Gas-phase reaction of (E)-β-farnesene with ozone: Rate coefficient and carbonyl products

The gas-phase ozonolysis of (E)-β-farnesene was investigated in a 3.91 m³ atmospheric simulation chamber at 296 ± 2 K and relative humidity of around 0.1%. The relative rate method was used to determine the reaction rate coefficient of (4.01 ± 0.17) × 10^?16 cm³ molecule^?1 s^?1, where the indicated errors are two least-squares standard deviations and do not include uncertainties in the rate coefficients for the reference compounds (γ-terpinene, cis-cyclooctene and 1,5-cyclooctadiene). Gas phase carbonyl products were collected using a denuder sampling technique and analyzed with GC/MS following derivatization with O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA). The reaction products detected were acetone, 4-oxopentanal, methylglyoxal, 4-methylenehex-5-enal, 6-methylhept-5-en-2-one, and (E)-4-methyl-8-methylenedeca-4,9-dienal. A detailed mechanism for the gas-phase ozonolysis of (E)-β-farnesene is proposed, which accounts for all of the products observed in this study. The results of this work indicate that the atmospheric reaction of (E)-β-farnesene with ozone has a lifetime of around 1 h and is another possible source of the ubiquitous carbonyls, acetone, 4-oxopentanal and 6-methylhept-5-en-2-one in the atmosphere.     

Evaluation of a detailed model of secondary organic aerosol formation from α-pinene against dark ozonolysis experiments

BOREAM, a detailed model for the gas-phase oxidation of α-pinene and its subsequent formation of Secondary Organic Aerosol (SOA), is tested against a large set of SOA yield measurements obtained in dark ozonolysis experiments. For the majority of experiments, modelled SOA yields are found to agree with measured yields to within a factor 2. However, the comparisons point to a general underestimation of modelled SOA yields at high temperatures (above 30 °C), reaching an order of magnitude or more in the worst cases, whereas modelled SOA yields are often overestimated at lower temperature (by a factor of about 2). Comparisons of results obtained using four different vapour pressure prediction methods indicate a strong sensitivity to the choice of the method, although the overestimated temperature dependence of the yields is found in all cases. Accounting for non-ideality of the aerosol mixture (based on an adapted UNIFAC method) has significant effects, especially at low yields. Our simulations show that the formation of oligomers through the gas-phase reactions of Stabilised Criegee Intermediates (SCI) with other molecular organic products could increase the SOA yield significantly only at very low relative humidity (below 1%). Further tests show that the agreement between model and measurements is improved when the ozonolysis mechanism includes additional production of non-volatile compounds.     

The effect of water on gas–particle partitioning of secondary organic aerosol. Part I: α-pinene/ozone system

The effect of relative humidity (RH) on aerosol formation by the semi-volatile oxidation products of the α-pinene/O₃ system has been comprehensively studied. Experiments were performed in the presence of ammonium sulfate (aqueous, dry), ammonium bisulfate seed (aqueous, dry), and aqueous calcium chloride seed aerosols to ascertain their effect on the partitioning of the oxidation products. The yield of organic aerosol varies little with RH, and is not affected by the presence of dry inorganic salt aerosols. Aqueous salt aerosols reduce the yield of organic aerosol compared to that under seed-free or dry seed conditions. The degree of reduction is electrolyte dependent, with aqueous ammonium sulfate leading to the largest reduction and aqueous calcium chloride the smallest. Hygroscopic growth of the organic aerosol from <2% to 85% RH was also monitored, and could be satisfactorily represented as the sum of the individual contributions of the organic and inorganic fractions. The implications of the growth factor measurements for concentration/activity relationships of the condensed phase organic material (assuming a liquid solution) was explored. The formation of the organic aerosol was investigated using a simple two component model, and also one including the 12 product compounds identified in a previous study. The experimental results for <2% and 50% RH (without salt seed aerosols) could be satisfactorily predicted. However, the aqueous salt seed aerosols are predicted to increase the overall yield due to the dissolution of the organic compounds into the water associated with the seed aerosol—the opposite effect to that observed. The implications of two distinct phases existing the aerosol phase were investigated.     

Modeling potential ozone impacts from natural hydrocarbons—I. Development and testing of a chemical mechanism for the nox-air photooxidations of isoprene and α-pinene under ambient conditions

A chemical mechanism has been developed to predict O₃ formation in mixtures of isoprene, α-pinene and NO_x in air. The mechanism was tested against 17 outdoor smog chamber data sets from the University of North Carolina chamber and was shown to predict maximum O₃ concentrations within ±20%. Reasonably good agreement was found between the predicted and measured time-concentration profiles of other species such as NO₂, peroxyacetyl nitrate (PAN) and aldehydes. Due to the greater availability of kinetic and mechanistic data for isoprene and to the more extensive comparison of this mechanism to experimental data, the mechanism is considered more reliable for isoprene than α-pinene.     

Production of OH radicals from the reactions of C4–C6 internal alkenes and styrenes with ozone in the gas phase

OH formation from the ozonolysis reactions of seven internal alkenes with 4–6 carbons, styrene, trans-β-methyl styrene, and α-methyl styrene was studied using complementary techniques. A small-ratio relative-rate technique in which small quantities of OH tracers are added to monitor OH formation yields provided the following results: trans-2-butene, 0.64±0.12; cis-2-butene, 0.33±0.05; trans-2-pentene, 0.46±0.08; cis-2-pentene, 0.29±0.06; trans-3-hexene, 0.53±0.08; cis-3-hexene, 0.36±0.07; and 2-methyl-2-butene, 0.98±0.24. For styrene, trans-β-methyl styrene, and α-methyl styrene, OH yields of 0.07±0.04, 0.22±0.09, and 0.23±0.12 were measured, respectively. A second method, which monitors product formation from the OH reaction with 2-butanol was used to derive OH formation yields from 2,3-dimethyl-2-butene, 2-methyl-2-butene and cis-2-pentene, and provided yields of 0.91±0.14, 0.80±0.12, and 0.27±0.07, respectively. The results are briefly discussed in terms of the relationship between structures of these alkenes and OH formation.     

On-line measurements of α-pinene ozonolysis products using an atmospheric pressure chemical ionisation ion-trap mass spectrometer

An on-line technique to investigate complex organic oxidation reactions in environmental chamber experiments is presented. The method is based on the direct introduction of the chamber air into an atmospheric pressure ion source of a commercial ion-trap mass spectrometer. To demonstrate the analytical potential of the method (atmospheric pressure chemical ionisation/mass spectrometry, APCI/MS), the ozonolysis of α-pinene was investigated in a series of experiments performed in various sized reaction chambers at atmospheric pressure and 296 K in synthetic air. Investigations were focussed on the influence of the water vapour concentration on the formation of the predominant oxidation product, pinonaldehyde, derived from the α-pinene/ozone reaction. Quantification of pinonaldehyde was achieved by conducting a standard addition technique. The molar yield of pinonaldehyde was found to depend strongly on the actual water vapour concentration between <1 and 80% relative humidity. Starting with an average yield of 0.23±0.05 at dry conditions, pinonaldehyde formation was approximately doubled by reaching a yield of 0.53±0.05 at a relative humidity of around 60%. Furthermore, the formation mechanism of pinonaldehyde was investigated in greater detail using isotopically labelled water. Applying on-line APCI/MS, pinonaldehyde formation under incorporation of ¹⁸O was observed, strongly supporting the reaction of the stabilised Criegee radical with water in the gas phase as suggested by Alvarado et al. (Journal of Geophysical Research 103 (1998) 25541–25551). Furthermore, the mass spectra recorded on-line were used to perform a semi-quantitative estimation of the decomposition pathway of the primary ozonide, indicating a branching ratio of 0.35/0.65.     

Application of ozone for the removal of bisphenol A from water and wastewater – A review

The extensive use of Bisphenol A (BPA) in the plastics industry has led to increasing reports of its presence in the aquatic environment, with concentrations of ng L^?1 to μg L^?1. Various advanced oxidation processes, including ozonation, have been shown to effectively degrade BPA. This paper reviews the current advancements in using ozone to remove BPA from water and wastewater.Most of the published work on the oxidation of BPA by ozone has focused on the efficiency of BPA removal in terms of the disappearance of BPA, and the effect of various operational parameters such as ozone feed rate, contact time and pH; some information is available on the estrogenic activity of the treated water. Due to increasing operational reliability and cost effectiveness, there is great potential for industrial scale application of ozone for the treatment of BPA. However, there is a significant lack of information on the formation of oxidation by-products and their toxicities, particularly in more complex matrices such as wastewater, and further investigation is needed for a better understanding of the environmental fate of BPA.     

Diurnal variation in the concentration of α- and β-pinene in the landes forest (France)

The study deals with the identification and the determination of the main monoterpenes (α- and β-pinene) released by the pines in the Landes Forest in France. The measurements were taken after preconcentration using TENAX-GC and thermal desorption. The diurnal variation of atmospheric concentration of α- and β-pinene is established; it is less than 0.5 ppbV in the daytime and varies from 2 to 4 ppbV in the night-time. These variations are explained by the fact that the photochemical reactions and the turbulence phenomena to which the terpenes are exposed change quite radically from day to night. The terpene concentration, higher at 5 m than at 25 m, would seem to confirm the existence of a terpene source at ground level.     

Quantification on source/receptor relationship of primary pollutants and secondary aerosols from ground sources—Part I. Theory

A new algorithm has been derived for trajectory models to determine the transfer coefficient of each source along or adjacent to a trajectory and to calculate the concentrations of SO₂, NO_x, sulfate, nitrate, fine particulate matter (PM) and coarse PM at a receptor. The transfer coefficient t_f (s m⁻¹) is defined to be the ratio between the contributed concentration ΔC (μg m⁻³) to the receptor from a ground source and the emission rate of the source q (μg m⁻² s⁻¹) at a grid, i.e. t_f≡ΔC/q. The model is developed by combining with a backward trajectory scheme and a circuit-type's parameterization. First, the transfer coefficients of grids along or adjacent a back-trajectory are calculated. Then, the contributed concentration of each emission grid is determined by multiplying its emission rate with the transfer coefficient of the grid. Finally, the concentration at the receptor is determined by the summation of all the contributed concentrations within the domain of simulation.     

Impact of reaction products from building materials and furnishings on indoor air quality—A review of recent advances in indoor chemistry

The variety of chemical substances present in modern building products, household products and furnishings provides potential for chemical reactions in the material (case 1), on the material surface (case 2) and in the gas phase (case 3). Such “indoor chemistry” is known as one of the main reasons for primary and secondary emissions. The conditions of production often cause unwanted side reactions and a number of new compounds can be found in finished products. Elevated temperatures are responsible for the degradation of cellulose, decomposition of non-heat-resistant additives and other thermally induced reactions like Diels–Alder synthesis. Heterogeneous chemistry takes place on the surface of materials. Well-known examples are the formation of aliphatic aldehydes from the oxidation of unsaturated fatty acids or the cleavage of photoinitiators under the influence of light. In case of composite flooring structures hydrolysis is one of the major pathways for the appearance of alcohols from esters. If different kinds of material are fixed together, emissions of new VOCs formed by inter-species reactions are possible. Other indoor air pollutants are formed by rearrangement of cleavage products or by metabolism. Compounds with –CC– bonds like terpenes, styrene, 4-phenylcyclohexene, etc. undergo gas phase reactions with O₃, NO_x, OH and other reactive gases. It has been shown that such products derived from indoor-related reactions may have a negative impact on indoor air quality due to their low odor threshold or health-related properties. Therefore, the understanding of primary and secondary emissions and the chemical processes behind is essential for the evaluation of indoor air quality. This publication gives an overview on the current state of research and new findings regarding primary and secondary emissions from building products and furnishings.     

Improved identification of transition metals in airborne aerosols by SEM–EDX combined backscattered and secondary electron microanalysis

The SEM EDX backscattered electron (BSE) atomic number contrast has been largely used in this work, in combination with conventional secondary electron microanalysis, to investigate the presence of metal particles in airborne particulate collected at three sites (industrial, residential, and rural background) in the Po Valley (Italy). Individual particle x-ray microanalysis was used for this aim. In many cases, the presence of metal particles was not evident by secondary electron imaging and it was instead revealed by BSE detection. Metal particles were observed either as isolated (not clustered to other particles), or gathered together (homogeneous clusters). In addition, the BSE microanalysis put on evidence two main types of association of metals to other particulate components: heterogeneous clusters and metals embedded or enclosed in other materials. In this study, the first association (heterogeneous clusters) was observed mostly between Fe-bearing metallic particles and soot aggregates (or other carbonaceous particles) and it was found in the particulate matter (PM) of all studied sites. The second association, conversely, seems to be characterized by more selective relationships between composition/size of metal particles and type of other particulate components. These associations could be evidenced only when using the BSE Z-contrast and mainly concern three cases: (1) unusual silicate–carbonate mixed aggregates were observed at the industrial site only. In these aggregates, embedded Mn, Cr, Co, Bi, W, and Zr fine particles were selectively observed. (2) Ni and V rich ultrafine particles were only observed as embedded particles in the surface structure of carbon cenospheres. (3) Pb or Pb–Zn bearing fine and ultrafine particles were largely detected only in oxygenated organic aerosols in the ultrafine PM.     

Size-resolved mass and chemical properties of dust aerosols from Australia’s Lake Eyre Basin

Australia is the dominant mineral dust source in the southern hemisphere, yet the physical, chemical and optical properties of Australian dust aerosol are presently poorly understood. We have investigated the properties of Australian aerosol at a site near Lake Eyre in central Australia, which is strongly influenced by mineral dust. During a field campaign in November 2007 we collected eight sets of size-resolved aerosol samples for laboratory analysis: six during quiescent conditions, and two during dust storms. Ion Beam Analysis was used to determine the elemental composition of all filter samples. Scatter plots showed that Fe, Al and Ti were well correlated with Si, and hence soil-derived. The Fe/Si ratio was consistently higher than the global crustal average, confirming that Australian dusts are comparatively rich in Fe. Scatter plots for Na and Cl against Si showed clear evidence of a second aerosol population, associated with maritime advection. Profiles of water soluble ions for two sample sets, showed the importance of marine influences on both the fine and coarse modes, as well as the presence of organic acids. Estimates of the mass fraction of NaCl in our samples suggest that, for quiescent days, roughly 0.5% of the sample mass was NaCl.     

Organic matter of the troposphere—III. Characterization and sources of petroleum and pyrogenic residues in aerosols over the western united states

Aerosols from urbanized areas of the western United States and Nigeria, as well as from rural air basins with elevated vehicular traffic, contain extractable organic matter composed mainly of petroleum residues, with subordinate waxes from vascular plants and minor polynuclear aromatic hydrocarbons. Petroleum residues can be distinguished from the natural background by their unique compound distributions and molecular marker signatures. The predominant source of the atmospheric petroleum residues is from vehicular exhaust in the form of lubricants. A minor component of PAH is found in aerosols receiving an input of smoke from wood combustion. These anthropogenic constituents are a significant part of urban aerosols and their molecular signature may prove of utility as tracers for air parcels from particular geographic regions and as specific tags for vehicular (especially diesel) emissions.     

17 β-estradiol mineralization in human waste products and soil in the presence and the absence of antimicrobials

Natural steroidal estrogens, such as 17 β-estradiol (E2), as well as antimicrobials such as doxycycline and norfloxacin, are excreted by humans and hence detected in sewage sludge and biosolid. The disposal of human waste products on agricultural land results in estrogens and antibiotics being detected as mixtures in soils. The objective of this study was to examine microbial respiration and E2 mineralization in sewage sludge, biosolid, and soil in the presence and the absence of doxycycline and norfloxacin. The antimicrobials were applied to the media either alone or in combination at total rates of 4 and 40 mg kg^?1, with the 4 mg kg^?1 rate being an environmentally relevant concentration. The calculated time that half of the applied E2 was mineralized ranged from 294 to 418 days in sewage sludge, from 721 to 869 days in soil, and from 2,258 to 14,146 days in biosolid. E2 mineralization followed first-order and the presence of antimicrobials had no significant effect on mineralization half-lives, except for some antimicrobial applications to the human waste products. At 189 day, total E2 mineralization was significantly greater in sewage sludge (38 ±0.7%) > soil (23 ±0.7%) > biosolid (3 ±0.7%), while total respiration was significantly greater in biosolid (1,258 mg CO₂) > sewage sludge (253 mg CO₂) ≥ soil (131 mg CO₂). Strong sorption of E2 to the organic fraction in biosolid may have resulted in reduced E2 mineralization despite the high microbial activity in this media. Total E2 mineralization at 189 day was not significantly influenced by the presence of doxycycline and/or norfloxacin in the media. Antimicrobial additions also did not significantly influence total respiration in media, except that total CO₂ respiration at 189 day was significantly greater for biosolid with 40 mg kg^?1 doxycycline added, relative to biosolid without antimicrobials. We conclude that it is unlikely for doxycycline and norfloxacin, or their mixtures, to have a significant effect on E2 mineralization in human waste products and soil. However, the potential for E2 to be persistent in biosolids, with and without the presence of antimicrobials, is posing a challenge for biosolid disposal to agricultural lands.     

Stratospheric ozone in the lower troposphere —I. Presentation and interpretation of aircraft measurements

The United States has instituted a number of air pollution regulations to control ozone, including an air quality standard for oxidants of 120 ppb for one hour. Accordingly, there is considerable interest in determining the magnitude of the natural (i.e. nonanthropogenic) component of ozone concentration near the ground, much of which is generally believed to come from the stratosphere. Toward this end, an extensive program of aircraft measurements of tropospheric ozone originating from the stratosphere was carried out over the Central U.S. in spring and fall 1978. On 10 of these flights, the vertical structure of stratospheric ozone intrusions was well mapped by aircraft penetrations at several altitudes extending between 2 and 8 km above sea level (ASL) in the southern portions of tropospheric low-pressure troughs.The field measurements show that stratospheric ozone intrusions into the troposphere occur more frequently than earlier studies had indicated. Ozone intrusions were found in virtually every trough, regardless of intensity, within which suitable measurements were taken. A close relationship was found between:

• 1.(1) maximum ozone concentrations in the intrusion; and
• 2.(2) trough intensity as characterized by maximum wind speed at 300 mb (approximately 10 km ASL).

The intrusions typically are characterized by peak ozone concentrations at higher altitudes (6–8 km ASL) in the range of 240–400 ppb, diminishing to 100–200 ppb at lower altitudes as mixing with surrounding air occurs. Measured concentrations during spring were almost twice as high as those measured during fall, but the intrusion structures were very similar during both seasons. The data show that stratospheric ozone intrusions are typically 100–300 km wide in the crosswind direction, are several hundreds of kilometers long, and can be tracked down at least as far as the top of the atmospheric boundary layer (about 2 km ASL). Possible mechanisms for downward transport within the boundary layer include normal convective mixing, organized convection associated with cloud and precipitation processes, and organized downward motion within frontal zones.     

Mesoscale modelling of vertical atmospheric transport in the Alps associated with the advection of a tropopause fold – a winter ozone episode

The role of vertical atmospheric transport (VAT) for a winter ozone episode (January 1988) in the Alps, observed both on the mountain crest (3580 m asl) and in the lee of the Alps (209 m asl), is investigated. Numerical simulations were carried out with a doubly nested mesoscale model (14 km horizontal resolution), characterised by a refined orography scheme. A comparison between the modelled vertical profiles with features observed in the aerological soundings over Payerne indicated that the model is able to reproduce the fold in the Alps down to 650 hPa. Frictional processes are found to be responsible for the fragmentation of the lower parts of the fold when it is advected over the mountains, thus enhancing ozone concentrations at the mountain crest with likely cross-tropopause mixing. Vertically propagating gravity waves and strong mesoscale vertical winds (nordfoehn) are responsible for the further downward transport of ozone-rich air to the lower troposphere. This mechanism leads to ozone concentrations up to 70 ppb(v) in the leeside. The study is important because tropospheric ozone trends in the lee of the Alps have been inferred, in the past, from ozone peaks associated with such nordfoehn conditions. It is now shown that nordfoehn may entrain air which has been recently exchanged across the tropopause.     

Characterization of atmospheric aerosols by SEM in a rural area in the western part of México and its relation with different pollution sources

Samples of particulate matter were collected during the period from October 2006 through September 2007 in a rural station located 12 km from the city of Colima. A total of 3600 particles were analyzed by SEM-EDS and then classified by their chemical composition and morphology in order of abundance: those rich in C, Fe, Si–Al, Cl–Na, Ca, Ba; and to a lesser abundance, particles rich in heavy metals such as Pb and V–Ni were observed. A factorial analysis was carried out to determine the main elements related with the emission sources such as crustal/farming; fuel-oil; marine; volcanic activity and industry. Trough the seasons, the dominant winds causes the presence of anthropogenic particles in the rural site. The information presented in this study aims to give insight and detailed of the analysis of the morphological characteristics and chemical composition of atmospheric particles at individual level in a rural site from Colima State, Mexico.     

NMOC,ozone, and organic aerosol in the southeastern United States, 1999–2007: 1. Spatial and temporal variations of NMOC concentrations and composition in Atlanta,Georgia

Volatile organic compounds (VOCs) are emitted from anthropogenic and natural (biogenic) sources into the atmosphere. Characterizing their ambient mixing ratios or concentrations is a challenge because VOCs comprise hundreds of species, and accurate measurements are difficult. Long-term hourly and daily-resolution data have been collected in the metropolitan area of Atlanta, Georgia, a major city dominated by motor vehicle emissions. A series of observations of daily, speciated C₂–C₁₀ non-methane organic compounds (NMOC) and oxygenated hydrocarbons (OVOC) in mid-town Atlanta (Jefferson Street, JST) are compared with data from three urban-suburban sites and a nearby non-urban site. Annual-average mixing ratios of NMOC and OVOC at JST declined from 1999 through 2007. Downward trends in NMOC, CO, and NO_y corroborate expected emission changes as reflected in emission inventories for Atlanta’s Fulton County. Comparison of the JST NMOC composition with data from roadside and tunnel sampling reveals similarities to motor vehicle dominated samples. The JST annual average VOC-OH reactivities from 1999 to 2007 were relatively constant compared with the decline in annual-average NMOC mixing ratios. Mean reactivity at JST, in terms of concentration*k_OH, was approximately 40% alkenes, 22% aromatics, 16% isoprene and 6% other biogenics, 13% C₇–C₁₀ alkanes and 3% C₂-C₆ alkanes, indicating that biogenic NMOCs are important but not dominant contributors to the urban reactive NMOC mix. In contrast, isoprene constituted ～50% of the VOC-OH reactivities at two non-urban sites. Ratios of 24-hour average CO/benzene, CO/isopentane, and CO/acetylene concentrations indicate that such species are relatively conserved, consistent with their low reactivity. Ratios of more-reactive to less-reactive species show diurnal variability largely consistent with expected emission patterns, transport and mixing of air, and chemical processing.