Measurements of the dry deposition of peroxides to a Canadian boreal forest

Hall, B. D.; Claiborn, Candis

doi:10.1029/97jd01113

Cited by 54 publications

(37 citation statements)

References 27 publications

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“…The present study suggests a best estimate for the 24 h mean of the dry deposition velocity of hydrogen peroxide of Gao et al (1993) 2.5 above forest Heikes et al (1996) 0.88 1.4×10 −5 South Atlantic Hall and Claiborn (1997) 1-5 coniferous forest in Canada Sillman et al (1998) ≈5 Tennessee Walcek (1987) theoretically calculated a value of 1 cm/s for the H 2 O 2 dry deposition velocity over the northeast United States which is roughly in agreement with our result for the rainforest and with the mean 1-D SCM result over land. Baer and Nester (1992) assessed an average v d (H 2 O 2 )=1.5 cm/s for the region of the Upper Rhine Valley (Germany) in March 1985 with a regional mesoscale diffusion model, again relatively close to our estimate.…”

Section: Comparison With Results From Other Studiesmentioning

confidence: 99%

“…Also the derived deposition rate of 1.4×10 −5 s −1 for H 2 O 2 (6×10 −6 s −1 for CH 3 OOH) at a marine BL height of 700 m is rather smaller than our value. From gradient measurements (modified Bowen method) Hall and Claiborn (1997) compute diurnal maxima of v d =5 cm/s for H 2 O 2 and 1.6 cm/s for organic peroxide as well as nocturnal values of 1 cm/s and 0.5 cm/s, respectively, over a coniferous forest in Canada. Their results show that the surface resistance is negligible in the case of H 2 O 2 and that the dry deposition of all peroxides is limited by turbulence.…”

Section: Comparison With Results From Other Studiesmentioning

confidence: 99%

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Chemistry, transport and dry deposition of trace gases in the boundary layer over the tropical Atlantic Ocean and the Guyanas during the GABRIEL field campaign

et al. 2007

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Abstract. We present a comparison of different Lagrangian and chemical box model calculations with measurement data obtained during the GABRIEL campaign over the tropical Atlantic Ocean and the Amazon rainforest in the Guyanas, October 2005. Lagrangian modelling of boundary layer (BL) air constrained by measurements is used to derive a horizontal gradient (≈5.6 pmol/mol km −1 ) of CO from the ocean to the rainforest (east to west). This is significantly smaller than that derived from the measurements (16-48 pmol/mol km −1 ), indicating that photochemical production from organic precursors alone cannot explain the observed strong gradient. It appears that HCHO is overestimated by the Lagrangian and chemical box models, which include dry deposition but not exchange with the free troposphere (FT). The relatively short lifetime of HCHO implies substantial BL-FT exchange. The mixing-in of FT air affected by African and South American biomass burning at an estimated rate of 0.12 h −1 increases the CO and decreases the HCHO mixing ratios, improving agreement with measurements. A mean deposition velocity of 1.35 cm/s for H 2 O 2 over the ocean as well as over the rainforest is deduced assuming BL-FT exchange adequate to the results for CO. The measured increase of the organic peroxides from the ocean to the rainforest (≈0.66 nmol/mol d −1 ) is significantly overestimated by the Lagrangian model, even when using high values for the deposition velocity and the entrainment rate. Our results point at either heterogeneous loss of organic peroxides and/or their radical precursors, underestimated photodissociation or missing reaction paths of peroxy radicals not forming peroxides in isoprene chemistry. We calculate a mean integrated daytime net ozone production (NOP) in the Correspondence to: A. Stickler (alexander.stickler@env.ethz.ch) BL of (0.2±5.9) nmol/mol (ocean) and (2.4±2.1) nmol/mol (rainforest). The NOP strongly correlates with NO and has a positive tendency in the boundary layer over the rainforest.

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Section: Comparison With Results From Other Studiesmentioning

confidence: 99%

Section: Comparison With Results From Other Studiesmentioning

confidence: 99%

Chemistry, transport and dry deposition of trace gases in the boundary layer over the tropical Atlantic Ocean and the Guyanas during the GABRIEL field campaign

et al. 2007

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“…However, the solubility of many hydroperoxides and other oxygenated organics is extremely uncertain and known to cover a wide range, with the measured Henry's law constants for methyl hydroperoxide and peroxyacetic acid being 2-3 orders of magnitude lower than that for H 2 O 2 (Lind and Kok, 1986). Observations of OVOC deposition velocities are sparse, with only a handful reported for forested regions (Hall and Claiborn, 1997;Valverde-Canossa et al, 29 Figure 13: Diurnal variation of the observed OH reactivity (black points) and a set of model simulations with different first order loss rates to represent the loss of model generated species to physical processes. The lifetime of species with respect to this first order loss are 1 (green), 12 (dark blue), 24 (red) 48 (pale blue), and 96 (yellow) h.…”

Section: Physical Lossmentioning

confidence: 99%

“…However, the solubility of many hydroperoxides and other oxygenated organics is extremely uncertain and known to cover a wide range, with the measured Henry's law constants for methyl hydroperoxide and peroxyacetic acid being 2-3 orders of magnitude lower than that for H2O2 [Lind and Kok, 1986]. Observations of OVOC deposition velocities are sparse, with only a handful reported for forested regions [Hall and Claiborn, 1997;Valverde-Canossa et al, 2006;Hall et al, 1999;Karl et al, 2004;Kuhn et al, 2002]. An observation of the deposition velocity of the sum of MVK and MACR in a Fig.…”

Section: Physical Lossmentioning

confidence: 99%

OH reactivity in a South East Asian tropical rainforest during the Oxidant and Particle Photochemical Processes (OP3) project

et al. 2013

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Abstract. OH (hydroxyl radical) reactivity, the inverse of the chemical lifetime of the hydroxyl radical, was measured for 12 days in April 2008 within a tropical rainforest on Borneo as part of the OP3 (Oxidant and Particle Photochemical Processes) project. The maximum observed value was 83.8 ± 26.0 s −1 with the campaign averaged noontime maximum being 29.1 ± 8.5 s −1 . The maximum OH reactivity calculated using the diurnally averaged concentrations of observed sinks was ∼ 18 s −1 , significantly less than the observations, consistent with other studies in similar environments. OH reactivity was dominated by reaction with isoprene (∼ 30 %). Numerical simulations of isoprene oxidation using the Master Chemical Mechanism (v3.2) in a highly simplified physical and chemical environment show that the steady state OH reactivity is a linear function of the OH reactivity due to isoprene alone, with a maximum multiplier, to account for the OH reactivity of the isoprene oxidation products, being equal to the number of isoprene OH attackable bonds (10). Thus the emission of isoprene constitutes a significantly larger emission of reactivity than is offered by the primary reaction with isoprene alone, with significant scope for the secondary oxidation products of isoprene to constitute the observed missing OH reactivity. A physically and chemically more sophisticated simulation (including physical loss, photolysis, and other oxidants) showed that the calculated OH reactivity is reduced by the removal of the OH attackable bonds by other oxidants and photolysis, and by physical loss (mixing and deposition). The calculated OH reactivity is increased by peroxide cycling, and by the OH concentration itself. Notable in these calculations is that the accumulated OH reactivity from isoprene, defined as the total OH reactivity of an emitted isoprene molecule and all of its oxidation products, is significantly larger than the reactivity due to isoprene itself and critically depends on the chemical and physical lifetimes of intermediate species. When constrained to the observed diurnally averaged concentrations of primary VOCs (volatile organic compounds), O 3 , NO x and other parameters, the model underestimated the observed diurnal mean OH reactivity by 30 %. However, it was found that (1) the short lifetimes of isoprene and OH, compared to those of the isoprene oxidation products, lead to a large variability in their concentrations and so significant variation Published by Copernicus Publications on behalf of the European Geosciences Union. P. M. Edwards et al.: OH reactivity in a South East Asian tropical rainforestin the calculated OH reactivity; (2) uncertainties in the OH chemistry in these high isoprene environments can lead to an underestimate of the OH reactivity; (3) the physical loss of species that react with OH plays a significant role in the calculated OH reactivity; and (4) a missing primary source of reactive carbon would have to be emitted at a rate equivalent to 50 % that of isoprene to account for the missing OH s...

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“…Due to strong mixing within the PBL, air masses near the surface are strongly affected by H 2 O 2 dry deposition. In addition, H 2 O 2 is removed by rainout in the lower troposphere (Heikes et al, 1996b;Hall and Claiborn, 1997;Hall et al, 1999). The combination of these effects results in an inverted "C-shaped" vertical profile for H 2 O 2 .…”

Section: Introductionmentioning

confidence: 99%

Distribution of hydrogen peroxide and formaldehyde over Central Europe during the HOOVER project

et al. 2011

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Abstract. In this study we report measurements of hydrogen peroxide (H 2 O 2 ), methyl hydroperoxide* (MHP* as a proxy of MHP based on an unspecific measurement of total organic peroxides) and formaldehyde (HCHO) from the HO x OVer EuRope (HOOVER) project (HO x = OH+HO 2 ). HOOVER included two airborne field campaigns, in October 2006 and July 2007. Measurement flights were conducted from the base of operation Hohn (Germany, 54 • N, 9 • E) towards the Mediterranean and to the subpolar regions over Norway. We find negative concentration gradients with increasing latitude throughout the troposphere for H 2 O 2 and CH 3 OOH * . In contrast, observed HCHO is almost homogeneously distributed over central and northern Europe and is elevated over the Mediterranean. In general, the measured gradients tend to be steepest entering the Mediterranean region, where we also find the highest abundances of the 3 species. Mixing ratios of these tracers generally decrease with altitude. H 2 O 2 and CH 3 OOH * show maxima above the boundary layer at 2-5 km, being more distinct over southern than over northern Europe.We also present a comparison of our data with simulations by two global 3-D-models, MATCH-MPIC and EMAC, and with the box model CAABA. The models realistically represent altitude and latitude gradients for both HCHO and hydroperoxides (ROOH). In contrast, the models have problems reproducing the absolute mixing ratios, in particular of H 2 O 2 . Large uncertainties about retention coefficients and Correspondence to: H. Fischer (horst.fischer@mpic.de) cloud microphysical parameters suggest that cloud scavenging might be a large source of error for the simulation of H 2 O 2 . A sensitivity study with EMAC shows a strong influence of cloud and precipitation scavenging on the budget of H 2 O 2 as simulations improve significantly with this effect switched off.

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Measurements of the dry deposition of peroxides to a Canadian boreal forest

Cited by 54 publications

References 27 publications

Chemistry, transport and dry deposition of trace gases in the boundary layer over the tropical Atlantic Ocean and the Guyanas during the GABRIEL field campaign

Chemistry, transport and dry deposition of trace gases in the boundary layer over the tropical Atlantic Ocean and the Guyanas during the GABRIEL field campaign

OH reactivity in a South East Asian tropical rainforest during the Oxidant and Particle Photochemical Processes (OP3) project

Distribution of hydrogen peroxide and formaldehyde over Central Europe during the HOOVER project

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