Sampling and determination of gas-phase hydrogen peroxide following removal of ozone by gas-phase reaction with nitric oxide

Abstract

1) Hunt, D. F.; Shabanowltz. J.; Harvey, T. M.; Coates, M. Anal. Chem. 1985, 5 7 , 525-537. McMuttrey, K. D.; Wildman, N. J.; Tai, H. Bull. Environ. Toxicol. 1983, 31 ~ 734-737. van Graas, 0.; de Leeuw, J. W.; Schenck, P. A. in Advances h Organic Geochemistry 1979; Douglas, A. G., Maxwell, J. R., Eds.; Pergamon: London. 1980 DD 485-494. van de W n t I D.; Brown, S. c.; philp, R. P.; Simonett, B. R. T. GWchlm. C o s m h l m . Acta W80, 4 4 , 999-1013. van de Meent, D.; de Leeuw, J. W.; Schenck, P. A. J. Anal. Appl. fvrol. 1980. 2 . 249-263. Schenck, P.' A.; de Leeuw, J. W.; Viets, T. C.; Haverkamp, J. I n Petroleom, Geochemkf?y and Exploration of Europe; Brooks, J., Ed.; Blackweil Scientlfic: 1983; pp 267-274. van der Kaaden. A.; Boon, J. J.; de Leeuw, J. W.; de Lange, F.; Schuyi, P. J. W.; Schulten, H. R.; Bahr, U. Anal. Chem. 1884, 56, SaizJimenez, C.; de Leeuw, J. W. Org. Geochem. 1984, 6 , SaizJimenez, C.; de Leeuw, J. W. Org. Geochem. 1984, 6 , Nlp. M.; de Leeuw. J. W.; Schenck, P. A.; Meuzeiaar, H. L. C.; Stout, S. A.; Given, P. H.; Boon, J. A method for the determlnatlon of hydrogen peroxide In the amblent atmosphere is described, using bnplnger or dlffuslon scrubber collectlon of H,02 wlth aqueous-phase analysis by an enzyme-catalyzed fluorescence technique. Interference from ozone at amblent levels Is removed by gas-phase reactlon wtth excess nltrlc oxlde. The lmplnger and dMuslon scrubber collectlon technlques glve equlvalenl results for atmospherlc gas-phase H202 wtth h l t s of detectkn of 0.1 ppbv for approximately 60-mln and 10-mln sampllng times, respectlvely . The development of techniques for measuring gaseous and aqueous HzOz and other hydroperoxy compounds has been the focus of substantial research effort following the recog-Permanent address: Practical Engineering College of Beer-Sheva, P.O. Box 45, Beer-Sheva, Israel.nition that HzOz could rapidly oxidize dissolved S(1V) compounds to sulfuric acid throughout the normal pH range of rain, cloud, and fog waters (pH 2-7) (1,2). The high solubility of HzOz in water (Henry's law constant -lo5 M atm-') leads to significant aqueous concentration (1-100 MM) in, e.g., cloud water, even a t low parts-per-billion by volume gaseous HzOz concentrations in air entering clouds (3-5). Several methods for determining aqueous-phase HzOz in atmospheric samples have been developed or improved recently based on luminol chemiluminescence (61, (p-hydroxypheny1)acetic acid (POH-PAA) dimer fluorescence (5, 7-9), scopoletin fluorescence quenching (lo), and peroxyoxalate chemiluminescence (I 1).Measurements of gas-phase hydrogen peroxide have been attempted by collection of the peroxide in aqueous solution using impingers or condensation collection devices (12).However, these efforts have been shown to give unreliable resulta due to the in situ formation of hydrogen peroxide from low-solubility constituents of ambient air and/or compressed air during collection (13-15). It has been suggested that this

The influence of the nocturnal boundary layer on secondary trace species in the atmosphere at Dorset, Ontario

“…For example, daytime maxima in ambient HzO z concentrations have been reported by Kins (1990), Olszyna et al (1988), Jacob et a1. (1990, Tanner et al (1986) and Das et al (1983), and although…”

Measurement of Hydrogen Peroxide in Ambient Air by Impinger and Diffusion Scrubber

“…The details of the apparatus by which hydrogen peroxide is sampled into impinger and diffusion scrubbers with prior removal of ozone have been presented (Tanner et al, 1986). A summary of the pertinent features and modifications used in the CSMCS is given below.…”

“…Recently reported approaches include several aqueous scrubbing techniques, both integrative sampling using impingers (Tanner et al, 1986) and continuous sampling using concurrent coil turbulent (Lazrus et al, 1986), or porous membrane diffusion scrubbers (Dasgupta, 1984;Kleindienst et al, 1988). A second measurement approach uses concurrent cryogenic trapping of H202(g) water vapor at dry acetone temperatures in an impinger (Sakugawa and Kaplan, 1987), or in a diffusion cell at ca.…”

“…Removal of the interferences noted above has been successfully incorporated into several sampling methods as follows: addition of excess NO in the gas phase to remove ozone prior to scrubbing of H,O, into the aqueous phase, thus eliminating the positive O3 interference (Tanner et al, 1986;Groblicki and Ang, 1986); collection of H202 in mM HCHO aqueous solutions to complex SO, as hydroxymethanesulfonate, eliminating its negative interference (Lazrus et al, 1986); and collection in dilute EDTA to complex trace metals which may interfere in the luminol H202(g) method (Ibusuki, 1983) and probably the enzyme-catalyzed fluorescence analysis technique (Y.-N. Lee, Brookhaven National Laboratory, unpublished results, 1987). Direct spectroscopic measurement of H202 by the TDLAS technique is not subject to the chemical interferences mentioned above, although inlet losses can still be a significant problem.…”

Trends in Atmospheric Trace Gas Measurement Instruments with Membrane-based Gas Diffusion Scrubbers

“…While efforts have been made to use the denuder equations for membrane-based DS devices, [25][26][27] in the case of the typical annular geometry DS, however, only the outer wall of the inner tube is effective in collecting the gas, as shown in Fig. 2 (c), while gas is collected on both tube walls in the annular denuder.…”