (2020), observed that the G2307's measurements were lower by 1-2 ppb HCHO compared to DNPH-based measurements. Glowania et al (2021), using a spectral fitting algorithm 85 updated after the Whitehill et al (2018) intercomparison (released Sep. 2019, found that low humidity conditions can lead to changes in reported HCHO concentrations as high as 1.75 ppb. These offsets are most significant at ≤ 0.2% H2O where the H2O spectral feature is not clearly observed.…”

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Evaluation of Aeris MIRA, Picarro CRDS G2307, and DNPH-based sampling for long-term formaldehyde monitoring efforts

Mouat

Siegel

Kaiser

2023

Preprint

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Abstract. Current formaldehyde measurement networks rely on the TO-11A offline chemical derivatization technique, which can be resource intensive and limited in temporal resolution. In this work, we evaluate the field performance of three new commercial instruments for continuous in-situ formaldehyde monitoring: the Picarro cavity ringdown spectroscopy (CRDS) G2307 gas concentration analyzer and Aeris Technologies’ mid-infrared absorption (MIRA) Pico and Ultra gas analyzers. All instruments require regular drift correction, with baseline drifts over a 1-week period of ambient sampling of 1 ppb, 4 ppb, and 20 ppb for the G2307, Ultra, and Pico, respectively. Baseline drifts are easily corrected with frequent instrument zeroing using DNPH scrubbers, while Drierite, molecular sieves, and heated hopcalite fail to remove all incoming HCHO. Drift-corrected 3σ limits of detection (LOD) determined from regular instrument zeroing were relatively comparable at 0.055 ppb (Picarro G2307), 0.065 ppb (Aeris Ultra), and 0.08 ppb (Aeris Pico) for a 20 min integration time. We find that after correcting for a 30–40 % bias in the Pico measurements, all instruments agree within 5 % and are well correlated with each other (all R2≥0.70). Picarro G2307 HCHO observations are more than 50 % higher than co-located TO-11A HCHO measurements (R2 = 0.92, slope = 1.47, int = 1 ppb HCHO), which is in contrast to previous comparisons where measurements were biased low by 1–2 ppb. We attribute this discrepancy to the previous versions of the spectral fitting algorithm as well as the zeroing method. The temperature stabilization upgrade of the Ultra offers improved baseline stability over the previously described Pico version, reducing the maximum drift rate by a factor of 13 and improves precision of a 10 min average by 13 ppt. Using a 6-month deployment period, we demonstrate that all instruments provide a reliable measurement of ambient HCHO concentrations in an urban environment and, when compared with previous observations, find that midday summertime HCHO concentrations have reduced by approximately 50 % in the last two decades.

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“…Measurements of formaldehyde (HCHO) concentrations were available from either one of three instruments which included an instrument making use of the Hantzsch reaction (AL4021, Aero Laser GmbH), the DOAS instrument that is also used for the detection of OH, and a cavity ring-down spectroscopy (CRDS) analyzer (Picarro G2307) (Glowania et al, 2021). Measurements using the Hantzsch method were available in the experiments in 2012, measurements with DOAS were available in the experiments in 2015, and measurements with CRDS were available in the experiments in 2019.…”

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confidence: 99%

Investigation of the limonene photooxidation by OH at different NO concentrations in the atmospheric simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber)

Pang¹,

Novelli²,

Kaminski³

et al. 2022

Atmos. Chem. Phys.

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Abstract. The oxidation of limonene by the hydroxyl (OH) radical and ozone (O3) was investigated in the atmospheric simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber) in experiments performed at different nitric oxide (NO) mixing ratios from nearly 0 up to 10 ppbv. For the experiments dominated by OH oxidation, the formaldehyde (HCHO) yield was experimentally determined and found to be (12 ± 3), (13 ± 3), and (32 ± 5) % for experiments with low (∼ 0.1 ppbv), medium (∼ 0.3 ppbv), and high NO (5 to 10 ppbv), respectively. The yield in an ozonolysis-only experiment was (10 ± 1) %, which agrees with previous laboratory studies. The experimental yield of the first-generation organic nitrates from limonene–OH oxidation is calculated as (34 ± 5) %, about 11 % higher than the value in the Master Chemical Mechanism (MCM), which is derived from structure–activity relationships (SARs). Time series of measured radicals, trace-gas concentrations, and OH reactivity are compared to results from zero-dimensional chemical box model calculations applying MCM v3.3.1. Modeled OH reactivity is 5 to 10 s−1 (25 % to 33 % of the OH reactivity at the start of the experiment) higher than measured values at the end of the experiments under all chemical conditions investigated, suggesting either that there are unaccounted loss processes of limonene oxidation products or that products are less reactive toward OH. In addition, model calculations underestimate measured hydroperoxyl radical (HO2) concentrations by 20 % to 90 % and overestimate organic peroxyl radical (RO2) concentrations by 50 % to 300 %. The largest deviations are found in low-NO experiments and in the ozonolysis experiment. An OH radical budget analysis, which uses only measured quantities, shows that the budget is closed in most of the experiments. A similar budget analysis for RO2 radicals suggests that an additional RO2 loss rate constant of about (1–6) × 10−2 s−1 for first-generation RO2 is required to match the measured RO2 concentrations in all experiments. Sensitivity model runs indicate that additional reactions converting RO2 to HO2 at a rate constant of about (1.7–3.0) × 10−2 s−1 would improve the model–measurement agreement of NOx, HO2, and RO2 concentrations and OH reactivity. Reaction pathways that could lead to the production of additional OH and HO2 are discussed, which include isomerization reactions of RO2 from the oxidation of limonene, different branching ratios for the reaction of RO2 with HO2, and a faster rate constant for RO2 recombination reactions. As the exact chemical mechanisms of the additional HO2 and OH sources could not be identified, further work needs to focus on quantifying organic product species and organic peroxy radicals from limonene oxidation.

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Comparison of formaldehyde measurements by Hantzsch, CRDS and DOAS in the SAPHIR chamber

Cited by 24 publications

References 55 publications

Atmospheric photooxidation and ozonolysis of Δ<sup>3</sup>-carene and 3-caronaldehyde: rate constants and product yields

Atmospheric photooxidation and ozonolysis of Δ<sup>3</sup>-carene and 3-caronaldehyde: rate constants and product yields

Evaluation of Aeris MIRA, Picarro CRDS G2307, and DNPH-based sampling for long-term formaldehyde monitoring efforts

Investigation of the limonene photooxidation by OH at different NO concentrations in the atmospheric simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber)

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Comparison of formaldehyde measurements by Hantzsch, CRDS and DOAS in the SAPHIR chamber

Cited by 24 publications

References 55 publications

Atmospheric photooxidation and ozonolysis of Δ&lt;sup&gt;3&lt;/sup&gt;-carene and 3-caronaldehyde: rate constants and product yields

Atmospheric photooxidation and ozonolysis of Δ&lt;sup&gt;3&lt;/sup&gt;-carene and 3-caronaldehyde: rate constants and product yields

Evaluation of Aeris MIRA, Picarro CRDS G2307, and DNPH-based sampling for long-term formaldehyde monitoring efforts

Investigation of the limonene photooxidation by OH at different NO concentrations in the atmospheric simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber)

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Atmospheric photooxidation and ozonolysis of Δ<sup>3</sup>-carene and 3-caronaldehyde: rate constants and product yields

Atmospheric photooxidation and ozonolysis of Δ<sup>3</sup>-carene and 3-caronaldehyde: rate constants and product yields