Anthropogenic NOx emissions alter the intrinsic water-use efficiency (WUEi) for Quercus cerris stands under Mediterranean climate conditions

We investigated the effect of N deposition (Ndep) on intrinsic water-use efficiency (WUE_i), the ratio of photosynthesis (A) to stomatal conductance (g_s), for two Quercus cerris stands at different distances to an oil refinery in Southern Italy. We used δ¹³C in tree rings for assessing changes in WUE_i; while the influence of climate and NO_x emission was explored through δ¹⁸O and δ¹⁵N, respectively. Differences in WUE_i between the two sites were significant, with trees exposed to different degrees of NO_x emissions showing an abrupt increase with the onset of pollution. Assuming similar g_s at the two sites, as inferred through δ¹⁸O, the higher N availability at the polluted site caused the shift of the A/g_s ratio in favour of A. Overall, our result suggests that an increase of Ndep may enhance tree WUE under a scenario of reduction of precipitation predicted for Mediterranean area.     

Tree-ring stable isotopes and historical perspectives on pollution - An overview

Hydrogen (δ²H), carbon (δ¹³C), oxygen (δ¹⁸O) and nitrogen (δ¹⁵N) isotopes of tree rings growing in field conditions can be indicative of past pollution effects. The characteristic δ¹³C trend is a positive shift generally explained by invoking closure of stomata, but experimental studies suggest that increased rates of carboxylation could also generate such trends. In many cases the δ¹⁸O and δ²H values decrease in trees exposed to pollution and exhibit inverse coinciding long-term trends with δ¹³C values. However, some trees exposed to diffuse pollution and experimental conditions can show an increase or no δ¹⁸O change even if δ¹³C values increase. These diverse responses depend on how stress conditions modify physiological functions such as stomatal conductance, carboxylation, respiration, and perhaps water assimilation by the root system. Recent studies suggest that δ¹⁵N changes in trees can be caused by soil acidification and accumulation of anthropogenic emissions with isotopic signals deviating from natural N.     

Response of stable carbon isotope in epilithic mosses to atmospheric nitrogen deposition

Epilithic mosses are characterized by insulation from substratum N and hence meet their N demand only by deposited N. This study investigated tissue C, total Chl and δ¹³C of epilithic mosses along 2 transects across Guiyang urban (SW China), aiming at testing their responses to N deposition. Tissue C and total Chl decreased from the urban to rural, but δ¹³C_moss became less negative. With measurements of atmospheric CO₂ and δ¹³CO₂, elevated N deposition was inferred as a primary factor for changes in moss C and isotopic signatures. Correlations between total Chl, tissue C and N signals indicated a nutritional effect on C fixation of epilithic mosses, but the response of δ¹³C_moss to N deposition could not be clearly differentiated from effects of other factors. Collective evidences suggest that C signals of epilithic mosses are useful proxies for N deposition but further works on physiological mechanisms are still needed.     

Carbon isotope analysis for source identification of atmospheric formaldehyde and acetaldehyde in Dinghushan Biosphere Reserve in South China

Formaldehyde and acetaldehyde are two most abundant carbonyls in ambient air. Biogenic emission has been proposed as a significant source other than anthropogenic emissions and atmospheric secondary formation. Here at a forest site in South China, the carbon isotopic compositions of formaldehyde and acetaldehyde emitted from leaves of three tree species (Litsea rotundifolia, Canarium album and Castanea henryi) were measured in comparison with the bulk carbon isotopic compositions of tree leaves. δ¹³C data of the emitted aldehydes (from ?31‰ to ?46‰) were quite different for tree species, which were all more depleted in ¹³C than the tree-leaf bulk δ¹³C values (from ?27‰ to ?32‰). Formaldehyde in ambient air at the forest site had δ¹³C values different from those of leaf-emitted formaldehyde, indicating other sources for ambient formaldehyde apart from direct emission from leaves, most probably the photooxidation of biogenic hydrocarbon like isoprene and monoterpene. The δ¹³C differences of acetaldehyde between ambient data and those of tree leaves emission were less than 1‰, implying direct biogenic emission as the dominant source.     

δ13C and δ15N of moss Haplocladium microphyllum (Hedw.) Broth. for indicating growing environment variation and canopy retention on atmospheric nitrogen deposition

Mosses have been recognized as a useful tool for biomonitoring atmospheric deposition and assessing regional environment. This study was carried on whether the same moss growing in areas with identical regional atmospheric deposition while under different growing environments would have the same indicating signals.Similar variations in mean δ¹³C and δ¹⁵N signatures were found between mosses collected from five habitats, with an increasing sequence from mosses under canopies to epilithic mosses, indicating that habitats were potentially regulating δ¹³C and δ¹⁵N values of mosses. Dryer habitats (lower water availability) and input of more aerosol N were the main reasons for higher δ¹³C and δ¹⁵N values of mosses at open sites (especially for epilithic species), while more negative values of mosses under canopies were attributed to their wetter habitats and less uptake of aerosol N. Additionally, δ¹⁵N values not δ¹³C varied linearly with canopy thickness from −7.84‰ (1 m) to −4.71±0.7‰ (4 m), suggesting δ¹⁵N was more sensitive for indicating canopy retention.Consequently, isotopic data of mosses under different environments could not be compared for atmospheric deposition research with each other even collected at the same site. Moss δ¹³C and δ¹⁵N were affected not only by regional atmospheric N sources but also by their growing environments. δ¹⁵N of epilithic Haplocladium microphyllum at open sites can be taken as confident bio-indicator of atmospheric N deposition, which would deepen the application of stable nitrogen isotope of bryophytes in atmosphere–plant system study.     

Using atmospheric chemistry and storm track information to explain the variation of nitrate stable isotopes in precipitation at a site in central Pennsylvania,USA

Stable isotopes of NO₃^? (δ¹⁵N–NO₃^? and δ¹⁸O–NO₃^?) were monitored in precipitation at a central Pennsylvania site during six storm events in 2005 to determine whether information on atmospheric oxidants (e.g., O₃, NO₂, and NO_x), and storm tracks (using the NOAA HYSPLIT model) were capable of explaining observed seasonal and within-storm isotopic variation. Results showed that δ¹⁵N–NO₃^? and δ¹⁸O–NO₃^? in precipitation varied significantly during individual storm events. Seasonally, δ¹⁵N–NO₃^? and δ¹⁸O–NO₃^? in precipitation followed a pattern of depletion during the summer months and enrichment during the winter months. NO₃^? precursor concentrations and atmospheric oxidants were useful for explaining the seasonal and within-storm variation of δ¹⁵N–NO₃^? for all six storm events as evidenced by negative relationships with NO₂:NO_x ratios and ozone (O₃). In comparison, δ¹⁸O–NO₃^? was positively related to O₃ in three dormant season storms, which suggested that the O₃ oxidation pathway was important for producing the high δ¹⁸O–NO₃^? observed in wintertime precipitation. Storm track information was especially useful for describing differences in δ¹⁵N–NO₃^?. Cool-sector storms originating from the E/NE produced slightly negative δ¹⁵N–NO₃^? values characteristic of automobile emissions, whereas warm-sector storms with tracks from the SW/S/SE produced slightly positive δ¹⁵N–NO₃^? values characteristic of coal-fired emissions. Lightning also may have been an important source of atmospheric NO₃^? during two warm-sector thunderstorms. This study showed that (1) information about oxidant levels can be useful to predict the seasonal and within-storm variation of NO₃^? stable isotopes in precipitation, and (2) knowledge of storm tracks (warm-sector versus cool-sector) may be important for determining sources of NO₃^? in wet deposition.     

The stable carbon isotope composition of PM2.5 and PM10 in Mexico City Metropolitan Area air

The sources and distribution of carbon in ambient suspended particles (PM_2.5 and PM₁₀) of Mexico City Metropolitan Area (MCMA) air were traced using stable carbon isotopes (¹³C/¹²C). Tested potential sources included rural and agricultural soils, gasoline and diesel, liquefied-petroleum gas, volcanic ash, and street dust. The complete combustion of LP gas, diesel and gasoline yielded the lightest δ¹³C values (?27 to ?29‰ vs. PDB), while street dust (PM₁₀) represented the isotopically heaviest endmember (?17‰). The δ¹³C values of rural soils from four geographically separated sites were similar (?20.7 ± 1.5‰). δ¹³C values of particles and soot from diesel and gasoline vehicle emissions and agricultural soils varied between ?23 and ?26‰. Ambient PM samples collected in November of 2000, and March and December of 2001 at three representative receptor sites of industrial, commercial and residential activities had a δ¹³C value centered around ?25.1‰ in both fractions, resulting from common carbon sources. The predominant carbon sources to MCMA atmospheric particles were hydrocarbon combustion (diesel and/or gasoline) and particles of geological origin. The significantly depleted δ¹³C values from the industrial site reflect the input of diesel combustion by mobile and point source emissions. Based on stable carbon isotope mass balance, the carbon contribution of geological sources at the commercial and residential sites was approximately 73% for the PM₁₀ fraction and 54% for PM_2.5. Although not measured in this study, biomass-burning emissions from nearby forests are an important carbon source characterized by isotopically lighter values (?29‰), and can become a significant contributor (67%) of particulate carbon to MCMA air under the prevalence of southwesterly winds. Alternative sources of these ¹³C-depleted particles, such as cooking fires and municipal waste incineration, need to be assessed. Results show that stable carbon isotope measurements are useful for distinguishing between some carbon sources in suspended particles to MCMA air, and that wind direction has an impact on the distribution of carbon sources in this basin.     

Isoprene emissions from a Florida scrub oak species grown in ambient and elevated carbon dioxide

The emission of isoprene (2-methyl-1,3-butadiene) by terrestrial vegetation is an important biosphere–atmosphere exchange which significantly impacts tropospheric chemistry. Isoprene emissions from Chapman oak (Quercus chapmanii) grown for over two years in elevated CO₂ levels were measured and compared to emissions from trees grown in ambient CO₂ levels in identical open-topped chambers, and emissions from ambient-grown trees were compared to emissions from trees grown in chamberless control plots. Emission rates were adjusted to 30 μmol m⁻² s⁻¹ of light intensity and 30°C, and standard T-tests were performed to compare emission rates. No significant differences in isoprene emission were found in ambient vs. elevated CO₂ grown trees, while emissions from ambient vs. control trees showed a significant chamber effect.     

Ozone uptake by citrus trees exposed to a range of ozone concentrations

The Citrus genus includes a large number of species and varieties widely cultivated in the Central Valley of California and in many other countries having similar Mediterranean climates. In the summer, orchards in California experience high levels of tropospheric ozone, formed by reactions of volatile organic compounds (VOC) with oxides of nitrogen (NO_x). Citrus trees may improve air quality in the orchard environment by taking up ozone through stomatal and non-stomatal mechanisms, but they may ultimately be detrimental to regional air quality by emitting biogenic VOC (BVOC) that oxidize to form ozone and secondary organic aerosol downwind of the site of emission. BVOC also play a key role in removing ozone through gas-phase chemical reactions in the intercellular spaces of the leaves and in ambient air outside the plants. Ozone is known to oxidize leaf tissues after entering stomata, resulting in decreased carbon assimilation and crop yield. To characterize ozone deposition and BVOC emissions for lemon (Citrus limon), mandarin (Citrus reticulata), and orange (Citrus sinensis), we designed branch enclosures that allowed direct measurement of fluxes under different physiological conditions in a controlled greenhouse environment. Average ozone uptake was up to 11 nmol s^?1 m^?2 of leaf. At low concentrations of ozone (40 ppb), measured ozone deposition was higher than expected ozone deposition modeled on the basis of stomatal aperture and ozone concentration. Our results were in better agreement with modeled values when we included non-stomatal ozone loss by reaction with gas-phase BVOC emitted from the citrus plants. At high ozone concentrations (160 ppb), the measured ozone deposition was lower than modeled, and we speculate that this indicates ozone accumulation in the leaf mesophyll.     

Atmospheric transport of urban-derived NH(x): Evidence from nitrogen concentration and delta(15)N in epilithic mosses at Guiyang, SW China

Nitrogen concentration and δ¹⁵N in 175 epilithic moss samples were investigated along four directions from urban to rural sites in Guiyang, SW China. The spatial variations of moss N concentration and δ¹⁵N revealed that atmospheric N deposition is dominated by NH_x-N from two major sources (urban sewage NH₃ and agricultural NH₃), the deposition of urban-derived NH_x followed a point source pattern characterized by an exponential decline with distance from the urban center, while the agricultural-derived NH_x was shown to be a non-point source. The relationship between moss N concentration and distance (y = 1.5e^−0.13x + 1.26) indicated that the maximum transporting distance of urban-derived NH_x averaged 41 km from the urban center, and it could be determined from the relationship between moss δ¹⁵N and distance [y = 2.54 ln(x) − 12.227] that urban-derived NH_x was proportionally lower than agricultural-derived NH_x in N deposition at sites beyond 17.2 km from the urban center. Consequently, the variation of urban-derived NH_x with distance from the urban center could be modeled as y = 56.272e^−0.116x − 0.481 in the Guiyang area.     

Stable sulphur and nitrogen isotopes of the moss Haplocladium microphyllum at urban,rural and forested sites

Elemental (S and N) and isotopic (δ³⁴S and δ¹⁵N) contents in the moss Haplocladium microphyllum at urban, rural and forested sites in acid rain area of South China have been analyzed for comparisons to show whether they are different and can be effectively used to identify S and N sources of atmospheric deposition. Average moss S content at rural sites (0.29 ± 0.06%) was found to be in between those at urban (0.35 ± 0.05%) and forested (0.25 ± 0.04%) sites, which are significantly different. Average N contents of urban (2.60 ± 0.56%) and rural mosses (2.84 ± 0.77%) are not significantly different, while both are significantly different to that of forested mosses at most areas, indicating that the atmosphere over rural sites has been polluted by N as seriously as that over urban sites. Nitrogen supply, relative to S supply, was in excess of the requirement for protein synthesis, especially at rural and forested sites. Moss stable isotope signatures have been proven to be effective tools for deciphering atmospheric S and N sources at these sites. Through moss δ³⁴S signatures, we found that atmospheric S at urban and forested sites was mainly from local coal combustion and domestic biomass burning, respectively, whereas northerly air masses contributed more S to forested sites. The relatively negative moss δ¹⁵N values (?7.5 ± 3.0, ?3.4 ± 2.1 and ?0.8 ± 2.1‰) demonstrated that the main form in the N deposition was NH_x in these sites. More negative δ¹⁵N signatures in urban mosses (?7.5 ± 3.0‰) indicated the contribution of NH₃ released from untreated city sewage and wastes, while relatively less negative δ¹⁵N for rural and forested mosses (3.4 ± 2.1 and ?0.8 ± 2.1‰) was largely derived from agricultural NH₃.     

Effects of canopy-deposition interaction on H+ supply to soils in Pinus banksiana and Populus tremuloides ecosystems in the Athabasca oil sands region in Alberta, Canada

Soil acidification has been of concern in the oil sands region in Alberta due to increased acid deposition. Using the canopy budget model, and accounting for H⁺ canopy leaching by organic acids, we determined sources and sinks of H⁺ in throughfall in jack pine (Pinus banksiana) and trembling aspen (Populus tremuloides) stands in two watersheds from 2006 to 2009. In pine stands, H⁺ deposition was greater in throughfall than in bulk precipitation while the opposite was true in aspen stands. The annual H⁺ interception deposition was 148.8-193.8 and 49.7-70.0 mol_c ha⁻¹ in pine and aspen stands, respectively; while the annual H⁺ canopy leaching was 127.1-128.7 and 0.0-6.0 mol_c ha⁻¹, respectively. The greater H⁺ supply in pine stands was caused by greater interception deposition of SO₄²⁻ and organic acids released from the pine canopy. Such findings have significant implications for establishing critical loads for various ecosystems in the oil sands region.     

Application of 15N–18O double stable isotope tracer technique in an agricultural nonpoint polluted river of the Yangtze Delta Region

One strategy to combat nitrate (NO₃-N) contamination in rivers is to understand its sources. NO₃-N sources in the East Tiaoxi River of the Yangtze Delta Region were investigated by applying a ¹⁵N–¹⁸O dual isotope approach. Water samples were collected from the main channel and from the tributaries. Results show that high total N and NO₃-N are present in both the main channel and the major tributaries, and NO₃-N was one of the most important N forms in water. Analysis of isotopic compositions (δ ¹⁸O, δD) of water suggests that the river water mainly originated from three tributaries during the sampling period. There was a wide range of δ ¹⁵N-NO₃ (?1.4 to 12.4 ‰) and a narrow range of δ ¹⁸O-NO₃ (3.7 to 9.0 ‰) in the main channel waters. The δ ¹⁵N and δ ¹⁸O-NO₃ values in the upper, middle, and lower channels along the river were shifted as 8.2, 3.5, and 9.5 ‰, and 9.0, 4.2, and 6.0 ‰, respectively. In the tributary South Tiao, the δ ¹⁵N and δ ¹⁸O-NO₃ values were as high as 9.5 and 7.0 ‰, while in the tributaries Mid Tiao and North Tiao, NO₃-N in most of the samples had relatively low δ ¹⁵N and δ ¹⁸O-NO₃ values from 2.3 to 7.5 ‰ and 4.7 to 7.0 ‰, separately. Our results also suggest that the dual isotope approach can help us develop the best management practice for relieving NO₃-N pollution in the rivers at the tributary scale.     

Nitrogen oxide fluxes between corn (Zea mays L.) leaves and the atmosphere

In the United States, fertilized corn fields, which make up approximately 5% of the total land area, account for approximately 45% of total soil NO_x emissions. Leaf chamber measurements were conducted of NO and NO₂ fluxes between individual corn leaves and the atmosphere in (1) field-grown plants near Champaign, IL (USA) in order to assess the potential role of corn canopies in mitigating soil–NO_x emissions to the atmosphere, and (2) greenhouse-grown plants in order to study the influence of various environmental variables and physiological factors on the dynamics of NO₂ flux. In field-grown plants, fluxes of NO were small and inconsistent from plant to plant. At ambient NO concentrations between 0.1 and 0.3 ppbv, average fluxes were zero. At ambient NO concentrations above 1 ppbv, NO uptake occurred, but fluxes were so small (14.3±0.0 pmol m⁻² s⁻¹) as to be insignificant in the NO_x inventory for this site. In field-grown plants, NO₂ was emitted to the atmosphere at ambient NO₂ concentrations below 0.9 ppbv (the NO₂ compensation point), with the highest rate of emission being 50 pmol m⁻² s⁻¹ at 0.2 ppbv. NO₂ was assimilated by corn leaves at ambient NO₂ concentrations above 0.9 ppbv, with the maximum observed uptake rate being 643 pmol m⁻² s⁻¹ at 6 ppbv. When fluxes above 0.9 ppbv are standardized for ambient NO₂ concentration, the resultant deposition velocity was 1.2±0.1 mm s⁻¹. When scaled to the entire corn canopy, NO₂ uptake rates can be estimated to be as much as 27% of the soil-emitted NO_x. In greenhouse-grown and field-grown leaves, NO₂ deposition velocity was dependent on incident photosynthetic photon flux density (PPFD; 400–700 nm), whether measured above or below the NO₂ compensation point. The shape of the PPFD dependence, and its response to ambient humidity in an experiment with greenhouse-grown plants, led to the conclusion that stomatal conductance is a primary determinant of the PPFD response. However, in field-grown leaves, measured NO₂ deposition velocities were always lower than those predicted by a model solely dependent on stomatal conductance. It is concluded that NO₂ uptake rate is highest when N availability is highest, not when the leaf deficit for N is highest. It is also concluded that the primary limitations to leaf-level NO₂ uptake concern both stomatal and mesophyll components.     

Compound specific carbon and hydrogen stable isotope analyses of volatile organic compounds in various emissions of combustion processes

This study presents carbon (δ¹³C) and hydrogen (δD) isotope values of volatile organic compounds (VOCs) in various emission sources using thermal desorption-gas chromatography-isotope ratio mass spectrometry (TD-GC-irMS). The investigated VOCs ranged from C6 to C10. Samples were taken from (i) car exhaust emissions as well as from plant combustion experiments of (ii) various C3 and (iii) various C4 plants. We found significant differences in δ values of analysed VOCs between these sources, e.g. δ¹³C of benzene ranged between (i) −21.7 ± 0.2‰, (ii) −27.6 ± 1.6‰ and (iii) −16.3 ± 2.2‰, respectively and δD of benzene ranged between (i) −73 ± 13‰, (ii) −111 ± 10‰ and (iii) −70 ± 24‰, respectively. Results of VOCs present in investigated emission sources were compared to values from the literature (aluminium refinery emission). All source groups could be clearly distinguished using the dual approach of δ¹³C and δD analysis. The results of this study indicate that the correlation of compound specific carbon and hydrogen isotope analysis provides the potential for future research to trace the fate and to determine the origin of VOCs in the atmosphere using thermal desorption compound specific isotope analysis.     

Belowground effects of enhanced tropospheric ozone and drought in a beech/spruce forest (Fagus sylvatica L./Picea abies [L.] Karst)

The effects of experimentally elevated O₃ on soil respiration rates, standing fine-root biomass, fine-root production and δ¹³C signature of newly produced fine roots were investigated in an adult European beech/Norway spruce forest in Germany during two subsequent years with contrasting rainfall patterns. During humid 2002, soil respiration rate was enhanced under elevated O₃ under beech and spruce, and was related to O₃-stimulated fine-root production only in beech. During dry 2003, the stimulating effect of O₃ on soil respiration rate vanished under spruce, which was correlated with decreased fine-root production in spruce under drought, irrespective of the O₃ regime. δ¹³C signature of newly formed fine-roots was consistent with the differing g_s of beech and spruce, and indicated stomatal limitation by O₃ in beech and by drought in spruce. Our study showed that drought can override the stimulating O₃ effects on fine-root dynamics and soil respiration in mature beech and spruce forests.     

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.     

Nitrogen isotopes: Tracers of origin and processes affecting PM10 in the atmosphere of Paris

Nitrogen in atmospheric particles in an urban environment is the result of complex primary and secondary processes, which renders identifying its origin somewhat complicated. Using the example of PM₁₀ in the atmosphere of Paris (France), it is shown that the use of stable nitrogen-isotope compositions (δ¹⁵N) alleviates this difficulty and provides clear information on the sources of primary and possibly of secondary nitrogen. Characterization of emissions of the different types of emitters in the city (road traffic, waste incinerators and heating sources) shows that these are clearly discriminated by specific isotope signatures. δ¹⁵N is particularly useful in showing that a substantial portion of the nitrogen is the result of secondary reactions, reactions that are different in summer and winter, as are the corresponding pollution sources. While it is unclear, among point sources, what the winter source of primary nitrogen is, road traffic appear to be the source of primary nitrogen in summer. Identification of the sources of the secondary nitrogen strongly depends on the nitrogen isotope fractionations (Δ¹⁵N) associated to atmospheric conversion of NO_x to nitrate, but hypothesises presented here hint at the possible corresponding pollution sources.     

Historical nitrogen content of bryophyte tissue as an indicator of increased nitrogen deposition in the Cape Metropolitan Area, South Africa

Information on changes in precipitation chemistry in the rapidly expanding Cape Metropolitan Area (CMA) of South Africa is scarce. To obtain a long-term record of N deposition we investigated changes in moss foliar N, C:N ratios and nitrogen isotope values that might reflect precipitation chemistry. Tissue from 9 species was obtained from herbarium specimens collected between 1875 and 2000 while field samples were collected in 2001/2002. There is a strong trend of increasing foliar N content in all mosses collected over the past century (1.32-1.69 %N). Differences exist between ectohydric mosses which have higher foliar N than the mixohydric group. C:N ratios declined while foliar δ¹⁵N values showed no distinct pattern. From relationships between moss tissue N and N deposition rates we estimated an increase of 6-13 kg N ha⁻¹ a⁻¹ since 1950. Enhanced N deposition rates of this magnitude could lead to biodiversity losses in native ecosystems.     

Compound specific carbon and hydrogen stable isotope analyses of volatile organic compounds in various emissions of combustion processes

This study presents carbon (δ¹³C) and hydrogen (δD) isotope values of volatile organic compounds (VOCs) in various emission sources using thermal desorption–gas chromatography–isotope ratio mass spectrometry (TD–GC–irMS). The investigated VOCs ranged from C6 to C10. Samples were taken from (i) car exhaust emissions as well as from plant combustion experiments of (ii) various C3 and (iii) various C4 plants. We found significant differences in δ values of analysed VOCs between these sources, e.g. δ¹³C of benzene ranged between (i) −21.7 ± 0.2‰, (ii) −27.6 ± 1.6‰ and (iii) −16.3 ± 2.2‰, respectively and δD of benzene ranged between (i) −73 ± 13‰, (ii) −111 ± 10‰ and (iii) −70 ± 24‰, respectively. Results of VOCs present in investigated emission sources were compared to values from the literature (aluminium refinery emission). All source groups could be clearly distinguished using the dual approach of δ¹³C and δD analysis. The results of this study indicate that the correlation of compound specific carbon and hydrogen isotope analysis provides the potential for future research to trace the fate and to determine the origin of VOCs in the atmosphere using thermal desorption compound specific isotope analysis.