Stable carbon isotopes in dissolved inorganic carbon: extraction and implications for quantifying the contributions from silicate and carbonate weathering in the Krishna River system during peak discharge

We present a comparative study of two offline methods, a newly developed method and an existing one, for the measurement of the stable carbon isotopic composition (δ¹³C) of dissolved inorganic carbon (DIC; δ¹³C_DIC) in natural waters. The measured δ¹³C_DIC values of different water samples, prepared from laboratory Na₂CO₃, ground and oceanic waters, and a laboratory carbonate isotope standard, are found to be accurate and reproducible to within 0.5 ‰\ (1σ). The extraction of CO₂ from water samples by these methods does not require pre-treatment or sample poisoning and can be applied to a variety of natural waters to address carbon cycling in the hydrosphere. In addition, we present a simple method (based on a two-end-member mixing model) to estimate the silicate-weathering contribution to DIC in a river system by using the concentration of DIC and its δ¹³C. This approach is tested with data from the Krishna River system as a case study, thereby quantifying the contribution of silicate and carbonate weathering to DIC, particularly during peak discharge.     

Spatial and seasonal variations in the stable C isotope composition of dissolved inorganic carbon and in physico-chemical water parameters in the Plitvice Lakes system

Plitvice Lakes waters were collected at 14 sampling points, including springs, tributaries and lakes, for the period 2002–2007. The results of the physical and chemical conditions of calcite precipitation as well as the δ¹³C values of dissolved inorganic carbon (DIC) were used to study the processes influencing calcite precipitation. Significant differences between spring, lake and stream waters as well as changes in the downstream direction were observed. The correlation between δ¹³C_DIC values and physico-chemical conditions for calcite precipitation showed that calcite precipitates in lake waters which are oversaturated with respect to CaCO₃ (I _sat values 4–10) and with δ¹³C_DIC values between?11.5 and?8.5 ‰. In spring waters, the δ¹³C_DIC values were more negative, from?14 to?12 ‰, and I _sat values of 1–2 indicated that equilibrium conditions for calcite precipitation were not attained. The downstream increase in δ¹³C_DIC correlated with the increase in the δ¹³C values of calcite in the lake sediments, suggesting that the freshwater calcite was mainly of autochthonous origin and precipitated within the water column in isotopic equilibrium with DIC.     

Effect of preservation on the δ13C value of dissolved inorganic carbon in different types of water samples

Recent studies have shown that the stable carbon isotope compositions of dissolved inorganic carbon (δ¹³C_DIC) of water samples preserved with HgCl₂ and CuSO₄ vary. Furthermore, mercury and cuprum compounds are toxic to the human or biological system and require proper waste disposal. To test the effect of preservation on the δ¹³C value of DIC in different types of water samples, a set of water samples with different DIC concentrations was preserved using different methods, including preserving with inhibitors (CuSO₄ or HgCl₂), preserving under frozen conditions, filtering through a 0.4 μ m paper filter, and the DIC species precipitated in the form of solid BaCO₃. Our results show that δ¹³C_DIC values of the samples preserved with CuSO₄ and HgCl₂ become more positive with increased storage time. The δ¹³C_DIC of the water samples preserved under frozen conditions and the precipitated DIC as BaCO₃ are also more positive than original water samples. However, the δ¹³C values were relatively stable for up to 90 days in all water samples filtered through the 0.4 μ m paper filter and stored under cool conditions (0–4 °C). Therefore, we suggest that the better method for the storage of water samples is to filter the samples through a 0.4 μ m paper filter while out in the field and preserve them under cool conditions, thereby avoiding the use of preservatives.     

C and O stable isotopic signatures of fast-growing dripstones on alkaline substrates: reflection of growth mechanism,carbonate sources and environmental conditions

Secondary carbonate precipitates (dripstones) formed on concrete surfaces in four different environments – Mediterranean and continental open-space and indoor environments (inside a building and in a karstic cave) – were studied. The fabric of dripstones depends upon water supply, pH of mother solution and carbonate-resulting precipitation rate. Very low δ¹³C (average?28.2‰) and δ¹⁸O (average?18.4‰) values showed a strong positive correlation, typical for carbonate precipitated by rapid dissolution of CO₂ in a highly alkaline solution and consequent disequilibrium precipitation of CaCO₃. The main source of carbon is atmospheric or biogenic CO₂ in the poorly ventilated karstic cave, which is reflected in even lower δ¹³C values. Statistical analysis of δ¹³C and δ¹⁸O values of the four groups of samples showed that the governing factor of isotope fractionation is not the temperature, but rather the precipitation rate.     

Conference Report

Soil from Free-Air Carbon dioxide Enrichment (FACE) plots (FAL, Braunschweig) under ambient air (375 ppm; δ¹³C–CO₂?9.8‰) and elevated CO₂ (550 ppm; for six years; δ¹³C–CO₂?23‰), either under 100% nitrogen (N) (180 kg ha^?1) or 50% N (90 kg ha^?1) fertilisation treatments, was analysed by thermogravimetry. Soil samples were heated up to the respective temperatures and the remaining soil was analysed for δ¹³C and δ¹⁵N by Isotope Ratio Mass Spectrometry (IRMS). Based on differential weight losses, four temperature intervals were distinguished. Weight losses in the temperature range 20–200 °C were connected mostly with water volatilisation. The maximum weight losses and carbon (C) content were measured in the soil organic matter (SOM) pool decomposed at 200–360 °C. The largest amount of N was detected in SOM pools decomposed at 200–360 °C and 360–500 °C. In all temperature ranges, the δ¹³C values of SOM pools were significantly more negative under elevated CO₂ versus ambient CO₂. The incorporation of new C into SOM pools was not inversely proportional to its thermal stability. 50% N fertilisation treatment gained higher C exchange under elevated CO₂ in the thermally labile SOM pool (200–360 °C), whereas 100% N treatment induced higher C turnover in the thermally stable SOM pools (360–500 °C, 500–1000 °C). Mean Residence Time of SOM under 100% N and 50% N fertilisation showed no dependence between SOM pools isolated by increasing temperature of heating and the renovation of organic C in those SOM pools. Thus, the separation of SOM based on its thermal stability was not sufficient to reveal pools with contrasting turnover rates of C.     

Field-based cavity ring-down spectrometry of δ13C in soil-respired CO2

Measurement of soil-respired CO₂ at high temporal resolution and sample density is necessary to accurately identify sources and quantify effluxes of soil-respired CO₂. A portable sampling device for the analysis of δ¹³C values in the field is described herein.

CO₂ accumulated in a soil chamber was batch sampled sequentially in four gas bags and analysed by Wavelength-Scanned Cavity Ring-down Spectrometry (WS-CRDS). A Keeling plot (1/[CO₂] versus δ¹³C) was used to derive δ¹³C values of soil-respired CO₂. Calibration to the δ¹³C Vienna Peedee Belemnite scale was by analysis of cylinder CO₂ and CO₂ derived from dissolved carbonate standards. The performance of gas-bag analysis was compared to continuous analysis where the WS-CRDS analyser was connected directly to the soil chamber.

Although there are inherent difficulties in obtaining absolute accuracy data for δ¹³C values in soil-respired CO₂, the similarity of δ¹³C values obtained for the same test soil with different analytical configurations indicated that an acceptable accuracy of the δ¹³C data were obtained by the WS-CRDS techniques presented here. Field testing of a variety of tropical soil/vegetation types, using the batch sampling technique yielded δ¹³C values for soil-respired CO₂ related to the dominance of either C₃ (tree, δ¹³C=?27.8 to?31.9 ‰) or C₄ (tropical grass, δ¹³C=?9.8 to?13.6 ‰) photosynthetic pathways in vegetation at the sampling sites. Standard errors of the Keeling plot intercept δ¹³C values of soil-respired CO₂ were typically<0.4 ‰ for analysis of soils with high CO₂ efflux (>7–9 μmol m^?2 s^?1).     

Two-step synthesis of ethylene glycol-D6 via isotope exchange of glycolic acid

Tracers can be used to monitor emissions of leachate from landfills in order to detect hydrological pathways and to evaluate environmental pollution. We investigated the stable carbon isotope ratio (δ¹³C–Σ CO ₂) in dissolved inorganic carbon and tritium (³H) in water, in addition to the tracers of pollution commonly found in relatively high concentrations in leachate, such as chloride (Cl), organic matter (COD), nitrogen (total and NH₄–N), iron (Fe), electrical conductivity (EC) and pH. The sampling was performed at seven landfills in the south-eastern part of Norway during a period of 5 years. The objective was to evaluate the potential for tracing leachate in the environment with emphasis on groundwater pollution. By measuring the δ¹³C–Σ CO ₂ in leachates, groundwaters and surface waters, the influence of leachate can be identified. The value of δ¹³C–Σ CO ₂ varied from?5.5 to 25.9 ‰ in leachate, from?25.4 to 14.7 ‰ in groundwater and from?19.7 to?13.1 ‰ in creeks. A comparison of the carbon isotope ratio with COD, EC and the concentrations of total and NH ₄–N, Cl and Fe showed that δ¹³C–Σ CO ₂ is a good tracer for leachate due to higher sensitivity compared to other parameters. The mean concentrations of all the studied parameters were higher in the leachate samples; however, only the carbon isotope ratio showed significant differences between all the groups with strong and middle pollution and samples with low pollution, showing that it can be used as a convenient tracer for leachate in groundwater and surface water. The carbon isotope ratio showed strong correlation between nitrogen, EC and bicarbonate, but not with pH. Tritium was only sporadically found in measureable concentrations and is not considered as a suitable tracer at the sampled locations.     

Influence of air pollution and site conditions on trends of carbon and oxygen isotope ratios in tree ring cellulose

Oxygen and carbon isotopic compositions of tree ring cellulose (δ¹³C_cell and δ¹⁸O_cell) were measured for pines growing at four sites in east Germany. Three sites differed markedly in soil water availability within a short distance and the fourth site served as a reference. The choice of the sites was guided by the desire to detect effects of air pollution on the long-term trend of isotopic compositions and to examine the influence of soil water availability on the relationship between the carbon and oxygen isotope ratios. Locations in east Germany are particularly well suited for the study of pollution effects because there was a steady increase in environmental contamination until the German Reunification in 1990, followed by a sharp decline due to the implementation of stricter environmental standards.

The long-term trend of δ¹³C_cell showed an extraordinary increase in the period 1945–1990 and a rapid decrease after 1990, whereas δ¹⁸O_cell remained nearly constant. The increase of δ¹³C_cell is explained by secondary fractionation caused by phytotoxicity of SO₂. Two effects are mainly responsible for the secondary fractionation under SO₂ exposure: increase of dark respiration, and changes in photosynthate allocation and partitioning. Both effects do not influence δ¹⁸O_cell. Furthermore, a significant positive correlation between the year-to-year variations of carbon and oxygen isotope ratios (δ¹³C_resid and δ¹⁸O_resid) has been found for all sites. The slopes of the relationship between δ¹³C_resid and δ¹⁸O_resid differ insignificantly. It is concluded that this relationship is not influenced by soil water availability but by climatic variables.     

Influence of Nitrogen Supply and Temperature on Stable Carbon Isotope Ratios in Plants of Different Photosynthetic Pathways (C3, C4, CAM)

Abstract

One representative species of each of the three photosynthetic pathways (C₃, C₄, CAM) were cultivated in growth chambers with high and low nitrogen nutrition level respectively once at 20°C day/13°C night temperature, once at 30°C day/13°C night. Leaf conductances and δ¹³C values of the leaves of each plant were determined. At 20°C day temperature the C₃ species showed higher leaf conductance with low nitrogen nutrition level than with high nitrogen level, which is also reflected in a more negative δ¹³C value, whereas both C₄ and CAM plants did not respond in this manner to nitrogen supply. An increase of day temperature to 30°C diminished the significant response of the C₃ plant, while the response of C₄ and CAM representatives to nitrogen nutrition did not change markedly.     

Soil matrix tracer contamination and canopy recycling did not impair 13CO2 plant–soil pulse labelling experiments

When conducting ¹³CO₂ plant–soil pulse labelling experiments, tracer material might cause unwanted side effects which potentially affect δ¹³C measurements of soil respiration (δ¹³C_SR) and the subsequent data interpretation. First, when the soil matrix is not isolated from the atmosphere, contamination of the soil matrix with tracer material occurs leading to a physical back-diffusion from soil pores. Second, when using canopy chambers continuously, ¹³CO₂ is permanently re-introduced into the atmosphere due to leaf respiration which then aids re-assimilation of tracer material by the canopy. Accordingly, two climate chamber experiments on European beech saplings (Fagus sylvatica L.) were conducted to evaluate the influence of soil matrix ¹³CO₂ contamination and canopy recycling on soil ¹³CO₂ efflux during ¹³CO₂ plant–soil pulse labelling experiments. For this purpose, a combined soil/canopy chamber system was developed which separates soil and canopy compartments in order to (a) prevent diffusion of ¹³C tracer into the soil chamber during a ¹³CO₂ canopy pulse labelling and (b) study stable isotope processes in soil and canopy individually and independently. In combination with laser spectrometry measuring CO₂ isotopologue mixing ratios at a rate of 1 Hz, we were able to measure δ¹³C in canopy and soil at very high temporal resolution. For the soil matrix contamination experiment, ¹³CO₂ was applied to bare soil, canopy only or, simultaneously, to soil and canopy of the beech trees. The obtained δ¹³C_SR fluxes from the different treatments were then compared with respect to label re-appearance, first peak time and magnitude. By determining the δ¹³C_SR decay of physical ¹³CO₂ back-diffusion from bare soils (contamination), it was possible to separate biological and physical components in δ¹³C_SR of a combined flux of both. A second pulse labelling experiment, with chambers permanently enclosing the canopy, revealed that ¹³CO₂ recycling at canopy level had no effect on δ¹³C_SR dynamics.     

Natural and anthropogenic variations in the Po river waters (northern Italy): insights from a multi-isotope approach

Po is the main Italian river and the δ¹⁸O and δ²H of its water reveal a similarity between the current meteoric fingerprint and that of the past represented by groundwater. As concerns the hydrochemisty, the Ca–HCO₃ facies remained constant over the last 50 year, and only nitrate significantly increased from less than 1?mg/L to more than 10?mg/L in the 1980s, and then attenuated to a value of 9?mg/L. Coherently, δ¹³C_DIC and δ³⁴S_SO4 are compatible with the weathering of the lithologies outcropping in the basin, while extremely variable δ¹⁵N_NO3 indicates contribution from pollutants released by urban, agricultural and zootechnical activities. This suggests that although the origin of the main constituents of the Po river water is geogenic, anthropogenic contributions are locally significant. Noteworthy, the associated aquifers have the same nitrogen isotopic signature of the Po river, but are characterized by significantly higher NO^– ₃ concentration. This implies that aquifers’ pollution is not ascribed to inflow of current river water, and that the attenuation of the nitrogen load recorded in the river is not occurring in the aquifers, due to their longer water residence time and delayed recovery from anthropogenic contamination.     

Effect of waterlogging on carbon isotope discrimination during photosynthesis in Larix gmelinii

Soil moisture is a major factor controlling carbon isotope discrimination (Δ¹³C), which has been demonstrated to decrease under dry conditions in many studies; however, few studies on Δ¹³C under waterlogging condition have been conducted. In this study, a pot experiment was conducted with Larix gmelinii, a major larch species in the east Siberian Taiga, to investigate the effect of waterlogging on Δ¹³C during photosynthesis. Assimilation rate and Δ¹³C_RD (instantaneous Δ¹³C calculated with Rayleigh distillation equation) decreased drastically soon after waterlogging, followed by recovery in their values, which was caused by a change in stomatal conductance. Thereafter, assimilation rate decreased gradually, whereas Δ¹³C_RD decreased more gently. These results were thought to be caused by the decrease in both stomatal conductance and carboxylation. Our results indicate that extreme wet events may cause a decrease in Δ¹³C, which is important information for detecting flooding events in the past using tree-ring isotope analyses and for studying impacts of flooding on plants in areas where waterlogging might occur.     

Estimation of microbial methane generation and oxidation rates in the municipal solid waste landfill of Kaluga city,Russia

Using a theoretical model and mass isotopic balance, biogas (methane and CO₂) released from buried products at their microbial degradation was analysed in the landfill of municipal and non-toxic industrial solid organic waste near Kaluga city, Russia. The landfill contains about 1.34×10⁶ tons of waste buried using a ‘sandwich technique’ (successive application of sand–clay and waste layers). The δ¹³C values of biogenic methane with respect to CO₂ were?56.8 (±2.5) ‰, whereas the δ¹³C of CO₂ peaked at+9.12‰ (+1.4±2.3‰ on average), reflecting a virtual fractionation of carbon isotopes in the course of bacterial CO₂ reduction at the landfill body. After passing through the aerated soil layers, methane was partially oxidised and characterised by δ¹³C in the range of?50.6 to?38.2‰, evidencing enrichment in ¹³C, while the released carbon dioxide had δ¹³C of?23.3 to?4.04‰, respectively. On the mass isotopic balance for the δ¹³C values, the methane production in the landfill anaerobic zone and the methane emitted through the aerated landfill surface to the atmosphere, the portion of methane oxidised by methanotrophic bacteria was calculated to be from 10 to 40% (averaged about 25%). According to the theoretical estimation and field measurements, the annual rate of methane production in the landfill reached about 2.9(±1.4)×10⁹ g C CH₄ yr^?1 or 5.3(±2.6)×10⁶ m³ CH₄ yr^?1. The average rates of methane production in the landfill and methane emission from landfill to the atmosphere are estimated as about 53 (±26) g C CH₄ m^?2 d^?1 (or 4 (±2) mol CH₄ m^?2 d^?1) and 33 (±12) g C CH₄ m^?2 d^?1 (or 2.7 (±1) mol CH₄ m^?2 d^?1), respectively. The calculated part of methane consumed by methanotrophic bacteria in the aerated part of the landfill was 13(±7) g C CH₄ m^?2 d^?1 (or 1.1(±0.6) mol CH₄ m^?2 d^?1) on average.     

Measuring δ13C values of atmospheric acetaldehyde via sodium bisulfite adsorption and cysteamine derivatisation

δ¹³C values of gaseous acetaldehyde were measured by gas chromatograph–combustion–isotope ratio mass spectrometer (GC–C–IRMS) via sodium bisulfite (NaHSO₃) adsorption and cysteamine derivatisation. Gaseous acetaldehyde was collected via NaHSO₃-coated Sep-Pak^® silica gel cartridge, then derivatised with cysteamine, and then the δ¹³C value of the acetaldehyde–cysteamine derivative was measured by GC–C–IRMS. Using two acetaldehydes with different δ¹³C values, derivatisation experiments were carried out to cover concentrations between 0.009×10^?3 and 1.96×10^?3 mg·l^?1) of atmospheric acetaldehyde, and then δ¹³C fractionation was evaluated in the derivatisation of acetaldehyde based on stoichiometric mass balance after measuring the δ¹³C values of acetaldehyde, cysteamine and the acetaldehyde–cysteamine derivative. δ¹³C measurements in the derivertisation process showed good reproducibility (<0.5 ‰) for gaseous acetaldehyde. The differences between predicted and measured δ¹³C values were 0.04–0.31 ‰ for acetaldehyde–cysteamine derivative, indicating that the derivatisation introduces no isotope fractionation for gaseous acetaldehyde, and obtained δ¹³C values of acetaldehyde in ambient air at the two sites were distinct (?34.00 ‰ at an urban site versus?31.00 ‰ at a forest site), implying potential application of the method to study atmospheric acetaldehyde.     

Spatial and temporal variability of stable isotopes and biological parameters for the Danube River in Serbia

This paper presents the results of hydrological, physicochemical, biological, and isotopic investigations of the Danube River along the stretch through Serbian territory conducted during four campaigns in September and November 2007, September 2008 and April 2009. The stable isotope values exhibited significant changes both in the Danube (?10.7 to?9.5‰ for δ¹⁸O and?73.7 to?67.1 ‰ for δ²H) and in its tributaries (?9.1 to?8.5‰ for δ¹⁸O and?69.4 to?59.4‰ for δ²H) depending on the time of survey, which could be partly attributed to the influences of seasonal effects. Results emphasise the dominant role of tributaries inflows from aquifers along the Danube. The very narrow range of δ¹³C_POC (from?28.9 to?27.4 ‰) was associated with relatively high C/N ratios (C/N>9), and together with δ¹⁵N_TPN values, the date suggested that, in early spring, a major fraction of particulate organic matter was derived from allochthonous matter. An orthogonal varimax rotation of the principal components analysis identified four latent factors (‘mineral related’, ‘biological’, ‘hardness’, and ‘soil inlets’) which are responsible for the data structure covering 79% of the observed variations among the variables studied. A reliable grouping of samples with respect to the season was found.     

Ecophysiological Studies on the Vegetation of Madagascar: A δ13C and δD Survey for Incidence of Crassulacean Acid Metabolism (Cam) Among Orchids From Montane Forests and Succulents from the Xerophytic Thorn-Bush

Abstract

The incidence of Crassulacean acid metabolism (CAM) in plants collected at various habitats in Madagascar was investigated by survey of carbon and hydrogen isotope ratios ((δ¹³C and δD values). In about 50% of the epiphytic orchids from evergreen higher and lower montane forests the δ¹³C values were indicative for CAM. The remainder of the species are presumably C₃ plants. In all samples of malagasy epiphytic leafless orchids comprising 9 species, the δ¹³C values suggest extreme CAM with CO₂ uptake proceeding entirely during the night. All terrestrial orchids collected in the lower montane forests obviously acquire external carbon by C₃-photosynthesis, whereas Lissochilus decaryi, a terrestrial orchid from the semi-arid south of Madagascar and various other species of this genus are CAM plants. This is the first report of CAM occurrence in sympodial terrestrial orchids.

Judged by the δ¹³C values, all succulents (mainly Didiereaceae, Euphorbiaceae, Crassulaceae and Asclepiadaceae) collected at the xerophytic thorn-bush of the semi-arid south perform pronounced CAM. Where it applies, our δ¹³C measurements in the thorn-bush succulents revealed values being practically identical with those found by K. Winter in samples of the same species collected at the same site nearly 10 years earlier. This shows extreme constancy over long duration of time in the mode of CAM performed by the succulents of the malagasy thorn-bush vegetation. Since the δ¹³C survey now comprises all 11 known species of the Didiereaceae, it is unequivocally clear that all members of this family are CAM plants. Most of the individuals of the species of the Didiereaceae grown in a glass-house had slightly more negative δ¹³C values compared with those grown at the natural stands suggesting some contribution of C₃-photosynthesis to carbon acquisition under the evaporatively less demanding glass-house conditions (and perhaps higher CO₂ concentrations in the gas phase).

Despite of the fact that the hydrogen isotope composition of meteoric waters depends to a large extent on the altitude and temperature-climate of the site where the concerned plants grow, it was found that in samples obtained in the cooler higher evergreen montane forest as well as in the warmer lower evergreen montane forest and the lowland thorn-bush of the hot, semiarid south of Madagascar the δ values found in the organic matter (δD^org) were in the same range (between about - 10‰ to about - 90‰). This suggests that in our case the hydrogen isotope compositions of the meteoric waters were of minor importance in bringing about the δD^org values found in the plants.     

Sulphur and Oxygen Isotopes in Sulphates in Natural Waters: (2) Deep-Waters from Horizons Below Baltic Sea Floor

Abstract

In this paper we consider deep waters from horizons located under the Baltic-Sea bottom. The samples were taken twice from wells bored in Hel peninsula. The δ¹⁸O and δD values of these waters show their glacial origin since they have significantly low values (δ¹⁸O from ?14 to ?11 whereas the modern groundwaters in Gdańsk area have ?10%₀). In contrast to surface waters the sulphates dissolved in these deep waters have rather high and uniform δ¹⁸O values which are correlated with δ¹⁸O of H₂O but not correlated with δ³⁴S. The isotope patterns may be explained assuming that the waters are very old, in which the slow process of oxygen isotope exchange at low temperatures, but extended in time, could enrich the sulphate in heavier oxygen isotopes.     

Aerosol source (biomass,traffic and coal emission) apportionment in Lithuania using stable carbon and radiocarbon analysis*

In the present study, a combination of the stable carbon isotope ratio (¹³C/¹²C) with radiocarbon data (¹⁴C) allowed us to perform the aerosol source apportionment. Filter samples of PM₁ were collected during the warm and cold periods in rural and urban sites in Lithuania. The ¹⁴C/¹²C ratio of total carbon (TC) was measured using the single stage accelerator mass spectrometer quantifying of fossil and non-fossil derived aerosol emissions. The δ¹³C value was measured using an elemental analyser interfaced with an isotope ratio mass spectrometer. We have found that the highest fraction of contemporary carbon (f_c?=?0.82) was measured during a warm period in a rural location. A higher fraction of fossil fuel-derived carbon was observed for air masses transported from highly industrialized Western European regions during both seasons. Isotope mass balance calculations revealed that the traffic emissions composed 15 and 25?% in rural and urban sites, respectively, and did not change during either season. Input from coal-derived aerosol particles was estimated to be 15?% at an urban site during the cold period. The combination of the stable carbon isotope ratio with the radiocarbon data allowed us to distinguish coal, liquid fossil fuel combustion, and non-fossil derived aerosol particle emissions.