首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 594 毫秒
1.
The gas-particle partitioning of select semivolatile organic compounds (SOCs) was studied by injecting the SOCs into a 190 m3 Teflon film chamber containing a secondary organic aerosol (SOA) generated by volatilizing liquid -pinene into an ozone-concentrated atmosphere. The concentration of total suspended particulates (TSP) and gas and particle-phase SOCs was measured over the course of three experiments spanning a temperature range of 268–297 K and a relative humidity range of 55–100%. An equilibrium partition coefficient, Kp, was calculated for each sampling event. Empirical relationships were then developed to predict the partitioning of the SOCs on the SOA particle source as a function of temperature. Partitioning in this SOA system was compared to that of a SOA generated by the photochemical reaction of NOx with m-xylene. The results indicate that partitioning is similar between the two SOA systems. The effects of multiple particle sources on partitioning was also examined, revealing that a weighted average of predicted Kp values for individual sources can be used to predict partitioning in aerosol mixtures.  相似文献   

2.
The amounts of SOA and reactive oxygen species (ROS) formed by the reaction of α-pinene with ozone (O3) in the presence of nitric oxide (NO) were studied by varying the ratio of O3 to NO in a chamber under conditions that simulate the indoor environment. The particle mass was measured using a tapered element oscillating microbalance (TEOM) and a scanning mobility particle sizer (SMPS) was used to obtain particle volume distributions. The concentrations of particle-bound reactive species (ROS) were quantitatively determined from collected filters by the measuring the oxidation of dichlorofluorescin (DCFH) to a fluorescent product. The measured fluorescent intensities were converted to equivalent H2O2 concentrations. Three sets of experiments using different concentration ratios of NO/O3 were conducted. Measured steady-state, particle-bound ROS concentrations ranged from 0.58 to 6.78 nmol/m3 of H2O2. The SOA yields were examined using Odum’s SOA yield model that relates the mass of SOA formed to the mass of hydrocarbon consumed. For the condition where NO and O3 were in a concentration ratio of 0.5, the SOA yield was the highest with 22 % of α-pinene converted to SOA. Under these experimental conditions, the highest concentration of nitrate radical in these experiments would have been produced.  相似文献   

3.
Nitrogen-containing organic compounds (NOC) formed from secondary organic aerosols (SOA) age via reaction with reduced nitrogen species are a vital class of brown carbon compounds. NOC compounds from ammonia (NH3) gas-aging of benzene SOA were investigated in present study, and the experiments were performed by irradiating benzene/CH3ONO/NO/NH3 air mixtures in a home-made smog chamber. The particulate NOC products of aged benzene SOA in the presence of NH3 were measured by UV-Vis spectrophotometer, attenuated total reflectance-Fourier transform infrared (ATR-FTIR), and aerosol laser time-of-flight mass spectrometer (ALTOFMS) coupled with Fuzzy C-Means (FCM) clustering algorithm, respectively. Experimental results demonstrated that NH3 has significant promotion effect on benzene SOA formation. Organic ammonium salts, such as ammonium glyoxylate, ammonium 6-oxo-2,4-hexadienoiclate, which are formed from NH3 reactions with gaseous organic acids were detected as the major particulate NOC products of NH3-aged benzene SOA. 1H–imidazole, 1H–imidazole-2-carbaldehyde and other imidazole products via the heterogeneous reactions between NH3 and dialdehydes of benzene SOA were successfully detected as important brown carbon constituents. The formation of imidazole products suggests that some ambient particles contained organonitrogen compounds may be come from this mechanism. The results of this study may provide valuable information for discussing NH3 deposition and SOA aging mechanisms.  相似文献   

4.
Rate constants have been measured for the reactions of hydroxyl radicals with alkyl nitrates and with some oxygen-containing organic compounds by a competitive technique. Mixtures of synthetic air containing a few ppm of nitrous acid, ethylene and the organic substrate were photolysed in a Teflon bag smog chamber. Based on the value k HO+C2H4}=8.1×10-12 cm3 molecule-1 s-1 the following rate constants were obtained for the hydroxyl radical reactions at 750 Torr and at 303 K in units of 10-12 cm3 molecule-1: CH3ONO2, 0.37±0.09; C2H5ONO2, 0.48±0.20; n-C3H7ONO2, 0.70±0.22; C2H5OH, 3.6±0.4; CH3COCH3, 0.26±0.08; CH3CO2 i-C3H7, 3.0±0.8; CH3CO2 n-C3H7, 2.4±0.2. The results are discussed in relation to the available literature data and the implications of the results are considered in terms of the smog reactivity of these molecules.  相似文献   

5.
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   

6.
In remote marine aerosol samples collected from the North Pacific ocean, Enewetak Atoll, American Samoa, and New Zealand, series of mid-chain ketocarboxylic acids in the range of C6-C18 were detected. All the positional isomers, except for the 2-oxo and 3-oxo species, were detected for major ketoacid families (e.g. C9, C11 and C13). Higher ketoacid concentrations (up to 19 ng/m3) were obtained in the northern North Pacific aerosol samples, which generally showed an odd carbon-numbered predominance with 5-oxoundecanoic acid being the major species. By contrast, lower concentrations were obtained in the lower-latitude or subtropical aerosol samples, where even carbon-numbered ketoacids were relatively abundant.The distribution patterns of the odd carbon-numbered ketoacids could not be explained by the primary emissions from source materials including terrestrial higher plants, soil particles, and ocean surfaces. We consider that the isomeric ketocarboxylic acids are produced in the atmosphere by the photochemical oxidation of semi-volatile monocarboxylic acids, which are counterparts of the oxidative degradation of unsaturated fatty acids emitted from seawater surfaces. Atmospheric production of the ketoacids is seemingly enhanced in the northern North Pacific, probably due to an enhanced primary productivity.  相似文献   

7.
  相似文献   

8.
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   

9.
To better understand the role of terpenic compounds in atmospheric chemistry the influence of sobrerol, a water-soluble product of photochemical autoxidation or ozonolysis of -pinene, on the rate of S(IV) autoxidation was studied. Laboratory experiments were performed under heterogeneous conditions, at constant supply with S(IV) by dissolution of CaSO3.1/2 H2O fine particles and with air oxygen by diffusion through a planar gas-liquid interface. The progress of S(IV) autoxidation, uncatalysed or catalysed by Fe2(SO4)3 or CoSO4, was followed conductometrically. The inhibiting effect of sobrerol was discussed in terms of the chain reaction terminated in a step linear with respect to sulphoxy radicals. A method was proposed for quantification of the inhibiting effect and the rate constant (2.0–3.8)108 M–1s–1 was given for the step eliminating sulphate radicals. Further consequences of the inhibition: shifting the reaction locus from the gas-liquid (droplet) interface to the liquid (droplet) bulk and strong oscillations in the rate of S(IV) autoxidation resulting of the activity of sobrerol-derived radicals were also shown.  相似文献   

10.
Henry's law constants KH (mol kg-1 atm-1) have been measured between 278.15 K and 308.15 K for the following organic acids: CH2FCOOH (ln(KH[298.15 K]) = 11.3 ± 0.2), CH2ClCOOH (11.59 ± 0.14), CH2BrCOOH (11.94 ± 0.21), CHF2COOH (10.32 ± 0.10), CHCl2COOH (11.69 ± 0.11), CHBr2COOH (12.33 ± 0.29), CBr3COOH (12.61 ± 0.21), and CClF2COOH (10.11 ± 0.12). The variation of KH with temperature was determined for all acids except CH2FCOOH and CBr3COOH, with r H° for the dissolution reaction ranging from –85.2 ± 2.6 to –57.1 ± 2.5 kJ mol-1, meaning that their solubility is generally more sensitive to temperature than is the case for the simple carboxylic acids. The Henry's law constants show consistent trends with halogen substitution and, together with their high solubility compared to the parent (acetic) acid (ln(KH[298.15 K]) = 8.61), present a severe test of current predictive models based upon molecular structure. The solubility of haloacetic acids and strong dissociation at normal pH mean that they will partition almost entirely into cloud and fog in the atmosphere (0.05–1.0 g H2O m-3), but can reside in both phases for the liquid water contents typical of aerosols (10-5-10-4 g H2O m-3).  相似文献   

11.
This paper examines changes in carbon (C) pools associated with land-use, synthesizing data from two experiments dealing with different aspects of tree plantation establishment in Central Panamá. First, we analysed soil profiles in a grazed pasture and an adjacent 5-year-old teak (Tectona grandis) plantation. There were small differences in soil C mass in the top 10 cm of the pasture and the plantation, though analysis of paired profiles suggested larger differences at greater depth. Analysis of the 13C signatures in the pasture soils and litter showed that 90% to 95% of the organic matter in the surface 5 cm was derived from C4 pasture plants, over the 45 years since the pasture was converted from forest. Comparison of the 13C signatures in the pasture and teak plantation profiles indicated substantial replacement of C4—derived organic matter with the dominantly C3—derived plantation tissues. Organic matter turnover times in the upper 10 cm of the soils ranged from 8 to 34 years and from 11 to 58 years in the upper 30 cm, depending on topographic location. We also present preliminary results, and technical challenges, for an eddy covariance experiment set up to provide a direct comparison between a grazed pasture and a native tree plantation. The two ecosystems studied are estimated to be small CO2 sinks, 92 g,C,m–2 yr–1 for the pasture, and 57 g,C,m–2 yr–1 for native species plantation in the first year after establishment. The pastures response to seasonal change was more pronounced, both in term of CO2 fluxes and in term of herbaceous productivity, than the plantations response. The storage below ground systems contained up 40% of the total sapling biomass.  相似文献   

12.
Henry's law constantsK H (mol kg–1 atm–1) have been determined at 298.15 K for the following organic acids: formic acid (5.53±0.27×103); acetic acid (5.50±0.29×103); propionic acid (5.71±0.34×103);n-butyric acid (4.73±0.18×103); isobutyric acid (1.13±0.12×103); isovaleric acid (1.20±0.11×103) and neovaleric acid (0.353±0.04×103). They have also been determined fromT=278.15 K toT=308.15 K forn-valeric acid (ln(K H)=–14.3371+6582.96/T);n-caproic acid (ln(K H)=–13.9424+6303.73/T) and pyruvic acid (ln(K H)=–4.41706+5087.92/T). The influence of 9 salts on the solubility of pyruvic acid at 298.15 K has been measured. Pyruvic acid is soluble enough to partition strongly into aqueous atmospheric aerosols. Other acids require around 1 g of liquid water m–3 (typical of clouds) to partition significantly into the aqueous phase. The degree of partitioning is sensitive to temperature. Considering solubility and dissociation (to formate) alone, the ratio of formic acid to acetic acid in liquid water in the atmosphere (at equilibrium with the gas phase acids) is expected to increase with rising pH, but show little variation with temperature.  相似文献   

13.
To systematically explain relations between light hydrocarbons, CO, and CO2 concentrations/emissions of biomassburning, we measured concentrations/emissions of carbon gases – CO,CO2, light hydrocarbons (CH4, C2H6,C2H4, C2H2, C3H8, C3H6,n-C4H10, i-C4H10, n-C5H12,i-C5H12), and THC (total hydrocarbon) – in the burning of dead plant material, mainly Imperata grass, byclosed-chamber experiments and by time-series analyses of gas concentrations in combustion plumes in relatively efficient and inefficient combustion situations. Concentrations of hydrocarbons measured were well correlated to [CO] although [C2H2] was exceptionally well correlated to[CO2]. The phase diagrams (relation between [CO]/ [CO2] and [hydrocarbon]/ [CO2]) obtained by the time-seriesexperiments well illustrated the variation in the overall emission rates of the closed-chamber experiments. The higher rates of decrease in hydrocarbon concentration with increasing carbon number in the efficient case compared with the inefficient case probably reflected the rate of oxidation and the amount of radicals. The overall concentrations (or emissions) of C2H4 and C3H6 were higher thanthose of C2H6 and C3H8, suggesting a linkage to mechanisms in whichthe predominant path of hydrocarbon oxidation is through the degradation of alkyl radicals, which can be immediately converted into or formed from alkenes. For C3 and C4 species, normal-chain species hadhigher emissions than iso-chain species under lower combustion efficiency. This may be attributable to the presence of tertiary C–H bonds in iso-species,which show more reactivity in the abstraction of H than secondary C–H bonds unless the carbon number is large.  相似文献   

14.
FOS/DECAFE 91 (Fire of Savannas/Dynamique et Chimie Atmosphérique en Forêt Equatoriale) was the first multidisciplinary experiment organized in Africa to determine gas and aerosol emissions by prescribed savanna fires. The humid savanna of Lamto in Ivory Coast was chosen for its ecological characteristics representative of savannas with a high biomass density (900 g m–2 dry matter). Moreover the vegetation and the climate of Lamto have been studied for more than twenty years. The emission ratios (X/CO2) of the carbon compounds (CO2, CO, NMHC, CH4, PAH, organic acids and aerosols), nitrogen compounds (NOx, N2O, NH3 and soluble aerosols) and sulfur compounds (SO2, COS and aerosols) were experimentally determined by ground and aircraft measurements. To perform this experiment, 4 small plots (100×100 m) and 2 large areas (10×10 km) were prepared and burnt in January 1991 during the period of maximum occurrence of fires in this type of savanna. The detailed ecological study shows that the carbon content of the vegetation is constant within 1% (42 g C for 100 g of vegetal dry matter), the nitrogen content (0.29 g N for 100 g of dry matter) may vary by 10% and the sulfur content (0.05 g S/100 d.m.) by 20%. These variations of the biomass chemical content do not constitute an important factor in the variation of the gas and particle emission levels. With the emission ratios characteristic of humid savanna and flaming conditions (CO/CO2 of 6.1% at the ground and 8% for airborne measurements), we propose a set of new emission factors, taking into account the burning efficiency which is about 80%: 74.4% of the carbon content of the savanna biomass is released to the atmosphere in the form of CO2, 4.6% as CO, 0.2% as CH4, 0.5% as NMHC and 0.7% as aerosols. 17.2% of the nitrogen content of the biomass is released as NOx, 3.5% as N2O, 0.6% as NH3 and 0.5% as soluble aerosols.  相似文献   

15.
The reactivity of some selected biogenic monoterpenecompounds towards important aqueous phase free-radicaloxidants, namely OH· and SO4 -·, have beeninvestigated using the complementary experimentaltechniques of pulse radiolysis and laser flashphotolysis ( = 248 nm). Rate constants forthe reactions of the OH· radical with cis-verbenol andmethacrolein have been determined to be (6.8 ± 0.5) ×109 dm3 mol-1 s-1 and (8.0± 0.7) × 109 dm3 mol-1s-1,respectively (T = 20 °C, pH 4.0, Ionic strength 0 mol dm-3). Rate constants and activationenergies for the reactions of the SO4 -·radical have been measured for the following compounds(T = 20 °C, pH 4.0, Ionic strength = 0.03 moldm-3): -pinene (k = (3.1 ± 0.1) ×109 dm3 mol-1 s-1;E act. =(8.9 ± 1.3) kJ mol-1), -terpineol(k = (4.1 ± 0.1) × 109 dm3mol-1s-1; E act. = (13.4 ± 0.6) kJmol-1), cis-verbenol (k = (3.2 ± 0.2) ×109 dm3 mol-1 s-1;E act. =(10.0 ± 0.7) kJ mol-1), verbenone (k = (1.6± 0.1) × 109 dm3 mol-1s-1;E act. = (6.1 ± 0.7) kJ mol-1), myrtenal(k = (1.85 ± 0.1) × 109 dm3mol-1s-1; E act. = (7.5 ± 0.7) kJmol-1)and methacrolein (k = (1.18 ± 0.1) × 109dm3 mol-1 s-1). In most instances theabsorption spectra of the intermediate products formedby these reactions have been measured which, inconjunction with strategic conductiometric studies,have been used to suggest plausible mechanisms for theoxidation in acidic de-oxygenated solution.  相似文献   

16.
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   

17.
Gaseous formic and acetic acids in the atmosphere of Yokohama,Japan   总被引：1，自引：1，他引：0  
Gaseous formic acid (HCOOHg) and acetic acid (CH3COOHg) were measured every 30 minutes during a 10 hour daylight period in August, and a 24 hour period in October, 1990 in the urban atmosphere of Yokohama, Japan. An aqueous nebulizer sampler and ion-chromatography exclusion (ICE) were used for the measurements. In the August experiment (0800–1800 local time) the mean HCOOHg concentration was found to be 7.3±2.5 ppbv. The mean CH3COOHg concentration was 3.8±1.2 ppbv. In the 24 hour experiment in October, concentrations of both acids were lower between 0800–1800 than during the same time-period in August (mean HCOOHg=4.4±2.7 ppbv, mean CH3COOHg=1.4±0.5 ppbv). In October, concentrations of both acids were higher in daylight hours than at night; sporadic high HCOOHg concentrations were observed. In both experiments the ratio HCOOHg/CH3COOHg of individual samples was usually 2.0 (mean ratio of 2.0 in August, 3.1 in October).  相似文献   

18.
A 2-D meridional model for the chemistry and transport in the troposphere is used to study the seasonal variation of the concentration of organic gases like C2H2, C2H6, C3H8, C6H6, C7H8. CHCl3 and C2Cl4 at high latitudes. The anthropogenic sources for these species were estimated, and the temporal and latitudinal distribution of OH and O3 was calculated using a complex photochemical reaction system. There is fair agreement between the calculated annual variation and the measured concentrations for C2H2, C2H6, C3H8, C7H8 and C2Cl4 at Spitsbergen during July 1982 and March/April 1983, with a distinct late winter maximum and summer minimum. For CHCl3, the direct anthropogenic source is minor compared to indirect anthropogenic or natural sources. For benzene, emission in car exhaust is important, but other anthropogenic sources are required for the calculations to agree with the measurements. Measured C2H4 and C3H6 concentrations are much higher than the calculated ones based on anthropogenic emissions, and show opposite seasonal trends. This indicates biogenic sources for these compounds.A buildup of PAN (300 pptv) is calculated at high latitudes during winter. This makes it the dominant source for NOx as the temperature increases in the spring. NOx is found to be a limiting factor for O3 production at high latitudes during spring.  相似文献   

19.
Air-sea bulk transfer coefficients in diabatic conditions   总被引：13，自引：0，他引：13  
On the basis of recent data for the roughness Reynolds number of the sea surface, and using the Owen-Thomson theory on the transfers of heat and mass between a rough surface and the flow above it, the bulk transfer coefficients of the sea surface have been estimated. For a reference height of 10 m, the neutral-lapse transfer coefficient for water vapor is larger by only a few percent than that for sensible heat. When the wind speed at the 10-m height is u 10>3 m s–1, the coefficient for sensible heat C H is larger by about 10% than that for momentum C D . For u 10<5 m s–1, however, the value of C D exceeds the value of C H , and for u 10=15 m s–1 it is shown that C H 0.8C D . It may be also proposed that 103 C D =1.11 to 1.70, 103 C E =1.18 to 1.30, and 103 C H =1.15 to 1.26 for a range of u 10=4 to 20 m s–1. A plot of diabatic transfer coefficients versus wind speed is obtained by using a parameter of the sea-air temperature difference. For practical purposes, the coefficients are approximated by empirical formulae.  相似文献   

20.
  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号