Volatile organic compounds (VOCs) emitted from 40 Mediterranean plant species:: VOC speciation and extrapolation to habitat scale

Forty native Mediterranean plant species were screened for emissions of the C5 and C10 hydrocarbons, isoprene and monoterpenes, in five different habitats. A total of 32 compounds were observed in the emissions from these plants. The number of compounds emitted by different plant species varied from 19 (Quercus ilex) to a single compound emission, usually of isoprene. Emission rates were normalised to generate emission factors for each plant species for each sampling event at standard conditions of temperature and light intensity. Plant species were categorised according to their main emitted compound, the major groups being isoprene, α-pinene, linalool, and limonene emitters. Estimates of habitat fluxes for each emitted compound were derived from the contributing plant species’ emission factors, biomass and ground cover. Emissions of individual compounds ranged from 0.002 to 505 g ha⁻¹ h⁻¹ (camphene from garrigue in Spain in autumn and isoprene from riverside habitats in Spain in late spring; respectively). Emissions of isoprene ranged from 0.3 to 505 g ha⁻¹ h⁻¹ (macchia in Italy in late spring and autumn; and riverside in Spain in late spring; respectively) and α-pinene emissions ranged from 0.51 to 52.92 g ha⁻¹ h⁻¹ (garrigue in Spain in late spring; and forest in France in autumn; respectively). Habitat fluxes of most compounds in autumn were greater than in late spring, dominated by emissions from Quercus ilex, Genista scorpius and Quercus pubescens. This study contributes to regional emission inventories and will be of use to tropospheric chemical modellers.     

Natural VOC emissions from forests in Poland

On the basis of the last inventory of forests and climatic conditions in Poland, a national evaluation of the emissions of reactive volatile organic compounds (VOCs) was carried out. Calculations took into account the composition and age structure of forests as well as the temperature dependencies of VOC emission rate for the main European forest-forming tree species. In the case of isoprene, the dependence on illumination level and day length was also taken into account. Estimations were made for all 49 administrative regions of Poland. Depending on weather conditions in different years, the total VOC emission of Polish forests can be in the range 186–763 kt yr⁻¹. For instance, for a moderately warm year, 1992, it was estimated at 440.6 kt, which represents 25% of the total VOC emissions in Poland.     

Seasonal patterns of non-terpenoid C6-C10 VOC emission from seven Mediterranean woody species

The seasonal pattern of non-terpenoid C6-C10 VOC emission by seven Mediterranean woody species (Bupleurum fruticosum, Cistus albidus, Pinus halepensis, Arbutus unedo, Erica arborea, Quercus coccifera, and Q. ilex) was studied under field conditions. Branch chamber samples were sorbed on carbotrap and analyzed by thermal desorption in combination with GC-MS. These non-terpenoid C6-C10 VOC emissions were large, almost of similar magnitude to those of terpenes. Overall, maximum values were recorded in spring and summer (up to 12 microg g(-1) DM h(-1) in Q. ilex) and minimum values in autumn and winter (up to 5 microg g(-1) DM h(-1) in Q. ilex). These C6-C10 VOC emissions represented 2.82% of the photosynthetic C fixation in summer and 0.22% in winter. Some compounds such as 2-ethoxyethyl acetate were emitted by most species, others such as 3-hexen-1-ol, phenol or decanal were significantly emitted only by few species. The greatest diversity of emitted non-terpenoid C6-C10 VOCs was observed in spring and in Q. ilex. Temperature seemed a strong driver of these seasonal changes but other species-specific and seasonal factors seem involved. These results indicate that C6-C10 non-terpenoid VOCs contribute a rather significant fraction of the total biogenic VOC flux from these Mediterranean species, especially in spring and summer, and therefore should be considered in VOC emission inventories and in model predictions of tropospheric chemistry.     

(M)VOC and composting facilities. Part 1: (M)VOC emissions from municipal biowaste and plant refuse

GOAL, SCOPE AND BACKGROUND: Malodorous volatiles derived from the decomposition of biowaste within the process of composting might pose a risk to human health. Different techniques of process engineering have been developed to minimise the burden of malodorous compounds in air possibly affecting compost workers and residents in the vicinity. METHODS: In the present study, three different composting facilities were examined for the emission of volatiles to estimate the impact of process engineering on the dispersal of odorous compounds and to discuss its relevance for human health. RESULTS AND DISCUSSION: Concentrations of single compounds belonging to alcohols, ketones, furanes, sulfur-containing compounds and especially terpenes ranged from 10(2) up to nearly 10(6) ng/m3 depending on the sampling sites and the process engineering. The ratio of MVOC and total VOC measured changed throughout the process of biodegradation. A certain combination of volatile compounds coincided with the occurrence of typical compost odour. CONCLUSION: The type of process engineering seemed to have a major impact on the emission of volatiles, as amounts of (microbial) volatiles emitted were characteristic for the different techniques used. Thus, the MVOC emission basically depends on the degree of biodegradation. It is likely that the concentrations workers are exposed to can have an impact on human health. RECOMMENDATIONS AND OUTLOOK: It is obvious that less sophisticated types of process engineering give rise to greater amounts of bioaerosols and volatiles and, therefore, technical devices have to be improved and controlled regularly to minimise adverse health effects on workers.     

Emission of volatile organic compounds (VOC) from tropical plant species in India

Foliar emission of volatile organic compounds (VOC) from common Indian plant species was measured. Dynamic flow enclosure technique was used and the gas samples were collected onto Tenax-GC/Carboseive cartridges. The Tenax-GC/Carboseive cartridges were attached to the thermal disorber sample injection system and the gas sample was analysed using gas chromatography (GC) with flame ionisation detection (FID). Fifty-one local plant species were screened, out of which 36 species were found to emit VOC (4 high emitter; 28 moderate emitter; and 4 low-emitter), while in the remaining 15 species no VOC emission was detected or the levels of emission were below detection limit (BDL). VOC emission was found to vary from one species to another. There was a marked seasonal and diurnal variation in VOC emission. The minimum and maximum VOC emission values were < 0.1 and 87 microgg(-1) dry leaf h(-1) in Ficus infectoria and Lantana camara respectively. Out of the 51 plant species studied, 13 species are reported here for the first time. Among the nine tree species (which were selected for detailed study), the highest average hourly emission (9.69+/-8.39 microgg(-1) dry leaf) was observed in Eucalyptus species and the minimum in Syzygium jambolanum (1.89+/-2.48 microgg(-1) dry leaf). An attempt has been made to compare VOC emission from different plant species between present study and the literature (tropical and other regions).     

Dimensionless correlations to predict VOC emissions from dry building materials

Based on the most recently published mass transfer model of volatile organic compound (VOC) emissions from dry building materials, it is found that the dimensionless emission rate and total emission quantity are functions of just four dimensionless parameters, the ratio of mass transfer Biot number to partition coefficient (Bi_m/K), the mass transfer Fourier number (Fo_m), the dimensionless air exchange rate (Nδ²/D_m) and the ratio of building material volume to chamber or room volume (Aδ/V). Through numerical analysis and data fitting, a group of dimensionless correlations for estimating the emission rate from dry building materials is obtained. The predictions of the correlations are validated against the predictions made by the mass transfer model. Using the correlations, the VOC emission rate from dry building materials can be conveniently calculated without having to solve the complicated mass transfer equations. Thus it is very simple to estimate VOC emissions for a given condition. The predictions of the correlations agree well with experimental data in the literature except in the initial few hours. Furthermore, based on the correlations, a relationship between the emission rates of a material in two different situations is deduced. With this relationship, the results for a given building material in a test chamber can be scaled to those under real conditions, if the dimensionless parameters are within the appropriate region for the correlations. The relationship also explicitly explains the impacts of air velocity, load ratio, and air exchange rate on the VOC emission rate, which determines the feasibility of assuming that the VOC emission rates in real conditions are the same as those in the test chambers.     

Effects of vehicle exhaust emissions on urban wild plant species

Very few investigations have examined the direct impacts of vehicle exhausts on plants and attempted to separate out the key pollutants responsible for observed effects. This paper describes a multi-phase investigation into this topic, using 12 herbaceous species typical of urban areas and representing different functional groups. Fumigations were conducted in solardomes with diesel exhaust pollutants at concentrations designed to simulate those close to a major highway in inner London. A wide range of effects were detected, including growth stimulation and inhibition, changes in gas exchange and premature leaf senescence. This was complemented by controlled fumigations with NO, NO(2) and their mixture, as well as a transect study away from a busy inner London road. All evidence suggested that NO(x) was the key phytotoxic component of exhaust emissions, and highlights the potential for detrimental effects of vehicle emissions on urban ecosystems.     

Smoke emissions from biomass burning in a Mediterranean shrubland

Gaseous and particulate samples from the smoke from prescribed burnings of a shrub-dominated forest with some pine trees in Lousã Mountain, Portugal, in May 2008, have been collected. From the gas phase Fourier transform infrared (FTIR) measurements, an average modified combustion efficiency of 0.99 was obtained, suggesting a very strong predominance of flaming combustion. Gaseous compounds whose emissions are promoted in fresh plumes and during the flaming burning phase, such as CO₂, acetylene and propene, produced emission factors higher than those proposed for savannah and tropical forest fires. Emission factors of species that are favoured by the smouldering phase (e.g. CO and CH₄) were below the values reported in the literature for biomass burning in other ecosystems. The chemical composition of fine (PM_2.5) and coarse (PM_2.5–10) particles was achieved using ion chromatography (water-soluble ions), instrumental neutron activation analysis (trace elements) and a thermal–optical transmission technique (organic carbon and elemental carbon). Approximately 50% of the particulate mass was carbonaceous in nature with a clear dominance of organic carbon. The organic carbon-to-elemental carbon ratios up to 300, or even higher, measured in the present study largely exceeded those reported for fires in savannah and tropical forests. More than 30 trace elements and ions have been determined in smoke aerosols, representing in total an average contribution of about 7% to the PM₁₀ mass.     

Water deficit stress induces different monoterpene and sesquiterpene emission changes in Mediterranean species. Relationship between terpene emissions and plant water potential

The effects of water deficit stress and plant water potential (psi) on monoterpene and sesquiterpene leaf emissions from Rosmarinus officinalis, Pinus halepensis, Cistus albidus and Quercus coccifera were studied over 11 days of water withholding (from t(1) to t(11)), after substrates had achieved their field capacity (control pots: t(0)). Volatile compounds were sampled from the same twig per plant all throughout the study, using a dynamic bag enclosure system. Volatiles, collected in Tenax TA, were studied by means of GC-FID and GC-MS. Monoterpene emissions of water stressed plants (t(1)-t(11)) were either similar to those of control seedlings (R. officinalis and Q. coccifera) or higher (P. halepensis and C. albidus). By contrast, sesquiterpene emissions were strongly reduced or inhibited after four days of water withholding, particularly for R. officinalis, thus altering terpene emission composition. Despite the positive effect of water stress on leaf monoterpene emissions of P. halepensis and C. albidus, the significant correlation between these emissions and psi showed a slow decrease of these emissions over long term water deficit periods. This contrasted with the rapid decline of sesquiterpene emissions of R. officinalis according to lower values of psi. These results provide an overall picture of the different responses of monoterpene and sesquiterpene emissions to progressive water loss. They also reveal the utility of using psi for estimating some emission rates of some species according to drought conditions.     

A survey of California plant species with a portable VOC analyzer for biogenic emission inventory development

An accurate estimate of the magnitude of biogenic volatile organic compound (BVOC) emissions in California's airsheds is critical for formulating effective strategies to reduce concentrations of fine particles, ozone, and other secondary air pollutants which affect human health and reduce yields of agricultural crops. However, California's natural and urban landscapes contain more than 6000 species, and the BVOC emissions from only a small fraction of these species have been characterized by quantitative measurements. A taxonomic method has been proposed to assign BVOC emission rate measurements to unmeasured species, but data are needed for additional plant families and genera to further develop and test this taxonomic approach. In the present study, BVOC emissions from more than 250 plant species were measured through a semi-quantitative method employing calibrated portable analyzers with photoionization detectors (PID). Replicate samples of live foliage were placed in plastic bags, in both light and darkened conditions, and the BVOC emissions categorized as low, medium or high. To validate our approach, for 63 plant species we compared our PID-measured BVOC emissions with published values, based on gas chromatography (GC) or GC–mass spectrometry, and found them to be well correlated. The method employed was more suited for detecting compounds with relatively higher emission rates, such as isoprene, than compounds with low emission rates, which could include monoterpenes and oxygenated compounds. For approximately 200 plant species not previously measured, the results provide further evidence that plant taxonomy can serve as a useful guide for generalizing the emissions behavior of many, but not all, plant families and genera.     

Estimation of the rate of VOC emissions from solvent-based indoor coating materials based on product formulation

Two computational methods are proposed for estimation of the emission rate of volatile organic compounds (VOCs) from solvent-based indoor coating materials based on the knowledge of product formulation. The first method utilizes two previously developed mass transfer models with two key parameters – the total vapor pressure and the average molecular weight for total volatile organic compounds (TVOCs) – being estimated based on the VOC contents in the product. The second method is based on a simple, first-order decay model with its parameters being estimated from the properties of both the source and the environment. All the model parameters can be readily obtained. Detailed procedures for computing the key parameters are described by using examples. The predictive errors were evaluated with small chamber data, and the results were satisfactory. Thus, the proposed methods provide a way to predict the VOC emissions in the indoor environment without having to conduct costly chamber testing. The two proposed methods work for both TVOCs and individual VOCs. Pros and cons for each method are discussed.     

Measurements of biogenic VOC emissions: sampling,analysis and calibration

We describe an experimental system and techniques for sampling and analyzing biogenic emissions of volatile organic compounds (VOC). The system uses a Teflon chamber to enclose a single branch of a tree. Temperature, photosynthetic active radiation (PAR), relative humidity and carbon dioxide concentration are continuously monitored with a time resolution of five minutes. VOCs are sampled on tubes containing solid adsorbents (Tenax TA and Carbotrap) with a time resolution of 1 h. Composition and concentration of VOC emissions are measured with a gas chromatographic system equipped with a flame ionization detector (FID) for quantitative and a mass spectrometer (MS) for qualitative analysis. To calibrate the system, a diffusion source was built to produce standard mixtures of up to 36 different compounds with mixing ratios at low concentrations and high accuracy. The diffusion rates were monitored over 17 months and showed variations between 0.2 and 7.6% for monoterpenes (expect for α-phellandrene, α-terpinene and γ-terpinene) and between 10.6 and 22.6% for sesquiterpenes. FID response factors calculated from calibration measurements were corrected using correction factors based on the effective carbon number concept. The individual response factors of 23 compounds were combined to a mean response factor (RF_m) with a value of 23,100 μV s ng⁻¹ and a standard deviation of 9%. The system described here was used to measure VOC emission rates of Scots pine (Pinus sylvestris) in 1998 and 1999.     

Monoterpene and sesquiterpene emissions of three Mediterranean species through calcareous and siliceous soils in natural conditions

Little is known about terpene emissions released by plants in response to abiotic factors, except for climate-related factors. Standard emissions (E_S) of monoterpenes (E_SM) and sesquiterpenes (E_SS) of Rosmarinus officinalis, Pinus halepensis and Cistus albidus in siliceous and calcareous sites were examined. Their dependency on some nutrients in these soils was also analyzed. The study was carried out in the south of France at the end of March, when C. albidus exhibited a leaf growth state, while the other two species exhibited a pre-budbreak state. The results revealed that E_S of all major monoterpenes released by R. officinalis and E_S of α-pinene and α-humulene of P. halepensis were higher in plants growing in calcareous soils. In contrast, for C. albidus, E_SM and E_S of β-bourbonene and α-humulene were higher in siliceous soils. E_SM of all species was mainly correlated with nitrogen (N) and available phosphorous (P_A), while dependency on Ca²⁺ or K⁺ was variable. None of these nutrients was significantly correlated with E_SS, suggesting that sesquiterpene synthesis pathway requires different nutrient supplies. While higher soil nutrient content stimulated E_SM of R. officinalis and P. halepensis, it had a negative effect on E_SM of C. albidus, probably because C. albidus exhibited a different phenological state. Considering the soil nature, and particularly N and P_A as inputs in plant terpene inventories could hence contribute to obtain more accurate terpene estimates.     

Comparison of models for describing measured VOC emissions from wood-based panels under dynamic chamber test condition

Measured emission factors are the experimental data used to represent emission characteristics of volatile organic compounds (VOCs) from testing materials under dynamic chamber test conditions. A simple empirical model that describes the measured emission factors will be very useful for practical purposes. In this study, a power law model was compared with a widely used first-order exponential decay model in their ability to describe measured emission factors of wood-based panel materials. It was demonstrated that the power law model is a better choice than the first-order model for describing emission characteristics for short-term (less than 100 h) experimental data. The power law model was also more superior in predicting long-term (up to 900 h) emission factors.     

A comparison of phytoremediation capability of selected plant species for given trace elements

In our experiment, As, Cd, Pb, and Zn remediation possibilities on medium contaminated soil were investigated. Seven plant species with a different trace element accumulation capacity and remediation potential were compared. We found good accumulation capabilities and remediation effectiveness of Salix dasyclados similar to studied hyperaccumulators (Arabidopsis halleri and Thlaspi caerulescens). We have noticed better remediation capability in willow compared to poplar for most of the elements considered in this experiment. On the contrary, poplar species were able to remove a larger portion of Pb as opposed to other species. Nevertheless, the removed volume was very small. The elements found in plant biomass depend substantially on the availability of these elements in the soil. Different element concentrations were determined in natural soil solution and by inorganic salt solution extraction (0.01 molL(-1) CaCl(2)). Extracted content almost exceeded the element concentration in the soil solution. Element concentrations in soil solution were not significantly affected by sampling time.     

Sensory and chemical characterization of VOC emissions from building products: impact of concentration and air velocity

The emissions from five commonly used building products were studied in small-scale test chambers over a period of 50 days. The odor intensity was assessed by a sensory panel and the concentrations of selected volatile organic compounds (VOCs) of concern for the indoor air quality were measured. The building products were three floor coverings: PVC, floor varnish on beechwood parquet and nylon carpet on a latex foam backing; an acrylic sealant, and a waterborne wall paint on gypsum board. The impacts of the VOC concentration in the air and the air velocity over the building products on the odor intensity and on the emission rate of VOCs were studied. The emission from each building product was studied under two or three different area-specific ventilation rates, i.e. different ratios of ventilation rate of the test chamber and building product area in the test chamber. The air velocity over the building product samples was adjusted to different levels between 0.1 and 0.3 m s^-1. The origin of the emitted VOCs was assessed in order to distinguish between primary and secondary emissions. The results show that it is reasonable after an initial period of up to 14 days to consider the emission rate of VOCs of primary origin from most building products as being independent of the concentration and of the air velocity. However, if the building product surface is sensitive to oxidative degradation, increased air velocity may result in increased secondary emissions. The odor intensity of the emissions from the building products only decayed modestly over time. Consequently, it is recommended to use building products which have a low impact on the perceived air quality from the moment they are applied. The odor indices (i.e. concentration divided by odor threshold) of primary VOCs decayed markedly faster than the corresponding odor intensities. This indicates that the secondary emissions rather than the primary emissions, are likely to affect the perceived air quality in the long run. Some of the building products continued to affect the perceived air quality despite the concentrations of the selected VOCs resulted in odor indices less than 0.1. Therefore, odor indices less than 0.1 as an accept criterion cannot guarantee that a building product has no impact on the perceived air quality.     

Intra- and inter-annual variability of VOC emissions from natural and semi-natural vegetation in Europe and neighbouring countries

Biogenic VOC emission estimates from the earth's surface are crucial input parameters in air quality models. Knowledge accumulated in the last years about BVOC source distributions and chemical compound species emission profiles in Europe as well as the demand of air quality modellers for a finer resolution in space and time of BVOC estimates have led to the set-up of new emission modelling systems. An updated fast BVOC emission modelling platform explicitly considering the seasonality of emission potentials and leaf temperature gradients in forest canopies by the semi-empirical emission module (seBVOC) will be proposed and used for estimating hourly values of chemical compound-specific emissions in Europe (33–68° north; 10° west to 40° east) in the years 1997, 2000, 2001, and 2003. Spatial resolution will be 10 km by 10 km. The database used contains latest land and forest distributions, updated foliar biomass densities, leaf area indices (LAI), and plant as well as chemical compound-specific emission potentials, if available. Meteorological input parameters for the respective years will be generated using the non-hydrostatic meteorological model MM5. Highest BVOC emissions occur in daytime hours around noon from the end of May to mid-August in the Mediterranean area and from the mid of June to the end of July in the boreal forests. Comparison of 3 BVOC model approaches will reveal that for July 2003, the European isoprene and monoterpene totals range from 1124 Gg to 1446 Gg and from 338 Gg to 1112 Gg, respectively. Small-scale deviations may be as high as ±0.6 Mg km^?2 for July 2003, reflecting the current uncertainty range for BVOC estimates. Key sources of errors in inventories are still insufficiently detailed land use data for some areas and lacking chemically speciated plant-specific emission potentials in particular in boreal, south-eastern, and northern African landscapes. The hourly emissions of isoprene, speciated terpenes, and oxyVOC have been made available by the NatAir database.