Photochemical production of low-molecular-weight carbonyl compounds in seawater and surface microlayer and their air-sea exchange

Zhou, Xianliang; Mopper, Kenneth

doi:10.1016/s0304-4203(96)00076-x

Cited by 219 publications

(296 citation statements)

References 28 publications

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“…In addition, precipitation, which removes particles more efficiently than most VOCs, was infrequent during NEAQS. Potentially complicating factors in the analysis, which will be briefly addressed, include the complex meso-scale meteorology of the New England coastal region [Angevine et al, 2004], the presence of oceanic VOC emissions [Bonsang et al, 1988;Zhou and Mopper, 1997], and the potential for halogen chemistry involving sea salt [Sander et al, 2003]. …”

Section: Introductionmentioning

confidence: 99%

Budget of organic carbon in a polluted atmosphere: Results from the New England Air Quality Study in 2002

et al. 2005

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[1] An extensive set of volatile organic compounds (VOCs) and particulate organic matter (POM) was measured in polluted air during the New England Air Quality Study in 2002. Using VOC ratios, the photochemical age of the sampled air masses was estimated. This approach was validated (1) by comparing the observed rates at which VOCs were removed from the atmosphere with the rates expected from OH oxidation, (2) by comparing the VOC emission ratios inferred from the data with the average composition of urban air, and (3) by the ability to describe the increase of an alkyl nitrate with time in terms of the chemical kinetics. A large part of the variability observed for oxygenated VOCs (OVOCs) and POM could be explained by a description that includes the removal of the primary anthropogenic emissions, the formation and removal of secondary anthropogenic species, and a biogenic contribution parameterized by the emissions of isoprene. The OVOC sources determined from the data are compared with the available literature, and a satisfactory agreement is obtained. The observed sub-mm POM was highly correlated with secondary anthropogenic gas-phase species, strongly suggesting that the POM was from secondary anthropogenic sources. The results are used to describe the speciation and total mass of gas-and particle-phase organic carbon as a function of the photochemical age of an urban air mass. Shortly after emission the organic carbon mass is dominated by primary VOCs, while after two days the dominant contribution is from OVOCs and sub-mm POM. The total measured organic carbon mass decreased by about 40% over the course of two days. The increase in sub-mm POM could not be explained by the removal of aromatic precursors alone, suggesting that other species must have contributed and/or that the mechanism for POM formation is more efficient than previously assumed.Citation: de Gouw, J. A., et al. (2005), Budget of organic carbon in a polluted atmosphere: Results from the New England Air

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Section: Introductionmentioning

confidence: 99%

Budget of organic carbon in a polluted atmosphere: Results from the New England Air Quality Study in 2002

et al. 2005

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“…[6][7][8] The LMW carbonyl compounds in natural water are biologically labile, because they are taken up quickly by microorganisms. 6,7 Aldehyde formation in the ozonization treatment for drinking water has been reported. The migration of carbonyl compounds from polyethylene terephthalate (PET) bottles into commercial bottled mineral water has also been investigated.…”

Section: Introductionmentioning

confidence: 99%

“…3,4 In natural water, LMW carbonyl compounds are produced by the photochemical degradation of dissolved organic matter (DOM). [6][7][8] The LMW carbonyl compounds in natural water are biologically labile, because they are taken up quickly by microorganisms. 6,7 Aldehyde formation in the ozonization treatment for drinking water has been reported.…”

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confidence: 99%

“…Kieber and Mopper have reported on the determination of picomolar concentrations of carbonyl compounds in seawater by using a DNPH derivatization/C-18 SPE cartridge with large-volume injection and large-bore column HPLC. [6][7][8] A gas chromatography (GC) method based on the DNPH derivatization was also reported, although DNPH derivatives have low volatility and poor thermal stability. 10 HPLCfluorescence using dansylacetamidooxyamine is also a sensitive method for the determination of carbonyl compounds.…”

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Rapid and Highly Sensitive Determination of Low-Molecular-Weight Carbonyl Compounds in Drinking Water and Natural Water by Preconcentration HPLC with 2,4-Dinitrophenylhydrazine

et al. 2006

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Low-molecular-weight (LMW) carbonyl compounds (i.e. aldehydes (RCOH) and ketones (RCOR′)) in the troposphere are mainly formed by photochemical oxidation process of anthropogenic and biogenic hydrocarbon. [1][2][3] They are also emitted directly by the combustion of fossil fuels and biomass by motor vehicles and industrial processes. 1 LMW carbonyl compounds in the atmosphere are easily dissolved in rain, cloud water and dew. 2,4 They are active participants in atmospheric chemical reactions in both gas and liquid phases, and they are involved in the generation of acids in atmospheric water. LMW carbonyl compounds are deposited on the ground and the sea surface as rain. For surface water, atmospheric deposition is one of the most important sources of formaldehyde, since the concentrations of formaldehyde in rain are higher than those in surface water such as seawater and river water, by three orders of magnitude, or more. LMW carbonyl compounds are exchanged directly between the surface water phase and the atmosphere. 3,4 In natural water, LMW carbonyl compounds are produced by the photochemical degradation of dissolved organic matter (DOM). [6][7][8] The LMW carbonyl compounds in natural water are biologically labile, because they are taken up quickly by microorganisms. 6,7 Aldehyde formation in the ozonization treatment for drinking water has been reported. The migration of carbonyl compounds from polyethylene terephthalate (PET) bottles into commercial bottled mineral water has also been investigated. 9 In Japan, the concentration of formaldehyde in tap water is regulated at less than 80 μg/L (= 2.7 μM), and is monitored regularly.Some analytical methods have been reported for LMW carbonyl compounds in water. The 2,4-dinitrophenylhydrazine (DNPH) derivatization method, in which aldehyde-DNPH derivatives are subsequently separated by high performance liquid chromatography (HPLC) and detected by ultraviolet absorption, has been applied to rain and dew samples. 3,4 A solid phase extraction (SPE) technique has been used in attempts to lower the detection limits for aqueous samples. Kieber and Mopper have reported on the determination of picomolar concentrations of carbonyl compounds in seawater by using a DNPH derivatization/C-18 SPE cartridge with large-volume injection and large-bore column HPLC. [6][7][8] A gas chromatography (GC) method based on the DNPH derivatization was also reported, although DNPH derivatives have low volatility and poor thermal stability. 10 HPLCfluorescence using dansylacetamidooxyamine is also a sensitive method for the determination of carbonyl compounds. 11 Gas chromatography/mass spectrometry (GC/MS) coupled with o- (2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBOA) derivatization is one of the most sensitive methods for determining aldehydes in water. 9,[12][13][14][15][16] The concentrations of 4 aldehydes in tap water and bottled mineral water, determined by using head space-GC/MS with PFBOA derivatization, have been reported. 13 In Japan, a method based on GC/MS with PFBOA deriv...

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“…humic substances), to produce LMW carbonyl compounds. [23] OH produced in Eqn 2 can react with itself by Eqn 4 to yield H 2 O 2 , which in turn can be photolysed by Eqn 5 to yield OH .…”

Section: Photochemical Sources Of Hchomentioning

confidence: 99%

Investigating the photo-oxidative and heterogeneous chemical production of HCHO in the snowpack at the South Pole, Antarctica

et al. 2014

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Environmental context. Snowpacks present a surprisingly active environment for photochemistry, leading to sunlight-induced oxidation of deposited organic matter and the subsequent emission of a variety of photochemically active trace gases. We seek to address questions regarding the ultimate fate of organic matter deposited onto snow in the remote regions of the world. The work is relevant to atmospheric composition and climate change.Abstract. We investigate snowpack fluxes of formaldehyde (HCHO) into the South Pole boundary layer using steadystate photochemical models. We study two chemical sources of HCHO within the snowpack. First, we study chemical production of HCHO from the processing of methyl hydroperoxide (CH 3 OOH): photolysis, reaction with the hydroxyl radical (OH ), and by an acid catalysed rearrangement. Assuming surface layer concentration effects for acidic solutes, we show that the acid catalysed production of HCHO within ice could contribute a non-negligible source to the snowpack HCHO budget. This novel source of HCHO complements existing explanations of HCHO fluxes based on physical emission of HCHO from snow. Secondly, we investigate HCHO production from the oxidation of organic matter (OM) by OH within snow to explain observed fluxes of photochemical origin from the South Pole snowpack. This work shows that laboratory-derived photochemical production rates of HCHO and our standard model are inconsistent with field observations, which has implications for the distribution of OM relative to oxidants within ice particles. We resolve this inconsistency using new laboratory measurements of the molecular dynamics of the OH photofragment from hydrogen peroxide (H 2 O 2 ) and nitrate (NO 3 À ) photolysis, which show that only OH produced in the outermost monolayers can contribute to gas phase and surface layer chemistry. Using these new measurements in conjunction with realistic treatments of ice grain size, H 2 O 2 and NO 3 À distribution within ice grains, diffusion of gas species within solid ice, and observed OM particle size distributions yields snowpack HCHO photochemical production rates more consistent with observations.

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Photochemical production of low-molecular-weight carbonyl compounds in seawater and surface microlayer and their air-sea exchange

Cited by 219 publications

References 28 publications

Budget of organic carbon in a polluted atmosphere: Results from the New England Air Quality Study in 2002

Budget of organic carbon in a polluted atmosphere: Results from the New England Air Quality Study in 2002

Rapid and Highly Sensitive Determination of Low-Molecular-Weight Carbonyl Compounds in Drinking Water and Natural Water by Preconcentration HPLC with 2,4-Dinitrophenylhydrazine

Investigating the photo-oxidative and heterogeneous chemical production of HCHO in the snowpack at the South Pole, Antarctica

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