Volatile Organic Compounds in the Po Basin. Part A: Anthropogenic VOCs

Measurements of volatile organic compounds (VOCs) were performed in the Po Basin, northern Italy in early summer 1998 within the PIPAPO project as well as in summer 2002 and autumn 2003 within the FORMAT project. During the three campaigns, trace gases and meteorological parameters were measured at a semi-rural station, around 35 km north of the city center of Milan. Low toluene and benzene concentrations and lower toluene to benzene ratios on weekends, on Sundays, and in August enabled the identification of a ‘weekend’ and a ‘vacation’ effect when anthropogenic emissions were lower due to less traffic and reduced industrial activities, respectively. Recurrent nighttime cyclohexane peaks suggested a periodical short-term release of cyclohexane close to the semi-rural sampling site. A multivariate receptor model analysis resulted in the distinction of different characteristic concentration profiles attributed to natural gas, biogenic impact, vehicle exhaust, industrial activities, and a single cyclohexane source.     

植物挥发性有机物的初步研究

2000年1～6月期间,美国国家大气研究中心(NCAR)和中国科学院大气物理研究所的科学家发展了一套自动的气相色谱系统和分析方法,用于分析大气中的挥发性有机物.此系统性能稳定,重复性好,对美国大气研究中心附近的大气进行了采样分析.作者简单介绍了此自动系统以及采样分析结果.     

Biogenic Volatile Organic Compounds (VOC): An Overview on Emission, Physiology and Ecology

This overview compiles the actual knowledge of the biogenic emissions of some volatile organic compounds (VOCs), i.e., isoprene, terpenes, alkanes, alkenes, alcohols, esters, carbonyls, and acids. We discuss VOC biosynthesis, emission inventories, relations between emission and plant physiology as well as temperature and radiation, and ecophysiological functions. For isoprene and monoterpenes, an extended summary of standard emission factors, with data related to the plant genus and species, is included. The data compilation shows that we have quite a substantial knowledge of the emission of isoprene and monoterpenes, including emission rates, emission regulation, and biosynthesis. The situation is worse in the case of numerous other compounds (other VOCs or OVOCs) being emitted by the biosphere. This is reflected in the insufficient knowledge of emission rates and biological functions. Except for the terpenoids, only a limited number of studies of OVOCs are available; data are summarized for alkanes, alkenes, carbonyls, alcohols, acids, and esters. In addition to closing these gaps of knowledge, one of the major objectives for future VOC research is improving our knowledge of the fate of organic carbon in the atmosphere, ending up in oxidation products and/or as aerosol particles.     

Emissions of Volatile Organic Compounds from Sunflower and Beech: Dependence on Temperature and Light Intensity

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.     

Emission of Biogenic Volatile Organic Compounds: An Overview of Field, Laboratory and Modelling Studies Performed during the `Tropospheric Research Program' (TFS) 1997–2000

The present paper summarises results on the emission of biogenicvolatile organic compounds (BVOC) achieved within the frame of thenational `German Tropospheric Research Programme' (TFS) between 1997 and2000. Field measurements were carried out at the meteorologicalmonitoring station `Hartheimer Wald' located in the vicinity of Freiburg(upper Rhine valley), Germany, within a pine plantation dominated byScots pine (Pinus sylvestris L.). The measured BVOC emissionrates were used to determine the daily and seasonal variation of BVOCemission and its dependence on important meteorological and plantphysiological parameters. In parallel, laboratory experiments usingyoung trees of pine (P. sylvestris), poplar (Populustremula ×P. alba) and pedunculate oak (Quercusrobur L.) were performed, and the influence of abiotic (e.g.,light, temperature, seasonality, flooding) factors on the biosynthesisand emission of BVOC was quantified. Based on these data, emissionalgorithms were evaluated and a process-oriented numerical model for thesimulation of the isoprene emission by plants was developed. Inaddition, newly calculated land use and tree species distributions wereused for the calculation of an actual BVOC emission inventory ofGermany.     

Emissions of Oxygenated Volatile Organic Compounds from Plants Part I: Emissions from Lipoxygenase Activity

Emissions of oxygenated volatile organic compounds (OVOC) from several plant species were measured in continuously stirred tank reactors (CSTR). High emission pulses of OVOCs were observed when plants were exposed to stress. Absolute emission rates were highly variable ranging up to 10^–13 mol · cm^–2 · s^–1. The temporal shape of these emissions was described by a formalism similar to that of a consecutive reaction of pseudo first order kinetics. The main emitted OVOC was (Z)-3-hexenol together with other C₆-aldehydes and alcohols, suggesting that lipoxygenase activity on linolenic acid was mainly responsible for OVOC production. Various stress factors induced lipoxygenase activity and subsequent emissions of OVOCs. These factors were exposure to high ozone concentrations, pathogen attack, and wounding. The pattern of OVOC emissions from tobacco was similar for different stress applications and the same products of lipoxygenase activity were emitted from all investigated plant species. Our results imply that these emissions occur as general response of the plants to stress. Since plants experience various abiotic or biotic stress factors in the environment, OVOC emissions as a response to stress are likely to be of significant importance for atmospheric chemistry.Now at     

Emissions of Oxygenated Volatile Organic Compounds from Plants Part II: Emissions of Saturated Aldehydes

Emissions of hexanal, heptanal, octanal, nonanal, and decanal from 6 different plant species were measured in continuously stirred tank reactors when the plants were exposed to ozone. Pathogen- and insect attack on plants also led to these emissions. The emission rates of individual aldehydes were related to each other implying a common mechanism for the emissions of these aldehydes. Furthermore, the emission pattern was similar in all cases indicating a similar emission mechanism for different plant species and different elicitors. Measurements with ozone exposed Scots pine plants (Pinus sylvestris L.) showed that the emission rates were dependent on temperature as well as on the ozone flux into the plants. The diurnal variation of aldehyde emissions from ozone exposed Scots pine were described quite well using a formalism including temperature and ozone flux as variables. Assuming the aldehyde emissions to be general for plants exposed to ozone, the global emissions were estimated to be in the range between 7 and 22 Tg/a. Because these emissions can be induced by other factors than ozone uptake alone this estimate may be a lower limit.Now atNow at     

Exchange of Short-Chain Oxygenated Volatile Organic Compounds (VOCs) between Plants and the Atmosphere: A Compilation of Field and Laboratory Studies

Field and laboratory investigations of the exchange of the short-chain organic acids – formic acid and acetic acid – as well as their homologous aldehydes are discussed. Both acids are substantially released from several plant species. Emission measurements under field conditions are compiled to give an overview of three years of measurements. Emission rates from several tree species were found in the range between zero and 60 nmoles m^–2 min^–1 for acetic acid and between zero and 90 nmoles m^–2 min^–1 for formic acid though also a deposition has been observed to orange trees. Investigations under laboratory conditions showed an order of magnitude lower emission rates with significant differences under light and dark conditions, and a deposition was observed under certain conditions. Hence, low emission rates or even a bi-directional exchange, emission as well as deposition have to be taken into account. Further differences between field and laboratory studies are discussed considering age of trees, stress effects and a potential production of acids by photochemical conversion of precursors inside enclosures during sampling. Field data on the exchange of form- and acetaldehyde show a complex behavior. We found emission as well as uptake. The bi-directional exchange is significantly triggered by the ambient mixing ratios of both aldehyde species and exhibits a compensation point. Further studies are needed for generalization of the exchange of these and potentially also for other compounds.     

Isoprene and Its Oxidation Products Methyl Vinyl Ketone, Methacrolein, and Isoprene Related Peroxides Measured Online over the Tropical Rain Forest of Surinam in March 1998

Airborne measurements of volatile organic compounds (VOC) were performed overthe tropical rainforest in Surinam (0–12 km altitude,2°–7° N, 54°–58° W) using the proton transferreaction mass spectrometry (PTR-MS) technique, which allows online monitoringof compounds like isoprene, its oxidation products methyl vinyl ketone,methacrolein, tentatively identified hydroxy-isoprene-hydroperoxides, andseveral other organic compounds. Isoprene volume mixing ratios (VMR) variedfrom below the detection limit at the highest altitudes to about 7 nmol/molin the planetary boundary layer shortly before sunset. Correlations betweenisoprene and its product compounds were made for different times of day andaltitudes, with the isoprene-hydroperoxides showing the highest correlation.Model calculated mixing ratios of the isoprene oxidation products using adetailed hydrocarbon oxidation mechanism, as well as the intercomparisonmeasurement with air samples collected during the flights in canisters andlater analysed with a GC-FID, showed good agreement with the PTR-MSmeasurements, in particular at the higher mixing ratios.Low OH concentrations in the range of 1–3 × 10⁵molecules cm^-3 averaged over 24 hours were calculated due to lossof OH and HO₂ in the isoprene oxidation chain, thereby stronglyenhancing the lifetime of gases in the forest boundary layer.     

Inhibition of the S(IV) Autoxidation in the Atmosphere by Secondary Terpenic Compounds

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.     

Vertical Evolution of Boundary Layer Volatile Organic Compounds in Summer over the North China Plain and the Differences with Winter

The vertical observation of volatile organic compounds(VOCs) is an important means to clarify the mechanisms of ozone formation. To explore the vertical evolution of VOCs in summer, a field campaign using a tethered balloon during summer photochemical pollution was conducted in Shijiazhuang from 8 June to 3 July 2019. A total of 192 samples were collected, 23 vertical profiles were obtained, and the concentrations of 87 VOCs were measured. The range of the total VOC concentration was 41–48 ppbv below 600 m. It then slightly increased above 600 m, and rose to 58 ± 52 ppbv at 1000 m.The proportion of alkanes increased with height, while the proportions of alkenes, halohydrocarbons and acetylene decreased. The proportion of aromatics remained almost unchanged. A comparison with the results of a winter field campaign during 8–16 January 2019 showed that the concentrations of all VOCs in winter except for halohydrocarbons were more than twice those in summer. Alkanes accounted for the same proportion in winter and summer. Alkenes,aromatics, and acetylene accounted for higher proportions in winter, while halohydrocarbons accounted for a higher proportion in summer. There were five VOC sources in the vertical direction. The proportions of gasoline vehicular emissions + industrial sources and coal burning were higher in winter. The proportions of biogenic sources + long-range transport, solvent usage, and diesel vehicular emissions were higher in summer. From the surface to 1000 m, the proportion of gasoline vehicular emissions + industrial sources gradually increased.     

Determination of Secondary Organic Aerosol Products from the Photooxidation of Toluene and their Implications in Ambient PM2.5

A laboratory study was carried out to investigate the secondary organic aerosol products from photooxidation of the aromatic hydrocarbon toluene. The laboratory experiments consisted of irradiating toluene/propylene/NO_x/air mixtures in a smog chamber operated inthe dynamic mode and collecting submicron secondary organic aerosol samples through a sampling train that consisted of an XAD denuder and a Zefluor^TM filter. Oxidation products in the filter extracts were treated using O-(2,3,4,5,6,-pentafluorobenzyl)-hydroxylamine (PFBHA) to derivatize carbonyl groups followed by treatment with N,O-Bis(trimethylsilyl)-acetamide (BSTFA) to derivatize OH groups. The derivatized products were detected with a positive chemical ionization (CI) gas chromatography ion trap mass spectroscopy (GC-ITMS) system. The results of the GC-ITMS analyses were consistent with the previous studies that demonstrated the formation of multi-functional oxygenates. Denuder results showed that many of these same compounds were present in the gas, as well as, the particle phase. Moreover, evidence was found for a series of multifunctional acids produced as higher order oxidation products of the toluene/NO_x system. Products having nearly the same mass spectrumwere also found in the ambient environment using identical analytical techniques. These products having multiple acid and alcoholic-OH moieties have substantially lower volatility than previously reported SOA products of the toluene photooxidation and might serve as an indicator for aromatic oxidation in the ambient atmosphere.     

Seasonal Variation of Dimethylsulfoxide in Rainwater at Amsterdam Island in the Southern Indian Ocean: Implications on the Biogenic Sulfur Cycle

A continuous record of dimethylsulfoxide (DMSO) in rainwater was performed at Amsterdam island (37°S 77°E) from December 1995 to February 1997. Eighty one rainwater samples were collected. DMSO, methanesulfonic acid (MSA), the major anions, and cations were analyzed. DMSO concentrations ranged from 7.0 to 369 nM, with a distinct seasonal variation. The mean concentrations during the summer and the winter periods were 90 nM and 25.6 nM respectively. The observed DMSO seasonal cycle is in line with the observations of DMS in the atmosphere and MSA in rainwater, measured simultaneously during the reported period. However, the summer to winter ratio of DMSO is significantly lower than that observed for DMS and MSA. The DMSO to MSA ratio and its observed seasonal variability are also presented. The implications on the biogenic sulfur cycle are discussed.     

Gas-Phase Formation of Water-Soluble Organic Compounds in the Atmosphere: A Retrosynthetic Analysis

Atmospheric particles contain a myriad of organiccompounds, including many multifunctional,water-soluble organic compounds. Many of thesecompounds are postulated to be secondary of origin. This work investigates the possible precursors ofseveral classes of multifunctional, water-solublesecondary organic compounds by analyzing the pathwaysleading to their formation, based on known gas-phasereactions. The analysis is termed `retrosynthetic'due to the backward direction of the analysis, fromproducts to precursors. Pathways for multi-functionalcompounds were generated combinatorially, consideringthe formation of one functional group at a time.Many multifunctional organic compounds with carboxylicacid, carbonyl, and hydroxy functional groups werefound to be first- or second-generation products ofcommon anthropogenic and biogenic volatile organiccompounds such as alkanes, alkenes, aromatics, andcyclic alkenes. The estimated yields of water-solubleorganic compounds from primary precursors ranged fromless than 1% to over 10%, based on stoichiometricconsiderations. The SOA formation index, whichcombines the concepts of yields and rates, was used tocompare the feasibility of the retrosyntheticpathways. Many of the candidate pathways involve theisomerization reaction of alkoxy radicals andoxygenated intermediate products such asmonocarboxylic acids and hydroxyaldehydes.     

辨识方法的计算效率(2):迭代算法

讨论了最小二乘迭代辨识算法及其计算效率问题.最小二乘迭代算法由于涉及矩阵求逆运算,为减小计算量,提出了基于块矩阵求逆的最小二乘迭代辨识算法.基于块矩阵求逆的最小二乘迭代辨识算法不是一种新算法,只是从辨识算法的实现方式上降低计算负担,它与最小二乘迭代算法产生相同的参数估计,但计算量小.文中研究了伪线性回归系统、多元伪线性回归系统、多变量伪线性回归系统的最小二乘迭代辨识算法及其基于块矩阵求逆的最小二乘迭代算法.     

Profiles and Source Apportionment of Nonmethane Volatile Organic Compounds in Winter and Summer in Xi’an,China, based on the Hybrid Environmental Receptor Model

Summer and winter campaigns for the chemical compositions and sources of nonmethane hydrocarbons(NMHCs)and oxygenated volatile organic compounds(OVOCs)were conducted in Xi’an.Data from 57 photochemical assessment monitoring stations for NMHCs and 20 OVOC species were analyzed.Significant seasonal differences were noted for total VOC(TVOC,NMHCs and OVOCs)concentrations and compositions.The campaign-average TVOC concentrations in winter(85.3±60.6 ppbv)were almost twice those in summer(47.2±31.6 ppbv).Alkanes and OVOCs were the most abundant category in winter and summer,respectively.NMHCs,but not OVOCs,had significantly higher levels on weekends than on weekdays.Total ozone formation potential was higher in summer than in winter(by 50%)because of the high concentrations of alkenes(particularly isoprene),high temperature,and high solar radiation levels in summer.The Hybrid Environmental Receptor Model(HERM)was used to conduct source apportionment for atmospheric TVOCs in winter and summer,with excellent accuracy.HERM demonstrated its suitability in a situation where only partial source profile data were available.The HERM results indicated significantly different seasonal source contributions to TVOCs in Xi’an.In particular,coal and biomass burning had contributions greater than half in winter(53.4%),whereas traffic sources were prevalent in summer(53.1%).This study’s results highlight the need for targeted and adjustable VOC control measures that account for seasonal differences in Xi’an;such measures should target not only the severe problem with VOC pollution but also the problem of consequent secondary pollution(e.g.,from ozone and secondary organic aerosols).     

金融领域的随机建模与基于软件R的Monte Carlo模拟(2):Cox-Ross-Rubinstein模型

主要讨论了 Cox-Ross-Rubinstein (CRR) 模型和广义的CRR模型,并研究了如何基于CRR模型和广义的CRR模型利用Monte Carlo模拟计算资产价格以及期权价值.     

Numerical Simulation of a Torrential Rain Event in the Northeast of Huaihe Basin. Part I: Model Verification andAnalysis of MCSs

A torrential rain event accompanying Typhoon Prapiroon occurred in 2000, with 24-h rainfall amount reaching 800mm near the typhoon center. This event is simulated by the nonhydrostatic mesoscale model ARPS (V5.2), with thriple one-way nested-grids. Grid spacings of 45, 15, and 5 km are chosen for thethree nested domains. The corresponding grid sizes are 75×75, 140×140, and 180×180, respectively.The NCEP/NCAR reanalysis data, radar echoes, and GMS-5 satellite images are assimilated with the ARPS model initially using a 3-D data assimilation system--ADAS. The simple ice phase scheme and the Kain-Fritsch cumulus parameterization scheme are used. There are 35 layers in the vertical, with a vertical grid spacing of about 625 m. The integration is performed up to 48 h from 0800 BT 29 to 0800 BT 31 August 2000. Compared with radar echoes, GMS-5 satellite images, and intensive surface observations, the results show that the heavy rain area down between the 500-hPa trough and the subtropical high in the left-front of Prapiroon is well simulated by the model ARPS, and the simulated rainfall centers are consistent with observations. A comparison of the radar echoes with these retrieved from the simulated hydrometeors reveals that there are meso-β scale convective systems that exhibit distinctive characteristics, and there are four convective belts converging in the vicinity of Xiangshui, where the maximum rainfall is observed. A further comparision of skew T-lgp diagrams from simulated and observed data demonstrates significant instability in this torrential rain process. The persistent vertical wind shear provides kinetic energy for the development of the MCSs, hence promoting the baroclinic development of convective cells, and the concentration of heavy rain at the specific location. The consistency between model results and observations encourages afurther study of the torrential rain event using the simulation data.     

Multi-Phase Chemistry of C<Subscript>2</Subscript> and C<Subscript>3</Subscript> Organic Compounds in the Marine Atmosphere

A box model is used to explore the detailed chemistry of C₂ and C₃ organic compounds in the marine troposphere by tracing the individual reaction paths resulting from the oxidation of ethane, ethene, acetylene, propane, propene and acetic acid. The mechanisms include chemical reactions in the gas phase and in the aqueous phase of clouds and aerosol particles at cloud level under conditions resembling those in the northern hemisphere. Organic hydroperoxides are found to be important intermediate products, with subsequent reactions leading partly to the formation of mixed hydroxy or carbonyl hydroperoxides that are readily absorbed into cloud water, where they contribute significantly to the formation of multifunctional organic compounds and organic acids. Organic hydroperoxides add little to the oxidation of sulfur dioxide dissolved in the aqueous phase, which is dominated by H₂O₂. Next to acetaldehyde and acetone, glycol aldehyde, glyoxal, methyl glyoxal and hydroxy propanone are prominent oxidation products in the gas and the aqueous phase. Acetaldehyde is not efficiently converted to acetic acid in clouds; the major local sources of acetic acid are gas-phase reactions. Other acids produced include hydroperoxy acetic, glycolic, glyoxylic, oxalic, pyruvic, and lactic acid. The mechanism of Schuchmann et al. (1985), which derives glycolic and glyoxylic acid from the oxidation of acetate, is found unimportant in the marine atmosphere. The principal precursors of glyoxylic acid are glyoxal and glycolic acid. The former derives mainly from acetylene and ethene, the latter from glycolaldehyde, also an oxidation product of ethene. The oxidation of glyoxylic acid leads to oxalic acid, which accumulates and is predicted to reach steady state concentrations in the range 30–90 ng m⁻³. This is greater, yet of the same magnitude, than the concentrations observed over the remote Pacific Ocean.