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1.
Diurnal and vertical ambient air measurements of the monoterpenes have been made in and above a Scots pine (Pinus sylvestris) forest of central Sweden, within the boreal northern coniferous biome. Sampling was done with Tenax TA, and analysis by GC and ion trap detection. Daytime mixing ratios were on the order of tenths of a ppbv from the forest floor to the top of the forest, and a factor of 2 or 3 lower above the forest. Mixing ratios at night were at the ppbv level, highest near the forest floor and the crown, and decreased with height above the forest. The highest total concentration observed was 8 ppbv inside the forest at 3 am (GMT). The average terpene composition was 3-carene 32%, -pinene 29%, limonene 18%, -pinene 10%, -phellandrene 7%, camphene 5%, and sabinene at less than 2%. The 3-carene/-pinene ratio varied with wind direction and speed, relative humidity, and wet/dry vegetation, but not with ozone or NO2 concentration, solar radiation, or temperature. Variations in the observed terpene composition at the sampling site are mainly caused by the influence of other vegetation in the vicinity of the site. It would seem that wet Scots pine emits more 3-carene relative to -pinene than does dry pine.  相似文献   

2.
Atmospheric oxidation of monoterpenes contributes to formation of tropospheric ozone and secondary organic aerosol, but their products are poorly characterized. In this work, we report a series of outdoor smog chamber experiments to investigate both gaseous and particulate products in the ozone oxidation of four monoterpenes: -pinene, -pinene, 3-carene, and sabinene. More than ten oxygenated products are detected and identified in each monoterpene/O3 reaction by coupling derivatization techniques and GC/MS detection. A denuder/filter pack sampling system is used to separate and simultaneously collect gas and aerosol samples. The identified products, consisting of compounds containing carbonyl, hydroxyl, and carboxyl functional groups, are estimated to account for about 34–50%, 57%, 29–67%, and 24% of the reacted carbon mass for -pinene, sabinene, -pinene, and 3-carene, respectively. The identified individual products account for >83%, 100%, >90%, and 61% of the aerosol mass produced in the ozone reaction of -pinene, sabinene, -pinene, and 3-carene. The uncertainty in the yield data is estimated to be ±50%. Many of the products partition between gas and aerosol phases, and their gas-aerosol partitioning coefficients are determined and reported here. Reaction schemes are suggested to account for the products observed.  相似文献   

3.
Upto 13% of -pinene and 3-carene had reacted after 213 s in this dark experimental set-up, where O3, NO and NO2 were mixed with terpenes at different relative humidities (RHs). The different experiments were planned according to an experimental design, where O3, NO2, NO, RH and reaction time were varied between high and low settings (25 and 75 ppb, 15 and 42%, 44 and 213 s). An increased amount of -pinene and 3-carene reacted in the chamber was observed, when the level of O3, NO and reaction time was increased and RH was decreased. In the study, it was found that different interactions affected the amount of terpene reacted as well. These interactions were between O3 and NO, O3 and reaction time, NO and RH, and between NO and reaction time.  相似文献   

4.
The reactions of alkoxy radicals determine to a large extent the products formed during the atmospheric degradations of emitted organic compounds. Experimental data concerning the decompositions, 1,5-H shift isomerizations and reactions with O2 of several classes of alkoxy radicals are inconsistent with literature estimations of their absolute or relative rate constants. An alternative, although empirical, method for assessing the relative importance under atmospheric conditions of the reactions of alkoxy radicals with O2 versus decomposition was derived. This estimation method utilizes the differences in the heats of reaction, (H)=(Hdecomposition–HO 2 reaction), between these two reactions pathways. For (H)[22–0.5(HO 2 reaction)], alkoxy radical decomposition dominates over the reaction with O2 at room temperature and atmospheric pressure of air, while for (H)[25-0.5(HO 2 reaction)], the O2 reaction dominates over decomposition (where the units of H are in kcal mol–1). The utility and shortcomings of this approach are discussed. It is concluded that further studies concerning the reactions of alkoxy radicals are needed.  相似文献   

5.
The gas and particle phase reaction products of a mixture of the atmospherically important terpenes -pinene and -pinene with the atmospheric oxidants O3 and OH/NOx were investigated using both gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC) for identification and quantification of reaction products. The nighttime oxidation of a mixture of -pinene and -pinene in the presence of O3/air, and the daytime oxidation of a mixture of -pinene + -pinene with NOx air in the presence of natural sunlight were carried out in the University of North Carolina's large outdoor smog chamber (190 m3) located in Chatham County, North Carolina. Mass balances for gaseous and aerosol reaction products are reported over the course of the reaction. More than twenty-nine products were identified and/or quantified in this study. On average, measured gas and particle phase products accounted for 74 to 80% of the reacted -pinen/-pinene mixture carbon. Measurements show that a number of reaction products were found in both O3 and NOx system [pinonaldehyde, pinic acid, pinonic acid, pinalic-3-acid, 4-hydroxypinalic-3-acid, 4-oxonopinone, 1-hydroxy-nopinone, 3-hydroxy-nopinone, and nopinone]. Pinonic acid, pinic acid, pinalic-3-acid, 4-hydroxypinalic-3-acid, and 10-hydroxypinonic acid were observed in the early stage in the aerosol phase and may play an important role in the early formation of secondary aerosols.  相似文献   

6.
Formation of Organic Aerosols from the Oxidation of Biogenic Hydrocarbons   总被引：15，自引：0，他引：15  
Measurements of aerosol formation during thephotooxidation of -pinene, -pinene,d-3-carene, d-limonene, ocimene, linalool, terpinene-4-ol, andtrans-caryophyllene were conducted in anoutdoor smog chamber. Daylight experiments in thepresence of and dark experiments withelevated ozone concentrations were performed. Theevolution of the aerosol was simulated by theapplication of a gas/particle absorption model inconnection with a chemical reaction mechanism. Thefractional aerosol yield is shown to be a function ofthe organic aerosol mass concentration andtemperature. Ozone and, for selected hydrocarbons, theNO3 reaction of the compounds were found torepresent efficient routes to the formation ofcondensable products. For initial hydrocarbon mixingratios of about 100 ppb, the fractional aerosol yieldsfrom daylight runs have been estimated to be 5%for open-chain hydrocarbons, such as ocimene andlinalool, 5–25% for monounsaturated cyclicmonoterpenes, such as -pinene, d-3-carene, orterpinene-4-ol, and 40% for a cyclic monoterpenewith two double bonds like d-limonene. For the onlysesquiterpene investigated, trans-caryophyllene, afractional aerosol yield of close to 100% wasobserved. The majority of the compounds studied showedan even higher aerosol yield during dark experimentsin the presence of ozone.  相似文献   

7.
Emissions of volatile organic compounds (VOCs) from sunflower (Helianthus annuus L. cv. giganteus) were measured in a continuously stirred tank reactor. The compounds predominantly emitted from sunflower were: isoprene, the monoterpenes -pinene, -pinene, sabinene, 3-carene and limonene, an oxygenated terpene, not positively identified so far and the sesquiterpene -caryophyllene. Emission rates ranged from 0.8 x 10–16 to 4.3 x 10 –15 mol cm–2 s–1 at a temperature of 25°C and at a light intensity of 820 µEm–2 s–1. A dependence of the emission rates on temperature as well as on light intensity was observed. The emission rates of -pinene, sabinene and thujene from beech (Fagus sylvatica L.) were also affected by temperature as well as by light intensity. Our results suggest that an emission algorithm for all compounds emitted from sunflower and beech has to consider temperature and light intensity simultaneously. The observations strongly indicate that the emissions of VOCs from sunflower and beech are in part closely coupled to the rate of biosynthesis and in part originate from diffusion out of pools. The emission rates can be described by an algorithm that combines the model given by Tingey and coworkers with the algorithm given by Guenther and coworkers after slight modification.  相似文献   

8.
The gas and particle phase products from the reaction of -pinene with the atmospheric oxidants O3 and OH radicals in the presence of NOx were investigated using both gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC) for identification and quantification of reaction products. The nighttime oxidation of -pinene in the presence of O3/air and the daytime oxidation of -pinene in the presence of NOx/air and natural sunlight were carried out in the University of North Carolina large outdoor smog chamber (190 m3) located in Chatham County, North Carolina. A Scanning Mobility Particle Sizer system (3936, TSI) and a Condensation Particle Counter (3025A, TSI) were used to study the secondary organic aerosol (SOA) formation, and a filter pack/denuder sampling system was used for simultaneously collecting gas and particle phase products for analysis. A gas chromatograph coupled to a mass spectrometer (GC-EIMS or GC-CIMS) was used for the identification and quantification of gas and aerosol products. A HPLC method was used for the measurement of small carbonyl compounds (aldehydes and ketones) as their 2,4-dinitrophenylhydrazones (DNPH) derivatives. Mass balances for gaseous and aerosol reaction products were reported over the course of the reaction. More than sixteen products were identified and/or quantified in this study. On average, measured gas and particle phase products accounted for 57 to 71% of the reacted -pinene carbon. Measurements showed that a number of reaction products were found in both O3 and NOx systems (pinic acid, pinalic-3-acid, 4-hydroxypinalic-3-acid, 4-oxonopinone, 1-hydroxynopinone, 3-hydroxynopinone, and nopinone). Pinic acid, pinalic-3-acid, and 4-hydroxypinalic-3-acid were observed in the early stage in the aerosol phase and may play an important role in the early formation of secondary aerosols. Detailed reaction schemes are presented to account for most of the observed reaction products.  相似文献   

9.
The yields of products have been calculated for the reactions of hydroxyl radicals and ozone with 19 of the two-through-six carbon anthropogenic alkenes. Based on their rate of reaction, mechanisms of reactions and the ambient air distribution for these alkenes their seasonal ambient air yields have been estimated.Aldehydes predominate as products irrespective of season, with smaller yields of several ketones. Other minor products include carboxylic acids, carbon monoxide, carbon dioxide, and alkenes. About a two-fold increase is estimated in the yields of hot biradicals and their products from summer to winter.One sensitivity analysis was made by recomputing yields at a different OH radical to O3 concentration than assumed most likely in the calculations discussed above. In addition, the sensitivity of product yields to an estimated range of seasonally averaged sunset-to-sunrise NO3 radical concentrations was calculated. The effects of free radical reactions are discussed, but these are believed to make a relatively minor contribution within the NO x -rich atmospheres that contain anthropogenic alkenes.The uncertainties in product yields associated with the range of NO3 radical concentrations assumed present is relatively small for aldehydes, as is the decrease in yield of the one carbon hot biradical. Larger uncertainties occur for ketones. Significant decreases in yields occur for larger hot biradicals, especially the branched-chain hot radicals in the presence of NO3 radicals.  相似文献   

10.
A liquid jet of 90 m diameter and variable length has been utilized to determine absorption rates and, hence, mass accommodation coefficients , of atmospheric trace gases. The compounds investigated are HCl (0.01), HNO3 (0.01), N2O5 (0.005), peroxyacetyl nitrate (>0.001), and HONO (0.005). It is concluded that the absorption of these trace gases by liquid atmospheric water is not significantly retarded by interfacial mass transport. The strengths and limitations of the liquid jet technique for measuring mass accommodation coefficients are explored.  相似文献   

11.
Laboratory experiments under controlled environmental conditions are a useful tool to investigate the influence of different environmental parameters on VOC emissions from plants individually. Before using the obtained results to interpret measurements under ambient conditions, it has to be ensured that the laboratory system is suitable for performing emission rate measurements under ambient-like conditions to derive algorithms describing the emissions of volatile organic compounds as a function of physical variables like temperature and light intensity. Here we compare results from monoterpene emission rate measurements with Scots pines (Pinus sylvestris L.) under both ambient environmental conditions using a mobile plant enclosure chamber, and under controlled laboratory conditions in a continuously stirred tank reactor. The different analytical instruments to quantify monoterpene emissions were compared in an intercalibration experiment. Measurements of the mixing ratios of -pinene, -pinene, 3-carene, camphene, and limonene on the order of some hundred parts per trillion differed by less than 20%. The laboratory system has proven capable of providing ambient-like conditions and results of monoterpene emission rate measurements under laboratory conditions could be extrapolated to the natural environment. Monoterpene emission rate measurements with identical specimens of Scots pines conducted within small temporal differences under similar laboratory and outdoor conditions agreed well. Both laboratory and outdoor experiments clearly showed that distinct and constant values neither exist for the standard emission rates nor for the emission pattern of monoterpenes from Scots pine. Temporal variations in the standard emission rates from identical specimens and plant-to-plant variations were on the order of one magnitude.  相似文献   

12.
The photooxidation of -humulene in the presence of NOx, natural sunlight, and rural background air was investigated using a combination of gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography (HPLC). Identification and quantification of gas and particulate reaction products were reported over the course of the reaction. The daytime photooxidation was carried out in a large outdoor smog chamber (190 m3). A wide range of ring retaining and ring opening products in the gas and particle phase are reported. On average, measured gas and particle phase products accounted for 44% of the reacted -humulene carbon. Measurements show that a number of reaction products with low vapor pressures (e.g. 3-seco--humulone aldehyde, 7-seco--humulone aldehyde, -humulal aldehyde, -humulene 3-oxide or -humulene 7-oxide, -humulaic/alic acid isomers, and 3-seco--14-hydroxyhumulone aldehyde) were found in the early stage of the reaction and may play an important role in the early formation of secondary organic aerosol. A detailed mechanism is proposed to account for most products observed in this investigation.  相似文献   

13.
The aim of this work is to study the reactivity of some naturally emitted terpenes, 2-carene, sabinene, myrcene, -phellandrene, d-limonene, terpinolene and -terpinene, towards NO3 radical to evaluate the importance of these reactions in the atmosphere and their atmospheric impact. The experiments with these monoterpenes have been carried out under second-order kinetic conditions over the range of temperature 298–433 K, using a discharge flow system and monitoring the NO3 radical by Laser Induced Fluorescence (LIF). This work is the first temperature dependence study for the reactions of the nitrate radical with the above-mentioned monoterpenes. The measured rate constants at 298 K for the reaction of NO3 with such terpenes are as follows: 2-carene, 16.6 ± 1.8, sabinene 10.7 ± 1.6, myrcene 12.8 ± 1.1, -phellandrene 42 ± 10, d-limonene 9.4 ± 0.9, terpinolene 52 ± 9 and -terpinene 24 ± 7, in units of 10-12 cm3 molecule-1 s-1. The proposed Arrhenius expressions, for the reactions of NO3 with 2-carene, sabinene, myrcene and -phellandrene are, respectively k1 = (1.4 ± 0.7) × 10-12 exp[(741 ± 190/T)] (cm3 molecule-1 s-1), k2=(2.3 ± 1.3) × 10-10 exp[–(940 ± 200/T)] (cm3 molecule-1 s-1), k3 = (2.2 ± 0.2) × 10-12 exp[(523 ± 35/T)] (cm3 molecule1 s-1) and k4 = (1.9 ± 1.3) × 10-9 exp[–(1158 ± 270/T)] (cm3 molecule-1 s-1). A decrease in the rate constants when raising the temperature has also been found for the reaction of d-limonene with NO3 while an increase in the rate constant with temperature has been observed for the reactions of terpinolene and -terpinene with NO3. Tropospheric half-lives for these terpenes have been calculated at night and during the day for typical NO3 and OH concentrations showing that both radicals provide an effective tropospheric sink for these compounds and that the night-time reaction with NO3 radical can be an important, if not dominant, loss process for these naturally emitted organics and for NO3 radicals.  相似文献   

14.
The formation and occurrence of hydroperoxides in the troposphere have been studied by laboratory experiments and by preliminary field measurements. Nine alkenes were reacted individually with ozone in a reaction chamber in the presence of excess water, and the amounts of hydrogen peroxide and of nine organic hydroperoxides produced in the gas and aerosol phases and deposited on the chamber walls determined by HPLC. The reactions of ethene, propene, 1-butene and isoprene gave hydroxymethyl hydroperoxide as the major product with no hydrogen peroxide observed. In the case of - and -pinene, 2-carene and limonene the major product was hydrogen peroxide. Cis-2-butene produced hydrogen peroxide and methyl hydroperoxide. Preliminary measurements of hydrogen peroxide and five organic hydroperoxides in ambient air were made at Niwot Ridge, Colorado from 24 July–4 August 1989. The gas-phase species were preconcentrated by cryotrapping with subsequent HPLC separation. The gas-phase concentrations of H2O2 ranged from 0.5–2 ppbv with the lowest concentrations being measured at night and the highest under conditions of strong photochemical activity. The maximum concentrations of hydroxymethyl hydroperoxide approximated those of H2O2. Methyl hydroperoxide concentrations ranged from <50 to 800 pptv and three other organic hydroperoxides were detected at concentrations below 200 pptv. High volume aerosol samples yielded H2O2 and methyl hydroperoxide concentrations <10 ng m-3 while H2O2 and six organic species were detected in rainwater at concentrations in the range <0.01–50 M.  相似文献   

15.
Smog chamber experiments have beenconducted in which cyclic monoterpenes were oxidisedin the gas phase by OH. The evolved secondary organicaerosol (SOA) was analysed by LC-MSn and thegas-phase products were analysed by FT-IR. Theconcentrations of the identified compoundscorresponded to carbon mass balances in the range of40%–90%. The identified compounds in the particularphase corresponded to 0.5%–4.2% of the reactedcarbon. The most abundant compounds in SOA fromterpenes with an endocyclic C=C double bond wereC10-keto-aldehydes, C10-keto-carboxylicacids, C10-hydroxy-keto-carboxylic acids, andC10-hydroxy-keto-aldehydes (pinonaldehyde,pinonic acid, hydroxy-pinonic acid isomers, andhydroxy-pinonaldehyde isomers from -pinene;3-caronaldehyde, 3-caronic acid, hydroxy-3-caronicacid isomers, and hydroxy-3-caronaldehyde isomers from3-carene). The most abundant compounds in SOA fromterpenes with an exocyclic C=C double bond wereC9-ketones, C9-dicarboxylic acids, andC10-hydroxy-keto-carboxylic acids (nopinone,pinic acid, and hydroxy-pinonic acid isomers from-pinene; sabinaketone, sabinic acid andhydroxy-sabinonic acid isomers from sabinene).Decarboxylated analogues of most of the compounds werepresent in SOA in minor concentrations, such asC9-keto-carboxylic acids (norpinonic acid,nor-3-caronic acid) and C8-dicarboxylic acids(norpinic acid, nor-3-caric acid, norsabinic acid). InSOA from limonene, which contains an endocyclic aswell as an exocyclic C=C double bond, the mostabundant compounds were a C10-keto-aldehyde andits oxo-derivative (limononaldehyde and keto-limononaldehyde) together with hydroxy-derivatives of aC10-keto-carboxylic acid (isomers ofhydroxy-limononic acid). Also aC10-keto-carboxylic acid (limononic acid) waspresent together with minor concentrations of aC9-dicarboxylic acids (limonic acid), itsoxo-derivative (keto-limonic acid), and itsdecarboxylated analogue (norlimonic acid). Mechanisticpathways for the formation of these products, some ofwhich are identified here for the first time, areproposed.  相似文献   

16.
Cloud water and interstitial aerosol samples collected at Mt. Sonnblick (SBO) were analyzed for sulfate and aerosol carbon to calculate in-cloud scavenging efficiencies. Scavenging efficiencies for sulfate (SO) ranged from 0.52 to 0.99 with an average of 0.80. Aerosol carbon was scavenged less efficiently with an average value (AC) of 0.45 and minimum and maximum values of 0.14 and 0.81, respectively. Both SO and AC showed a marked, but slightly different, dependence on the liquid water content (LWC) of the cloud. At low LWC, SO increased with rising LWC until it reached a relatively constant value of 0.83 above an LWC of 0.3 g/m3. In the case of aerosol carbon, we obtained a more gradual increase of AC up to an LWC of 0.5 g/m3. At higher LWCs, _ remained relatively constant at 0.60. As the differences between SO and A varied across the LWC range observed at SBO, we assume that part of the aerosol carbon was incorporated into the cloud droplets independently from sulfate. This hypothesis is supported by size classified aerosol measurements. The differences in the size distributions of sulfate and total carbon point to a partially external mixture. Thus, the different chemical nature and the differences in the size and mixing state of the aerosol particles are the most likely candidates for the differences in the scavenging behavior.  相似文献   

17.
To determine if Cu mediated reactions on atmospheric particles are important to HO2 chemistry in the ambient atmosphere, Cu molalities were calculated from measured Cu aerosol particle concentrations, mass and number size distribution data from a site in central Sweden. A comparison of characteristic times indicates that at low relative humidities the reaction is limited by the mass transport of gas phase HO2 to the particle surface and not by the chemical kinetics of the aqueous reaction. Comparison of half-lives for particle reactions and the gas phase destruction of HO2 to form H2O2 indicate that heterogeneous reactions on aerosol particles may have important consequences on the chemistry of HO2 and H2O2 in the troposphere.  相似文献   

18.
The NO3 radical initiated oxidation of cyclopentene, cyclohexene and 1-methyl-cyclohexene has been studied. The products formed in an N2O5-NO2-N2-O2-cycloalkene-static reactor system, at 0.1 MPa and 296 K, were investigated using long path FTIR. The principal products were aldehydes formed via a ring opening process. The reactions also resulted in significant yields of three types of ring retaining nitrooxy-substituted compounds. The average yields of alkyl nitrates from, e.g., reactions with cycloalkene were 25.1% 2-oxo-cyclohexyl nitrate, 22.8% 2-hydroxy-cyclohexyl nitrate and 4.0% 1,2-cyclohexyl dinitrate. The mechanisms involved resembles those proposed for acyclic alkenes. In absence of NO, -oxo and -hydroxy-cycloalkyl nitrates are formed via self reactions of -nitrooxy substituted cycloalkyl peroxy radicals. Estimated branching ratios for the reactants leading to ring retaining products in the presence and in the absence of NO are given and the possible relevance of these reactions for cycloalkenes under tropospheric conditions is discussed.  相似文献   

19.
Summary During an expedition to the high Andes of Southern Peru in June–July 1977, measurements of direct solar radiation in four spectral bands (0.270–0.530–0.630–0.695–2.900 ) were conducted at six sites in elevations ranging from sea level to 5645 m. These measurements were evaluated in Langley plots to determine total optical depths () and irradiances at the top of the atmosphere. In addition, water vapor optical depths (wv) were calculated from the mean radiosounding over Lima during the expedition, and Rayleigh (ray) and ozone (oz) optical depths were obtained from published tabulations. Subtracting ray, oz, and wv from yielded estimates of aerosol optical depth aer. The components ray and oz decrease from the shorter towards the longer wavelength bands and from the lower towards the higher elevation sites; aer also decreases towards the higher elevations. Particularly pronounced is the decrease of aer and from the lowlands of the Pacific coast to the highlands of the interior, reflecting the effect of a persistent lower-tropospheric inversion and the contrast from the marine boundary layer to the clear atmosphere of the high Andes.With 4 Figures  相似文献   

20.
Tropospheric photodissociation rate coefficients (J values) were calculated for NO2, O3, HNO2, CH2O, and CH3CHO using high spectral resolution (0.1 mm wavelength increments), and compared to the J values obtained with numerically degraded resolution (=1, 2, 4, 6, 8, and 10 nm, and several commonly used nonuniform grids). Depending on the molecule, substantial errors can be introduced by the larger increments. Thus for =10 nm, errors are less than 1% for NO2, less than 2% for HNO2, +6.5% to -16% for CH2O, -6.9% to +24% for CH3CHO, and -24% to +110% for O3. The errors for CH2O arise from the fine structure of its absorption spectrum, and are prevalently negative (underestimate of J). The errors for O3, and to a lesser extent for CH3CHO, arise mainly from under-resolving the overlap of the molecular action spectrum and the tropospheric actinic flux in the wavelength region of stratospheric ozone attenuation. The sign of those errors depends on whether the actinic flux is averaged onto the grid before or after the radiative transfer calculation. In all cases studied, grids with 2 nm produced errors no larger than 5%.  相似文献   

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