Pine weevil feeding on Norway spruce bark has a stronger impact on needle VOC emissions than enhanced ultraviolet-B radiation

Plants can respond physiologically to damaging ultraviolet-B radiation by altering leaf chemistry, especially UV absorbing phenolic compounds. However, the effects on terpene emissions have received little attention. We conducted two field trials in plots with supplemented UV-B radiation and assessed the influence of feeding by pine weevils, Hylobius abietis L., on volatile emissions from 3-year old Norway spruce trees (Picea abies L. Karst.). We collected emissions from branch tips distal to the feeding weevils, and from whole branches including the damage sites. Weevil feeding clearly induced the emission of monoterpenes and sesquiterpenes, particularly linalool and (E)-β-farnesene, from branch tips, and the sums of monoterpenes and sesquiterpenes emitted by whole branches were substantially increased. We discovered little effect of UV-B radiation up to 30% above the ambient level on volatile emissions from branch tips distal to damage sites, but there was a possible effect on bark emissions from damage sites.     

Study of the dispersion of VOCs emitted by a municipal solid waste landfill

The dispersion of VOCs emitted by a municipal solid waste landfill was studied for a period of over one year. Sixteen VOCs were monitored: linear alkanes from C₇ to C₁₁, BTEX, trimethylbenzene, trichlorethylene, tetrachlorethylene, α and β-pinenes, limonene. The analytical procedure was first comprised of static long-term sampling of about 2 months using radial diffusion Radiello tubes containing activated carbon, followed by extraction by solvent (i.e. CS₂) and GC/MS analysis. The results were initially analysed on the basis of the total concentration of the quantified VOCs, then by examining the concentrations of certain selected compounds. The influence of different parameters such as operating conditions, meteorological conditions and site morphology was highlighted on the basis of total VOC concentrations. In order to study the VOC's dispersion more closely, 5 compounds were chosen: toluene, benzene, limonene, and the sum trichlorethylene + tetrachlorethylene, as a “marker”, to verify the origin of the VOCs emitted. The results showed that the main source of VOCs is the open cell and lead to different hypotheses on interferences from neighbouring sources and to the proposal of solutions to limit the emission of VOCs and their dispersion. To our knowledge, this type of study has not been accomplished until this day.     

Volatile organic compound emissions from municipal solid waste disposal sites: A case study of Mumbai,India

Improper solid waste management leads to aesthetic and environmental problems. Emission of volatile organic compounds (VOCs) is one of the problems from uncontrolled dumpsite. VOCs are well known to be hazardous to human health and many of them are known or potential carcinogens. They also contribute to ozone formation at ground level and climate change as well. The qualitative and quantitative analysis of VOCs emitting from two municipal waste (MSW) disposal sites in Mumbai, India, namely Deonar and Malad, are presented in this paper. Air at dumpsites was sampled and analyzed on gas chromatography–mass spectrometry (GC-MS) in accordance with U.S. Environmental Protection Agency (EPA) TO-17 compendium method for analysis of toxic compounds. As many as 64 VOCs were qualitatively identified, among which 13 are listed under Hazardous Air Pollutants (HAPs). Study of environmental distribution of a few major VOCs indicates that although air is the principal compartment of residence, they also get considerably partitioned in soil and vegetation. The CO₂ equivalent of target VOCs from the landfills in Malad and Deonar shows that the total yearly emissions are 7.89E+03 and 8.08E+02 kg, respectively. The total per hour ozone production from major VOCs was found to be 5.34E-01 ppb in Deonar and 9.55E-02 ppb in Malad. The total carcinogenic risk for the workers in the dumpsite considering all target HAPs are calculated to be 275 persons in 1 million in Deonar and 139 persons in 1 million in Malad.

Implications: This paper describes the hazards of VOC emission from open dumpsites, a common practice, in an Indian metro city. The subsequent partitioning of the emitted VOCs in other environmental compartment from air is presented. The global warming potential and the health hazards to the dumpsite workers from the emitted VOCs have also been estimated.     

Identification of volatiles from Pinus silvestris attractive for Monochamus galloprovincialis using a SPME-GC/MS platform

Introduction

A myriad of volatile organic compounds (VOCs) released by terrestrial vegetation plays an important role in environmental sciences. A thorough chemical identification of these species at the molecular level is essential in various fields, ranging from atmospheric chemistry to ecology of forest ecosystems. In particular, the recognition of VOCs profiles in a context of plant?Cinsect communication is a key issue for the development of forest protection tools.

Purpose

This work was aimed at the development of a simple, robust and reliable method for the identification of volatiles emitted from plant materials, which can attract or deter pest insects. Specifically, volatiles emitted from the bark of Pinus sylvestris were studied, which might attract the black pine sawyer beetle Monochamus galloprovincialis??a serious pest of the tree and a vector of a parasitic nematode Bursaphelenchus xylophius.

Method

The volatiles from bark samples were collected using a solid-phase micro-extraction technique, and subsequently analysed by gas-chromatography/mass-spectrometry (GC/MS). The characterisation of the volatile fraction was based on the comparison with data in mass spectral libraries, and in most cases, with the available authentic standards. The identified compounds were screened against the available entomological data to select insect attractors.

Results

The identified components included terpenes (??-pinene, ?-3-carene, and para-cymenene), oxygenated terpenes (??-terpineol and verbenone), sesquiterpenes (??-longipinene, longifolene, E-??-farnesene, ??-cadinene and pentadecane), and diterpenes (manoyl oxide and (+)-pimaral). Of these, longifolene and (+)-pimaral are of particular interest as plausible attractors for the M. galloprovincialis beetle that might find application in the construction of insect bait traps.     

Emission of non-methane volatile organic compounds (VOCs) from boreal peatland microcosms—effects of ozone exposure

Non-methane volatile organic compounds (VOCs) emitted from boreal peatland microcosms were semiquantitatively determined using gas chromatography–mass spectrometry techniques in a growth chamber experiment. Furthermore, effects of vegetation composition and different ozone concentrations on these emissions were estimated by multivariate data analyses. The study concentrated on the less-studied VOCs, and isoprene was not analyzed. The analyses suggest that a sedge Eriophorum vaginatum is associated with emissions of the four most-emitted VOC groups (cyclic, aromatic, carbonyl and aliphatic hydrocarbon compounds) and also with VOCs emitted in smaller amounts (terpenoids and N-containing compounds). A woody dwarf shrub Andromeda polifolia was strongly associated with emissions of aromatic, carbonyl and terpenoid compounds. Results suggest that exposure to an ozone concentration of 150 ppb leads to an increased emission of most VOC groups. Emission of aromatic compounds seems to increase linearly with increasing ozone concentration. These observations indicate that peatlands may be a source of a vast range of volatile compounds to the atmosphere. For more accurate assessment of the impact of elevated tropospheric ozone on the terpenoid and non-terpenoid VOC emissions from peatlands, well-replicated open-air ozone-exposure experiments should be conducted.     

History effect of light and temperature on monoterpenoid emissions from Fagus sylvatica L.

Monoterpenoid emissions from Fagus sylvatica L. trees have been measured at light- and temperature-controlled conditions in a growth chamber, using Proton Transfer Reaction Mass Spectrometry (PTR-MS) and the dynamic branch enclosure technique.De novo synthesized monoterpenoid Standard Emission Factors, obtained by applying the G97 algorithm (Guenther, 1997), varied between 2 and 32 μg g_DW^?1 h^?1 and showed a strong decline in late August and September, probably due to senescence.The response of monoterpenoid emissions to temperature variations at a constant daily light pattern could be well reproduced with a modified version of the MEGAN algorithm (Guenther et al., 2006), with a typical dependence on the average temperature over the past five days.The diurnal emissions at constant temperature showed a typical hysteretic behaviour, which could also be adequately described with the modified MEGAN algorithm by taking into account a dependence on the average light levels experienced by the trees during the past 10–13 h.The impact of the past light and temperature conditions on the monoterpenoid emissions from F. sylvatica L. was found to be much stronger than assumed in previous algorithms.Since our experiments were conducted under low light intensity, future studies should aim at confirming and completing the proposed algorithm updates in sunny conditions and natural environments.     

Real-world vehicle emissions and VOCs profile in the Taipei tunnel located at Taiwan Taipei area

An in situ field experiment was conducted in a highway road tunnel in the Taipei City to determine the motor vehicle emission factors (EF) of different kinds of air pollution species. These are carbon monoxide (CO), oxides of nitrogen (NO_x), non-methane hydrocarbons (NMHC) and VOCs species. About 56 species of VOCs were sampled by canister sampler and followed by the GC-MS analyzing. Furthermore, the tunnel-drafting rate was determined by SF₆ tracer method.The EF for the highway vehicles determined from this experiment are 3.64, 0.90, 0.44 and 0.24 gm km⁻¹ veh⁻¹ for CO, NO_x, NMHC and the totally measured VOCs, respectively. A comparison of the EFs from the road tunnel experiment to the estimates by the USEPA MOBILE5b (M5b) and the modified Taiwan EPA MOBILE-TAIWAN2.0 (MT2.0) provides a first-hand evaluation of the model characteristics. M5b and MT2.0 both tend to underpredict CO by 10% and 20%, respectively. While M5b overpredicts NO_x and NMHC by 40% and 20%, respectively; MT2.0 has fairly good predictions for these two species. From the GC-MS analysis of the canister samples, it was found that the most abundant species from the traffic-emitted VOCs in Taipei road tunnel are toluene, ethene and 1,2,4-trimethyl-benzene (1,2,4-TMB) by the weight basis. However, ethene, acetylene and toluene are the most abundant in VOCs based on volume. The VOCs’ weight composition in terms of the carbon bond classification is 28% by the paraffins, 33% by the olefins and 39% by the aromatics, respectively. In order to evaluate the ozone formation potential from the typical road emission in Taipei area, the maximum increment reactivity is calculated. It was found that about 1015 mg of O₃ is induced by per vehicle per kilometer traveled emission. Among them, ethene, 1,2,4-TMB and propene from the road vehicle's emission contribute most to the ozone-formation reactivity.     

The scale-free network behavior of ambient volatile organic compounds

A scale-free network model with surface and vertical field measurements was used to identify the connectivity distribution of the scale-free network behavior of ambient volatile organic compounds (VOCs). The results show that the carbon number (C _n ) with the total amount of C _n compounds (P(C _n )) possesses an explicit relationship with the scale-free network behavior. The proportionate coefficient (α) and exponent ( γ) of the scale-free network model with spatial and temporal variations are estimated and discussed. The analytical results demonstrate that although photochemical reactions cause the VOCs fraction variation, they do not alter the fraction of C _n compounds observably. Therefore, the values of α and of γ did not vary with time, but with local regional characteristics. The results indicate that the influence of local VOCs emissions occurs at a height of 100 m, but becomes insufficient at a height of 300 m. Air mass mixing increases with greater height; thus, the influence of regional characteristics at a height of 700 m is low. Finally, a successful empirical model was established to evaluate the distribution of surface VOCs in various regions.     

Changes in photosynthesis, mesophyll conductance to CO2, and isoprenoid emissions in Populus nigra plants exposed to excess nickel

Poplar (Populus nigra) plants were grown hydroponically with 30 and 200 μM Ni (Ni₃₀ and Ni₂₀₀). Photosynthesis limitations and isoprenoid emissions were investigated in two leaf types (mature and developing). Ni stress significantly decreased photosynthesis, and this effect depended on the leaf Ni content, which was lower in mature than in developing leaves. The main limitations to photosynthesis were attributed to mesophyll conductance and metabolism impairment. In Ni-stressed developing leaves, isoprene emission was significantly stimulated. We attribute such stimulation to the lower chloroplastic [CO₂] than in control leaves. However chloroplastic [CO₂] did not control isoprene emission in mature leaves. Ni stress induced the emission of cis-β-ocimene in mature leaves, and of linalool in both leaf types. Induced biosynthesis and emission of isoprenoids reveal the onset of antioxidant processes that may also contribute to reduce Ni stress, especially in mature poplar leaves.     

C2–C10 nonmethane hydrocarbons measured in Dallas,USA—Seasonal trends and diurnal characteristics

Nonmethane hydrocarbons (NMHCs) are important precursors of ozone and other photo oxidants. We presented continuous hourly average concentrations of 45 C₂–C₁₀ NMHCs measured in urban area of Dallas, USA from 1996 to 2004. Most of the selected compounds are good variables with less noise. The top 10 species with high ozone-generating potential were identified according to their concentrations and reactivities. The ambient concentrations of abundant anthropogenic emission hydrocarbons measured in Dallas were about 2–4 times of the background values measured in the remote areas with adjacent latitude. The time series for anthropogenic emission hydrocarbons showed an obvious seasonal cycle with relatively high concentration in winter and low concentration in summer. The sinusoidal function with a linearly decreasing factor could well fit the time series of NMHCs. The phase of seasonal cycle for the aromatic hydrocarbons of toluene, m/p xylene and o-xylene that might come from both vehicle emission and solvent utilities evaporation was about 1 month earlier than that for alkanes and alkenes that mainly came from vehicle emission. Ambient NMHCs in Dallas decreased with a stable rate during 1996–2004. For most of compounds with high ozone-generating potential, the rate of ambient concentration decrease was higher or much higher than the rate of volatile organic compounds (VOCs) source emission reduction estimated by EPA's National Emission Inventory. On weekdays, the morning hydrocarbon concentration peak was coincident with morning traffic rush time in Dallas. Another concentration peak was delayed to afternoon traffic rush time. The characteristics of VOCs sources, photochemical removal processes and atmospheric dilution could be interpreted by the diurnal variations of benzene/ethylbenzene (B/E), toluene/ethylbenzene (T/E) and xylene/ethylbenzene (X/E). The ratio of VOC/NO_x measured in Dallas was substantially smaller than that calculated for USA cities. Ozone formation in Dallas was VOC sensitive.     

Tree and stand growth of mature Norway spruce and European beech under long-term ozone fumigation

In a 50- to 70-year-old mixed stand of Norway spruce (Picea abies (L.) Karst.) and European beech (Fagus sylvatica L.) in Germany, tree cohorts have been exposed to double ambient ozone (2×O₃) from 2000 through 2007 and can be compared with trees in the same stand under the ambient ozone regime (1×O₃). Annual diameter growth, allocation pattern, stem form, and stem volume were quantified at the individual tree and stand level. Ozone fumigation induced a shift in the resource allocation into height growth at the expense of diameter growth. This change in allometry leads to rather cone-shaped stem forms and reduced stem stability in the case of spruce, and even neiloidal stem shapes in the case of beech. Neglect of such ozone-induced changes in stem shape may lead to a flawed estimation of volume growth. On the stand level, 2×O₃ caused, on average, a decrease of 10.2 m³ ha⁻¹ yr⁻¹ in European beech.     

Quantitative analysis of volatile organic compounds (VOCs) in atmospheric particles

There are a number of difficulties associated with the quantitative analysis of volatile organic compounds (VOCs) in atmospheric particles. Therefore, majority of the previous studies on VOCs associated with particles have been qualitative. Air samples were collected in Izmir, Turkey to determine ambient particle and gas phase concentrations of several aromatic, oxygenated and halogenated VOCs. Samples were quantitatively analyzed using thermal desorption–gas chromatography/mass spectrometry. Gas-phase concentrations ranged between 0.02 (bromoform) and 4.65 μg m⁻³ (toluene) and were similar to those previously measured at the same site. Particle-phase concentrations ranged from 1 (1,3-dichlorobenzene) to 933 pg m⁻³ (butanol). VOCs were mostly found in gas-phase (99.9±0.25%). However, the particulate VOCs had comparable concentrations to those reported previously for semivolatile organic compounds. The distribution of particle-phase VOCs between fine (d_p<2.5 μm) and coarse (2.5 μm<d_p<10 μm) fractions was also investigated. It was found that VOCs were mostly associated with fine particles.     

Volatile organic compound emissions from Siberian larch

We determined hourly emissions of isoprene, monoterpenes and sesquiterpenes from Siberian larch, one of the major tree species in Siberian forests. Summer volatile organic compounds (VOCs) emission from Siberian larch consisted mainly of monoterpenes (about 90%). The monoterpene emission spectrum remained constant during the measurement period, almost half was sabinene and other major monoterpenes were Δ³-carene, β- and α-pinene. During spring and summer, about 10% of the VOCs were sesquiterpenes, mainly α-farnesene. The sesquiterpene emissions declined to 3% in the fall. Isoprene, 2-methyl-3-buten-2-ol (MBO) and 1,8-cineole contributed to less than 3% of the VOC emission during the whole period. The diurnal variation of the emissions could be explained using a temperature-dependent parameterization. Emission potentials normalized to 30 °C were 5.2–21 μg g_dw⁻¹ h⁻¹ (using β-value of 0.09 °C⁻¹) for monoterpenes and 0.4–1.8 μg g_dw⁻¹ h⁻¹ (using β-value of 0.143 °C⁻¹, mean of determined values) for sesquiterpenes. Normalized monoterpene emission potentials were highest in late summer and elevated again in late fall. Sesquiterpene emission potentials were also highest in late summer, but decreased towards fall.     

Volatile organic inputs from an ocean outfall near Barceloneta,Puerto Rico

Volatile organic compounds (VOCs) discharged from an ocean outfall near Barceloneta, Puerto Rico were found to be present at significant levels (μg/L) in a large area of the Atlantic Ocean north of Puerto Rico. The VOCs in the waste treatment plant effluent, which receives mainly industrial wastes, consisted predominantly of a series of straight and highly branched alkanes between n-C₁₄ and n-C₁₈.     

Effects of chronic elevated ozone exposure on gas exchange responses of adult beech trees (Fagus sylvatica) as related to the within-canopy light gradient

The effects of elevated O₃ on photosynthetic properties in adult beech trees (Fagus sylvatica) were investigated in relation to leaf mass per area as a measure of the gradually changing, within-canopy light availability. Leaves under elevated O₃ showed decreased stomatal conductance at unchanged carboxylation capacity of Rubisco, which was consistent with enhanced δ¹³C of leaf organic matter, regardless of the light environment during growth. In parallel, increased energy demand for O₃ detoxification and repair was suggested under elevated O₃ owing to enhanced dark respiration. Only in shade-grown leaves, light-limited photosynthesis was reduced under elevated O₃, this effect being accompanied by lowered F_v/F_m. These results suggest that chronic O₃ exposure primarily caused stomatal closure to adult beech trees in the field regardless of the within-canopy light gradient. However, light limitation apparently raised the O₃ sensitivity of photosynthesis and accelerated senescence in shade leaves.     

Surface chemistry of a pine-oil cleaner and other terpene mixtures with ozone on vinyl flooring tiles

Indoor environments are dynamic reactors where consumer products (such as cleaning agents, deodorants, and air fresheners) emit volatile organic compounds (VOCs) that can subsequently interact with indoor oxidants such as ozone (O₃), hydroxyl radicals, and nitrate radicals. Typically, consumer products consist of mixtures of VOCs and semi-VOCs which can react in the gas-phase or on surfaces with these oxidants to generate a variety of oxygenated products. In this study, the reaction of a pine-oil cleaner (POC) with O₃ (100 ppb) on a urethane-coated vinyl flooring tile was investigated at 5% and 50% relative humidity. These results were compared to previous α-terpineol + O₃ reactions on glass and vinyl surfaces. Additionally, other terpene and terpene alcohol mixtures were formulated to understand the emission profiles as seen in the POC data. Results showed that the α-terpineol + O₃ reaction products were the prominent species that were also observed in the POC/O₃ surface experiments. Furthermore, α-terpineol + O₃ reactions generate the largest fraction of oxygenated products even in equal mixtures of other terpene alcohols. This finding suggests that the judicial choice of terpene alcohols for inclusion in product formulations may be useful in reducing oxidation product emissions.     

Investigation of partitioning mechanism for volatile organic compounds in a multiphase system

Laboratory experiments were performed to investigate the partitioning behavior of a set of diverse volatile organic compounds (VOCs). After equilibration at a temperature of 25 °C, the VOC concentrations were measured by headspace method in combination with gas chromatography/mass spectrometry (GC/MS). The obtained data were used to determine the partition coefficients (K_P) of VOCs in a gas-liguid-solid system. The results have shown that the presence and nature of solid materials in the working solution control the air-water partitioning of dissolved VOCs. The air/solution partitioning of BTEX and C₉-C₁₀ aldehydes was most affected in the presence of diesel soot. K_P values decreased by a factor ranging from 1.5 for toluene to 3.0 for ethylbenzene. The addition of mineral dust in the working solution exhibited greater influence on the partitioning of short aldehydes. K_P values decreased by a factor of 1.8. The experimental partition coefficients were used to develop a predictive model for partitioning of BTEX and n-aldehydes between air, water and solid phases.     

Temporal variation of volatile organic compounds and their major emission sources in Seoul, Korea

This study examines the characteristics of volatile organic compounds (VOCs) and their major emission sources at the Bulgwang site in Seoul, Korea. The annual levels of VOCs (96.2–121.1 ppb C) have shown a decreasing trend from 2004 to 2008. The most abundant component in Seoul was toluene, which accounted for over 23.5 % of the total VOCs on the parts per billion on a carbon basis, and the portions of alkanes with two to six carbons constituted the largest major lumped group, ranging from 40.1 to 48.4 % (45.3?±?3.7 %) of the total VOCs. Major components of the solvent (toluene, m/p-xylene, o-xylene, and ethylbenzene) showed high in daytime and summer and low in nighttime and winter due mainly to the variation of the ambient temperature. The species mostly emitted from gasoline vapor (i/n-butane, i/n-pentane, n-hexane, and 2-methylpentane) and vehicular exhaust (ethylene, acetylene, and benzene) showed bimodal peaks in the diurnal variation around the commuting hours because of the high traffic volume. For the 14 out of 15 highest concentration species, the weekend effect was only evident on Sundays because of the stepwise implementation of the 5-day work-week system. Principal components analysis (PCA) was applied in order to identify the sources of the 15 highest concentration VOCs and, as a result, three principal components such as gasoline vapor (48.9 %), vehicular exhaust (17.9 %), and evaporation of solvents (9.8 %) were obtained to explain a total of 76.6 % of the data variance. Most influential contributing sources at the sampling site were traffic-related ones although the use of solvent was the dominant emission source based on the official emission inventory.     

Polar and non-polar volatile organic compounds (VOCs) in urban Algiers and saharian sites of Algeria

For the first time, polar and non-polar organic compounds from C₄ to C₂₀ have been identified and quantified in one urban and two saharan sites located in Algeria. They were collected on adsorption traps filled with graphitic carbons and analyzed by high-resolution gas chromatography–mass spectrometry after thermal desorption. More than 190 compounds released by man-made and biogenic sources or formed in air by degradation of photochemical smog precursors were identified in the city center of Algiers. Some of them were never reported before. During our determinations, high levels of pollution characterized the city. Transport of anthropogenic pollutants together with some biogenic emission from date palm trees was mainly responsible for the levels of VOCs measured in Melika oasis located at the entrance of the Sahara desert. Background tropospheric levels of VOCs were instead detected in Bouchene sandy site of the Sahara desert where no biogenic sources were present.     

Characteristics of gaseous pollutants from biofuel-stoves in rural China

The research team analyzed the emission characteristics of gaseous pollutants, including volatile organic compounds (VOCs), from biomass combustion in improved stoves in rural China. The research included measurements from five biofuels and two stove types in the months of January, April, and September. The measurements were conducted according to U.S. EPA Method 25 using a collection system with a cooling device and two-level filters. CO, CO₂, NO_x, CH₄ and THC analyzers were used for in-field, real-time emission measurements. The emission data indicate that gaseous pollutants were emitted at higher concentrations in the early combustion stage and lower concentrations in the later stage. CH₄ and THC, as well as CO and CO₂, presented positive relationships during the whole entire combustion process for all tests. The chemical profiles of flue gas samples were analyzed by GC/MS and GC/FID/ECD. Aromatics, carbonyls, and alkenes & alkynes dominated the VOC emissions, respectively accounting for 37%, 33%, and 23% of total VOC emissions by volume. Benzene was the most abundant VOC species, consisting of 17.3 ± 8.1% of VOCs, followed by propylene (11.3 ± 3.5%), acetone (10.8 ± 8.2%), toluene (7.3 ± 5.7%) and acetaldehyde (6.5 ± 7.3%). Carbon mass balance approach was applied to calculate CO, CO₂, CH₄, NO_x, and VOC species emission factors. This analysis includes a discussion of the differences among VOC emission factors of different biofuel-stove combinations.