Effect of vegetation removal and water table drawdown on the non-methane biogenic volatile organic compound emissions in boreal peatland microcosms

Biogenic volatile organic compound (BVOC) emissions are important in the global atmospheric chemistry and their feedbacks to global warming are uncertain. Global warming is expected to trigger vegetation changes and water table drawdown in boreal peatlands, such changes have only been investigated on isoprene emission but never on other BVOCs. We aimed at distinguishing the BVOCs released from vascular plants, mosses and peat in hummocks (dry microsites) and hollows (wet microsites) of boreal peatland microcosms maintained in growth chambers. We also assessed the effect of water table drawdown (?20 cm) on the BVOC emissions in hollow microcosms. BVOC emissions were measured from peat samples underneath the moss surface after the 7-week-long experiment to investigate whether the potential effects of vegetation and water table drawdown were shown. BVOCs were sampled using a conventional chamber method, collected on adsorbent and analyzed with GC–MS. In hummock microcosms, vascular plants increased the monoterpene emissions compared with the treatment where all above-ground vegetation was removed while no effect was detected on the sesquiterpenes, other reactive VOCs (ORVOCs) and other VOCs. Peat layer from underneath the surface with intact vegetation had the highest sesquiterpene emissions. In hollow microcosms, intact vegetation had the highest sesquiterpene emissions. Water table drawdown decreased monoterpene and other VOC emissions. Specific compounds could be closely associated to the natural/lowered water tables. Peat layer from underneath the surface of hollows with intact vegetation had the highest emissions of monoterpenes, sesquiterpenes and ORVOCs whereas water table drawdown decreased those emissions. The results suggest that global warming would change the BVOC emission mixtures from boreal peatlands following changes in vegetation composition and water table drawdown.     

Impact of biogenic VOC emissions on a tropical cyclone-related ozone episode in the Pearl River Delta region,China

For quantitative estimate of biogenic volatile organic compound emissions (BVOCs) in South China and their impact on the regional atmospheric chemistry, a 3-day tropical cyclone-related ozone episode was modeled using chemical transport model CMAQ, which was driven by the mesoscale meteorological model MM5. Hourly biogenic emission inventories were constructed using the Sparse Matrix Operator Kernel Emissions (SMOKE) model. The simulation results show good agreement with observation data in air temperature, ozone and NO_x levels. The estimated biogenic emissions of isoprene, terpene, and other reactive VOCs (ORVOCs) during this tropical cyclone-related episode are 8500, 3400, and 11 300 ton day⁻¹, respectively. The ratio of isoprene to the total BVOCs was 36.4%. Two test runs were carried out with one incorporated biogenic emissions and the other without. The simulations show that Guangdong province, particularly the Pearl River Delta (PRD) region, was the area most reactive to biogenic emissions in South China. More ozone was produced in all layers under 1500 m when biogenic emissions were included in comparison to that without BVOCs. The net formation of ozone from 9:00 to 15:00 h was the highest near the surface and could reach 38 ppb, which include 4 ppb attributed to biogenic impact. The enhanced ozone due to biogenic emissions first appeared in the PRD region and slowly spread to a greater area in South China. Process analysis indicated that the surface ozone budget was dominated by the vertical transport and dry deposition. The horizontal transport and gas-phase chemical production were relatively small in the surface layer. Presumably, ozone was produced in upper layers within the atmospheric boundary layer and convected down to surface where it is destroyed. When BVOCs was included, apart from the enhancement of gas-phase chemical production of ozone, both the surface deposition and vertical transport were also augmented.     

Estimating Taiwan biogenic VOC emission: Leaf energy balance consideration

The goal of the present study is to provide a comprehensive model to estimate biogenic volatile organic compounds (BVOCs) in Taiwan. In addition to metrological data, the model consists of (1) 83 land-use patterns, (2) emission factors for various vegetations, (3) energy balance equation to account for leaf temperature, and (4) correction terms for photosynthetically active radiation. The model output includes 4 categories of 33 BVOCs [isoprene, methylbutenol (MBO), 14 species of monoterpenes and 17 other BVOCs]. The results of model verification based on several approaches include: (1) predicted isoprene emission flux correlates relatively good with the observed isoprene concentration (R² = 0.66); (2) correlation between leaf temperature and observed isoprene levels is better than that between ambient temperature and isoprene concentrations (R² = 0.63 vs. 0.58); (3) model-predicted isoprene fluxes match well with observed 3-day diurnal isoprene concentration variations; and (4) subsequent model-predicted O₃ concentrations with the BVOC input obtained in the present study match well than that with previous estimated BVOC data with the observed 6-day diurnal O₃ levels in 8 air quality monitoring stations.Based on the meteorological data in 2000, the total emission of BVOCs in Taiwan was simulated to be about 433,000 ton (33% of total VOCs) of which both isoprene and 14 species of monoterpenes account for about 34%, with 17 species of other BVOCs being 31% and <2% contribution from MBO. Total emissions of BVOCs are higher in lower and medium altitude (300–1000 m) mountain areas with an average of around 15–30 ton km⁻² y⁻¹. The implication of the other results is also discussed.     

Biogenic volatile organic compound emissions (BVOCs). II. Landscape flux potentials from three continental sites in the U.S

Landscape flux potentials for biogenic volatile organic compounds (BVOCs) were derived for three ecosystems in the continental U.S. (Fernbank Forest, Atlanta, GA; Willow Creek, Rhinelander, WI; Temple Ridge, CO). Analytical data from branch enclosure measurements were combined with ecological survey data for plant species composition and biomass. Other quantitative flux measurements at the leaf and landscape level were incorporated to scale the results from the enclosure measurements to the landscape level. Flux estimates were derived by using a one week ambient temperature and light record (30 min time resolution) and adjusting all emission rates to these conditions with temperature and light correction algorithms.     

Tethered balloon measurements of biogenic VOCs in the atmospheric boundary layer

Biogenic volatile organic compounds (BVOCs) were measured on tethered balloon platforms in 11 deployments between 1985 and 1996. A series of balloon sampling packages have been used to describe boundary layer dynamics, BVOC distribution, chemical transformations of BVOCs, and to estimate BVOC emission rates from terrestrial vegetation. Measurements indicated a slow decrease of concentration for BVOCs with altitude in the mixed layer when sampling times were greater than average convective turnover time; surface layer concentrations were more variable because of proximity to various emission sources in the smaller surface layer footprint. Mixed layer concentrations of isoprene remained fairly constant in the middle of the day, in contrast to canopy-level isoprene concentrations, which continued to increase until early evening. Daytime emissions, which increase with temperature and light, appear to be balanced by changes in entrainment and oxidation. Daytime measurements of methacrolein and methyl vinyl ketone, reaction products of the atmospheric oxidation of isoprene, showed fairly constant ratio to each other with altitude throughout the mixed layer. BVOC emission flux estimates using balloon measurements and from the extrapolation of leaf level emissions to the landscape scale were in good agreement.     

Isoprene emissions and climate

Biogenic volatile organic compounds (BVOCs) play an important role in atmospheric chemistry and the carbon cycle. Isoprene is quantitatively the most important of the non-methane BVOCs (NMBVOCs), with an annual emission of about 400–600 TgC; about 90% of this is emitted by terrestrial plants. Incorporating a mechanistic treatment of isoprene emissions within land-surface schemes has recently become a focus for the modelling community, the aim being to quantify the potential magnitude of associated climate feedbacks. However, these efforts are hampered by major uncertainties about why plants emit isoprene and the relative importance of different environmental controls on isoprene emission. The availability and reliability of observations of isoprene fluxes from different types of vegetation is limited, and this also imposes constraints on model development. Nevertheless, progress is being made towards the development of mechanistic models of isoprene emission which, in conjunction with atmospheric chemistry models, will ultimately allow improved quantification of the feedbacks between the terrestrial biosphere and climate under past and future climate states.     

Variation in biogenic volatile organic compound emission pattern of Fagus sylvatica L. due to aphid infection

Volatile organic compounds (VOCs) have been the focus of interest to understand atmospheric processes and their consequences in formation of ozone or aerosol particles; therefore, VOCs contribute to climate change. In this study, biogenic VOCs (BVOCs) emitted from Fagus sylvatica L. trees were measured in a dynamic enclosure system. In total 18 compounds were identified: 11 monoterpenes (MT), an oxygenated MT, a homoterpene (C₁₄H₁₈), 3 sesquiterpenes (SQT), isoprene and methyl salicylate. The frequency distribution of the compounds was tested to determine a relation with the presence of the aphid Phyllaphis fagi L. It was found that linalool, (E)-β-ocimene, α-farnesene and a homoterpene identified as (E)-4,8-dimethyl-1,3,7-nonatriene (DMNT), were present in significantly more samples when infection was present on the trees. The observed emission spectrum from F. sylvatica L. shifted from MT to linalool, α-farnesene, (E)-β-ocimene and DMNT due to the aphid infection. Sabinene was quantitatively the most prevalent compound in both, non-infected and infected samples. In the presence of aphids α-farnesene and linalool became the second and third most important BVOC emitted. According to our investigation, the emission fingerprint is expected to be more complex than commonly presumed.     

Validation of in-situ measurements of volatile organic compounds through flask sampling and gas chromatography/mass spectrometry analysis

Continuous monitoring of ambient non-methane hydrocarbons (NMHCs) by automated gas chromatographs equipped with flame ionization detection (termed in-situ GC/FID) with hourly data resolution was instated in ozone non-attainment areas throughout Taiwan. Performance of these on-site in-situ GCs was validated by manual flask sampling, as well as by in-lab gas chromatography/mass spectrometry (GC/MS) analysis. More than 50 VOCs from C₂ to C₁₁ were analyzed by both methods. Ninety flask samples were collected in series near an in-situ GC monitoring station in order to closely compare with the in-situ measurements. Both time-series and scatter plots from the two methods are displayed and discussed. It was found that over-simplified, un-humidified single-point calibration leading to surface loss was responsible for the bias in the in-situ method, resulting in greater error in accuracy as VOC volatility decreased. Although this over-estimate of the concentrations was found across all target VOCs, both methods were able to consistently capture the variability of ambient VOCs, with R² values greater than 0.9 for most of the major VOCs.     

Measurement of Volatile Organics at Part per Billion Concentrations Using a Cold Trap Inlet and High Speed Gas Chromatography

Direct inlet gas chromatography (GC) is becoming one of the most frequently used techniques for measurement of volatile organics in air. Although GC is an effective tool, its usefulness as a field method can be limited by retention times of several minutes or more, and by the limits of detection. In order to address these issues, a high speed GC system featuring a capillary cold trap inlet and variable speed electrometeramplifier was developed and tested.

The gas cooled inlet was used to collect and focus organic vapors from injection volumes of up to 1 ml. Resistance heating of the metal cold trap produced a narrow injection band that allowed simple separations to be completed in 5 to 20 seconds. Use of a variable speed electrometer-amplifier allowed the response time and noise suppression characteristics to be adjusted to the needs of the specific analysis.

Simple mixtures of organics including aromatics, alkanes and chlorinated hydrocarbons were separated in 20 seconds or less. The limits of detection for 13 test compounds ranged from less than 1 part per billion by volume (ppbv) to about 50 ppbv. Data presented here indicate that high speed GC using a cold trap inlet may be a feasible approach for near real-time measurement of volatile organics in ambient air.     

Polar organic marker compounds in PM2.5 aerosol from a mixed forest site in western Germany

The molecular composition of PM2.5 (particulate matter with an aerodynamic diameter <2.5 microm) aerosol samples collected during a very warm and dry 2003 summer period at a mixed forest site in Jülich, Germany, was determined by gas chromatography/mass spectrometry in an effort to evaluate photooxidation products of biogenic volatile organic compounds (BVOCs) and other markers for aerosol source characterization. Six major classes of compounds represented by twenty-four individual organic species were identified and measured, comprising tracers for biomass combustion, short-chain acids, fatty acids, sugars/sugar alcohols, and tracers for the photooxidation of isoprene and alpha-/beta-pinene. The tracers for the photooxidation of alpha-/beta-pinene include two compounds, 3-hydroxyglutaric acid and 3-methyl-1,2,3-butanetricarboxylic acid, which have only recently been elucidated. The characteristic molecular distribution of the fatty acids with a strong even/odd number carbon preference indicates a biological origin, while the presence of isoprene and terpene secondary organic aerosol products suggests that the photooxidation of BVOCs contributes to aerosol formation at this site. The sum of the median concentrations of the isoprene oxidation products was 21.2 ng m(-3), while that of the terpene oxidation products was 19.8 ng m(-3). On the other hand, the high median concentration of malic acid (37 ng m(-3)) implies that photooxidation of unsaturated fatty acids should also be considered as an important aerosol source process. In addition, the occurrence of levoglucosan and pyrogallol indicates that the site is affected by biomass combustion. Their median concentrations were 30 and 8.9 ng m(-3), respectively.     

Biogenic volatile organic compound emissions from a lowland tropical wet forest in Costa Rica

Twenty common plant species were screened for emissions of biogenic volatile organic compounds (BVOCs) at a lowland tropical wet forest site in Costa Rica. Ten of the species examined emitted substantial quantities of isoprene. These species accounted for 35–50% of the total basal area of old-growth forest on the major edaphic site types, indicating that a high proportion of the canopy leaf area is a source of isoprene. A limited number of canopy-level BVOC flux measurements were also collected by relaxed eddy accumulation (REA). These measurements verify that the forest canopy in this region is indeed a significant source of isoprene. In addition, REA fluxes of methanol and especially acetone were also significant, exceeding model estimates and warranting future investigation at this site. Leaf monoterpene emissions were non-detectable or very low from the species surveyed, and ambient concentrations and REA fluxes likewise were very low. Although the isoprene emission rates reported here are largely consistent with phylogenetic relations found in other studies (at the family, genus, and species levels), two species in the family Mimosaceae, a group previously found to consist largely of non-isoprene emitters, emitted significant quantities of isoprene. One of these, Pentaclethra macroloba (Willd.) Kuntze, is by far the most abundant canopy tree species in the forests of this area, composing 30–40% of the total basal area. The other, Zygia longifolia (Humb. & Bonpl.) Britton & Rose is a common riparian species. Our results suggest that the source strength of BVOCs is important not only to tropical atmospheric chemistry, but also may be important in determining net ecosystem carbon exchange.     

Determination of PAHs in wastewater irrigated agricultural soil using accelerated solvent extraction

A procedure was developed for determination of 16 polycyclic aromatic hydrocarbons (PAHs) in heavily contaminated paddy soil from wastewater irrigated farmland near Tianjin. The sample was distilled with accelerated solvent extraction (ASE), purified by a silica gel column, and measured with GC/MS. The optimal conditions for the distillation were at 140 degrees C (1500 psi) with a 1:1 mixture of dichloromethane and acetone for 5 min. Application of cyclohexane for extract transfer improved the recovery when the ASE extraction was followed by a silica gel cleanup procedure. Recoveries from the method for 16 PAHs ranged from 57-140% with the coefficients of variation of the results ranging from 0.35% to 5.75%. The total 16 PAHs in a composite sample collected from a wastewater irrigated paddy field near Tianjin was 3.90 mg/kg.     

Nonylphenols in freshwaters of the hydrologic system of an Italian district: association with human activities and evaluation of human exposure

A sampling campaign for the determination of concentrations of nonylphenol isomers (NPs) in freshwaters and sediments of the hydrologic system of the Rieti district (central Italy) was conducted from 2002 to 2003. Eighteen sampling points, selected on the basis of the different human activities in the vicinity, were monitored; six series of water samples (from June 2002 to February 2003) and one of sediment samples (summer 2002) were analyzed by GC/MS.

There was a direct relationship between concentrations of NPs and the presence of urban or industrial activities near the sampling point. However, concentrations of NPs in water were in the range of <0.1–1.4 μg l⁻¹, and their presence limited to short distances from the sources of contamination. Accumulation factors in sediment samples ranged from 10² to 5 × 10³.     

Integrating remote sensing and local vegetation information for a high-resolution biogenic emissions inventory--application to an urbanized, semiarid region

This paper presents a methodology for the development of a high-resolution (30-m), standardized biogenic volatile organic compound (BVOC) emissions inventory and a subsequent application of the methodology to Tucson, AZ. The region's heterogeneous vegetation cover cannot be modeled accurately with low-resolution (e.g., 1-km) land cover and vegetation information. Instead, local vegetation data are used in conjunction with multispectral satellite data to generate a detailed vegetation-based land-cover database of the region. A high-resolution emissions inventory is assembled by associating the vegetation data with appropriate emissions factors. The inventory reveals a substantial variation in BVOC emissions across the region, resulting from the region's diversity of both native and exotic vegetation. The importance of BVOC emissions from forest lands, desert lands, and the urban forest changes according to regional, metropolitan, and urban scales. Within the entire Tucson region, the average isoprene, monoterpene, and OVOC fluxes observed were 454, 248, and 91 micrograms/m2/hr, respectively, with forest and desert lands emitting nearly all of the BVOCs. Within the metropolitan area, which does not include the forest lands, the average fluxes were 323, 181, and 70 micrograms/m2/hr, respectively. Within the urban area, the average fluxes were 801, 100, and 100 micrograms/m2/hr, respectively, with exotic trees such as eucalyptus, pine, and palm emitting most of the urban BVOCs. The methods presented in this paper can be modified to create detailed, standardized BVOC emissions inventories for other regions, especially those with spatially complex vegetation patterns.     

Determination and potential importance of diterpene (kaur-16-ene) emitted from dominant coniferous trees in Japan

Reactive volatile organic compounds (VOCs) are known to affect atmospheric chemistry. Biogenic VOCs (BVOCs) have a significant impact on regional air quality due to their large emission rates and high reactivities. Diterpenes (most particularly, kaur-16-ene) were detected in all of the 205 enclosure air samples collected over multiple seasons at two different sites from Cryptomeria japonica and Chamaecyparis obtusa trees, the dominant coniferous trees in Japan,. The emission rate of kaur-16-ene, was determined to be from 0.01 to 7.1 μg dwg⁻¹ h⁻¹ (average: 0.61 μg dwg⁻¹ h⁻¹) employing branch enclosure measurements using adsorbent sampling followed by solid phase-liquid extraction techniques. The emission rate was comparable to that of monoterpenes, which is known major BVOC emissions, collected from the same branches. In addition, total emission of kaur-16-ene at 30 °C was estimated to exceed that of total anthropogenic VOC emissions.     

Characterization of incense smoke by solid phase microextraction—Comprehensive two-dimensional gas chromatography (GC×GC)

Comprehensive two-dimensional gas chromatography in tandem with flame ionization detection (GC×GC-FID) was used for the qualitative fingerprint characterisation of four different types of powdered incense headspace (H/S), and incense smoke. Volatile organic compounds (VOCs) in the incense powder and smoke were extracted by using solid phase microextraction (SPME) with a polydimethylsiloxane/divinylbenzene (PDMS/DVB) 65 μm fiber. Low-polarity/polar, and polar/non-polar phase combinations were tested to contrast the GC×GC separation of components in these two column sets.A total of 324 compounds were tentatively identified, with more than 100 compounds in incense powders and more than 200 compounds in the incense smoke, by using GC coupled to quadrupole mass spectrometric detection. Identification required at least 90% match with the NIST library; otherwise they were considered as unidentified. The smoke stream comprised compounds originating from the incense powder, and combustion products such as PAH, N-heterocyclics, and furans. However, GC×GC was able to separate many more volatile compounds (possibly hundreds more) present in the complex smoke samples, many of which cannot be separated by conventional 1D-GC; this is a direct consequence of the high-resolution power of GC×GC. GC×GC fingerprint comparison of powder H/S with smoke allows facile subtraction of the former from the latter to assist identification of compounds generated from burning incense.     

Emissions of biogenic VOC from forest ecosystems in central Europe: Estimation and comparison with anthropogenic emission inventory

This paper describes a method of estimating emission fluxes of biogenic volatile organic compounds (BVOCs) based on the approach proposed by Guenther et al. (1995) and the high-resolution Corine land-cover 2000 database (1 × 1 km resolution). The computed emission fluxes for the Czech Republic (selected for analysis as being representative of a heavily cultivated, central European country) are compared with anthropogenic emissions, both for the entire country and for individual administrative regions. In some regions, BVOC emissions are as high as anthropogenic emissions; however, in most regions the BVOC emissions are approximately 50% of the anthropogenic emissions. The yearly course of BVOC emissions (represented by monoterpenes and isoprene) is presented, along with the spatial distribution of annual mean values. Differences in emission distributions during winter (January) and summer (June) are also considered.     

Comparison of gas chromatography and immunoassay methods in quantifying fenitrothion residues in grape juice processed into alcoholic drinks.

Wine and Arak, the national alcoholic drink in Lebanon, were prepared from grape juice fortified with fenitrothion to a concentration of 20ppm. Samples of the 11 fractions produced by the fermentation and distillation steps were analyzed for fenitrothion residues using gas chromatography (GC) and enzyme-linked immunosorbent assay (ELISA). Results of residue analyses showed that the two techniques were highly correlated (r = 0.978) and indicated that fenitrothion was stable during the fermentation steps but not during distillation. The clarified wine 35 days later contained about 85% (15.3 ppm) of the fenitrothion concentration found in the juice as determined by GC analysis. Arak was prepared by a two-steps distillation of the clarified wine. The alcohol distillate and undistilled fraction from the first distillation contained 2.5 ppm and 5.8 ppm of fenitrothion, respectively. No fenitrothion residues were detected by both techniques in the four fractions collected from the second distillation step.     

Contamination of fish by 2,3,7,8-tetrachlorodibenzo-P-dioxin: A survey of fish from major watersheds in the United States

A survey of contamination of fish from major watersheds in the United States by 2,3,7,8-TCDD has been conducted by the U.S. EPA. Bottom feeding and predator fish were collected at 90 statistically selected and 305 regionally selected sites and analyzed by GC/MS. It was found that 19% of the statistically sampled sites and 31% of the regionally selected sites were contaminated at or above a minimum level of detection varying from 0.5 to 2.0 pg/g. Ten percent of all samples were contaminated at levels greater than 5.0 pg/g. It was also observed that a subset of samples collected at sites near discharge from pulp/paper manufacture (N=28) had a higher frequency of TCDD contamination above 5.0 pg/g (38%). This subset of samples also contained the sample of the greatest level of TCDD contamination (85 pg/g).     

2,4-D levels in the South Saskatchewan River in 1973 as determined by GLC method.

2,4-D levels in the South Saskatchewan River near Saskatoon in 1973 at the height of the spraying season, and at harvestime, were determined by a method involving direct glc analysis, ankaline hydrolysis, followed by n-butylation of the liberated free acid after acidification of the alkaline solution, and confirmed by subsequent n-octylation. GC/MS also confirmed the presence of 2,4-D. 2,4-D was detected during the spraying season but not at harvest time or in river mud samples. The average level was ca. 2mug of acid equivalent to 2,4-D per liter of river water at the height of the spraying season.