Differential Accumulation of Volatile Organic Compounds by Leaves and Roots of Two Guianese Philodendron Species, P. fragrantissimum Kunth and P. melinonii Brongn.

Leaf and root essential oils of two closely related but ecologically distant Philodendron species were extracted in natural conditions in French Guiana and analysed by GC/MS to i) describe the blends of volatile organic compounds (VOCs) produced by those species and ii) analyse species and environment-based variations in extracts composition. A total of 135 VOCs were detected with a majority of aliphatic sesquiterpenes. P. fragrantissimum produced mainly ß-bisabolene (on average 29.12% of the extract) as well as α- and ß-selinene (14.52% and 17.50%, respectively) while in P. melinonii, four aliphatic sesquiterpenes could alternatively be the main component: (E)-ß-farnesene (up to 91.42% of the extract), germacrene-D (73.74%), ß-caryophyllene (51.63%) and trans-α-bergamotene (41.26%). A significant effect of species and organs on extracts composition was observed while the environment (sun exposure) only affected the relative proportions of monoterpenes and sesquiterpenes in roots of P. melinonii. These results are discussed in the light of the potential role of leaf and root terpenes in Philodendron species.

On the ultrafast photo-induced dynamics of α-terpinene.

The ultrafast relaxation pathway of α-terpinene was studied by photoionization-photoelectron spectroscopy for a range of excitation conditions. Time-resolved spectra were obtained upon optical excitation with ultrashort laser pulses at 5.56 eV, 4.96 eV, 4.76 eV, and 4.56 eV, followed by ionization with 3.06 eV pulses. The experiments yielded spectra of the initially excited state, which decays with a time constant of 66 fs, independent of the excitation wavelength. We also observed a sequential series of Rydberg peaks, including the s, p, and d states with n = 3-6, which capture the travel times on the ensuing reaction path. There is no statistically significant dependence of the travel time on the excitation energy. A comparison of the time-dependent signals with those of the un-substituted parent molecule, 1,3-cyclohexadiene, shows that the substituents on α-terpinene slow the reaction down by a factor of about 2.

Portable photocatalytic air cleaners: efficiencies and by-product generation.

Portable photocatalytic air cleaners were investigated in 24 and 48 m(3) emission test chambers with regard to efficiency and by-product generation. For this purpose, formaldehyde, decane, 1,2-dichlorobenzene, toluene, α-pinene and heptanal were doped at sub-ppm concentration levels into the chambers individually and in mixtures. By way of specified test protocols, efficiencies could be distinguished but were strongly dependant on the choice of test compounds, especially on whether single or multi compound dosing was used, and on long-term effects. Initial clean air delivery rates (CADRs) up to 137 m(3)/h were measured. Typical by-products were found in significant concentrations. The main ones were formaldehyde up to 50 ppb (62 µg/m(3)) and acetone up to 80 ppb (190 µg/m(3)). Other aldehydes were also found, but at smaller levels. The detection of chloroacetone, a strong irritating compound, at concentrations up to 15 ppb (57 µg/m(3)) strengthens the importance of such investigations especially in cases were chloro-organic compounds are involved.

Volatile organic compounds characterized from grapevine (Vitis vinifera L. cv. Malbec) berries increase at pre-harvest and in response to UV-B radiation.

Ultraviolet-B solar radiation (UV-B) is an environmental signal with biological effects in plant tissues. Recent investigations have assigned a protective role of volatile organic compounds (VOCs) in plant tissues submitted to biotic and abiotic stresses. This study investigated VOCs in berries at three developmental stages (veraison, pre-harvest and harvest) of Vitis vinifera L. cv. Malbec exposed (or not) to UV-B both, in in vitro and field experiments. By Head Space-Solid Phase Micro Extraction-Gas Chromatography-Electron Impact Mass Spectrometry (HS-SPME-GC-EIMS) analysis, 10 VOCs were identified at all developmental stages: four monoterpenes, three aldehydes, two alcohols and one ketone. Monoterpenes increased at pre-harvest and in response to UV-B in both, in vitro and field conditions. UV-B also augmented levels of some aldehydes, alcohols and ketones. These results along with others from the literature suggest that UV-B induce grape berries to produce VOCs (mainly monoterpenes) that protect the tissues from UV-B itself and other abiotic and biotic stresses, and could affect the wine flavor. Higher emission of monoterpenes was observed in the field experiments as compared in vitro, suggesting the UV-B/PAR ratio is not a signal in itself.

Effect of gamma-irradiation on some chemical characteristics and volatile content of linseed.

The effect of irradiation (2.5, 4.0, 5.5, and 7.0 kGy) on chemical properties and volatile contents of linseed was investigated. Consistent decreases were observed in both protein and oil content of the irradiated linseed samples with increasing irradiation doses. The ash content of the irradiated linseed samples increased significantly (P<.05) with increasing irradiation doses except for 5.5 kGy. Irradiation treatment caused irregular changes in palmitic and stearic acid content. Although styrene and p-xylene content decreased as a result of irradiation, 1-hexanol content only decreased at 7.0 kGy. Benzaldehyde, p-cymene, and nonanol were not determined at irradiation doses above 4.0 kGy.

Conformational space and photochemistry of alpha-terpinene.

Alpha-terpinene is a natural product that is isolated from a variety of plant sources and is used in the pharmaceutical and perfume industries. In the atmosphere, under the influence of sunlight, alpha-terpinene undergoes a series of photochemical transformations and contributes to the formation of the secondary organic aerosols. In the present work, alpha-terpinene has been isolated in low-temperature xenon and argon matrices, and its structure and photochemistry were characterized with the aid of FTIR spectroscopy and DFT calculations. The theory predicts three conformers resulting from the rotation of the exocyclic CH(CH(3))(2) framework, that is, Trans (T) and Gauche (G+ and G-) forms. The two Gauche conformers were estimated to be higher in energy, by ca. 1.75 kJ mol(-1), than the most stable Trans form. The signatures of all three conformers were found to be present in the experimental low-temperature matrix spectra with the T form dominating in diluted matrices. The conformational ratio was found to shift in favor of the G+/G- forms upon annealing of the matrices as well as in the neat alpha-terpinene liquid. UV-C (lambda > 235 nm) irradiation of matrix-isolated alpha-terpinene led to its isomerization into an open-ring species, which is produced in the Z configuration and in the conformations that require the smallest structural rearrangements of both the reagent and matrix.

Influence of aerosol acidity on the formation of secondary organic aerosol from biogenic precursor hydrocarbons.

Secondary organic carbon (SOC) concentrations in steady-state aerosol were measured in a series of alpha-pinene/NOx and one series of beta-caryophyllene/NOx irradiation experiments. The acidity of the inorganic seed aerosol was varied while the hydrocarbon and NOx concentrations were held constant in each series of experiments. Measurements were made for acidity levels and SOC concentrations much closer to ambient levels than had been previously achieved for alpha-pinene, while there are no previous measurements for SOC increases due to acidity for beta-caryophyllene. The observed enhancement in SOC concentration linearly increases with the measured hydrogen ion concentration in air for each system. For the conditions of these studies, SOC increased by 0.04% per nmol H+ m(-3) for alpha-pinene under two conditions where the organic carbon concentration differed by a factor of 5. For alpha-pinene, this level of response to acidic aerosol was a factor of 8 lower than was reported by Surratt et al. for similar series of experiments for SOC from the photooxidation of isoprene/NOx mixtures. By contrast, SOC from beta-caryophyllene showed an increase of 0.22% per nmol H+ m(-3), roughly two-thirds of the response in the isoprene system. Mass fractions for SOC particle-phase tracers for alpha-pinene decreased slightly with increasing aerosol acidity, although remaining within previously stated uncertainties. Below 200 nmol H+ m(-3), the mass fraction of beta-caryophyllenic acid, the only identified tracer for beta-caryophyllene SOC, was constant although beta-caryophyllenic acid showed a substantial decrease for acidities greater than 400 nmol H+ m(-3).

Contributions of toluene and alpha-pinene to SOA formed in an irradiated toluene/alpha-pinene/NO(x)/ air mixture: comparison of results using 14C content and SOA organic tracer methods.

An organic tracer method, recently proposed for estimating individual contributions of toluene and alpha-pinene to secondary organic aerosol (SOA) formation, was evaluated by conducting a laboratory study where a binary hydrocarbon mixture, containing the anthropogenic aromatic hydrocarbon, toluene, and the biogenic monoterpene, alpha-pinene, was irradiated in air in the presence of NO(x) to form SOA. The contributions of toluene and alpha-pinene to the total SOA concentration, calculated using the organic tracer method, were compared with those obtained with a more direct 14C content method. In the study, SOA to SOC ratios of 2.07 +/- 0.08 and 1.41 +/- 0.04 were measured for toluene and (alpha-pinene SOA, respectively. The individual tracer-based SOA contributions of 156 microg m(-3) for toluene and 198 microg m(-)3 for alpha-pinene, which together accounted for 82% of the gravimetrically determined total SOA concentration, compared well with the 14C values of 182 and 230 microg m(-3) measured for the respective SOA precursors. While there are uncertainties associated with the organic tracer method, largely due to the chemical complexity of SOA forming chemical mechanisms, the results of this study suggest the organic tracer method may serve as a useful tool for determining whether a precursor hydrocarbon is a major SOA contributor.

Secondary organic carbon and aerosol yields from the irradiations of isoprene and alpha-pinene in the presence of NOx and SO2.

A laboratory study was carried out to investigate the secondary organic carbon (SOC) yields of alpha-pinene and isoprene in the presence of SO2, which produces acidic aerosol in the system. Experiments were based on irradiating each hydrocarbon (HC) with NOx in a 14.5 m3 smog chamber operated in the dynamic mode. The experimental design consisted of several multi-part experiments for each HC. In the first part of each experiment, an HC/NOx irradiation was conducted in the absence of SO2 and was followed by irradiations with the addition of SO2 in subsequent parts. Filter-based analyses for organic carbon were made using a thermal-optical approach either with an off-line instrument or in situ with an automated instrument. For isoprene in the absence of SO2, the SOC yield was approximately 0.001, a value consistent with earlier work from this laboratory. With the addition of up to 200 ppb SO2, the yield increased by a factor of 7. For alpha-pinene in the absence of SO2, the SOC yield of the irradiated mixture was found to average 0.096 from two experiments. With SO2 in the system, the SOC yield increased on average to 0.132. These results suggest that SO2, and by inference acidic aerosol, may play a role in increasing the yield of SOC from the photooxidation products of biogenic hydrocarbons or by the direct uptake of biogenic hydrocarbons onto acidic aerosol.

Identification and quantification of aerosol polar oxygenated compounds bearing carboxylic or hydroxyl groups. 2. Organic tracer compounds from monoterpenes.

In this study, a comparison is made of polar organic compounds found in the field with those produced in secondary organic aerosol from laboratory irradiations of natural hydrocarbons and oxides of nitrogen (NOx). The field samples comprised atmospheric particulate matter (PM2.5) collected at Research Triangle Park (RTP), NC, during the summer of 2003, and the laboratory samples originated from the photooxidation of the following monoterpenes: alpha-pinene, beta-pinene, and d-limonene. To determine the structural characteristics of the polar compounds, the filter samples were solvent extracted and derivatized using a technique based on single and multistep derivatizations. The resulting compound derivatives were analyzed by GC-MS in the methane-Cl and El modes. In addition to previously reported biogenic oxidation products (pinic acid, pinonic acid, norpinic acid, nopinone, and pinonaldehyde), seven multifunctional organic compounds were found in both field and laboratory samples. These compounds, which are proposed as possible atmospheric tracers for secondary organic aerosol from monoterpenes, were consistent with the following identifications: 3-isopropyl pentanedioic acid; 3-acetyl pentanedioic acid; 3-carboxy heptanedioic acid; 3-acetyl hexanedioic acid; 2-isopropyl-1,2-dihydroxybutanol; 4-isopropyl-2,4-dihydroxyhexanol; and 3-(2-hydroxy-ethyl)-2,2-dimethyl-cyclobutane carboxylic acid. Initial attempts have been made to quantify the concentrations of these tracer compounds on the basis of surrogate compound calibrations. The occurrence of these compounds in both laboratory and field measurements suggests that secondary organic aerosol originating from biogenic hydrocarbons are contributing to the regional aerosol burden in the southeastern United States. Several of these compounds also appear to contribute to the global aerosol burden in that they have also been identified in Europe and Brazil.

PROPHIS: parabolic trough-facility for organic photochemical syntheses in sunlight.

The PROPHIS facility is an efficient tool for the synthesis of chemicals with moderately concentrated sunlight on a semi-technical scale. The feasibility of selected solar photochemical reaction classes--including heterogeneous and homogeneous reactions--has been demonstrated using various set-ups of the plant. This paper outlines the potential of solar photochemistry by representative examples.

Generation of reactive oxygen species from Hinokitiol under near-UV irradiation.

Near-UV irradiation caused the decomposition of hinokitiol in an aqueous solution. During the photochemical reaction, the distinct electron spin resonance signal characteristic of the adduct of 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) with the hydroxyl radical was accompanied by small signals corresponding to the adduct of DMPO with the superoxide anion radical. More than 95% of Escherichia coli cells were killed by the incubation with hinokitiol under near-UV irradiation by BLB fluorescent lamps. These results indicated the generation of reactive oxygen species during photochemical reaction of hinokitiol under near-UV irradiation.