Distribution of stable isotopes in surface water along the Danube River in Serbia

Stable hydrogen and oxygen isotopes were analysed in water samples from the River Danube and its tributaries during a longitudinal survey performed in August 2005 on Serbian territory. Danube river water data ranged from-80 per thousand to-66 per thousand for delta2H, and from-11.2 per thousand to-9.3 per thousand for delta18O with delta values increasing downstream. The isotopic signatures of the adjacent tributaries (the Tisza, the Sava and the Velika Morava) sampled at the locations close to their confluence with the Danube (Titel, Ostruznica and Ljubicevski most, respectively) just about the time of the campaign were enriched (-67 per thousand and-63 per thousand for delta2H, and-9.3 per thousand and-8.9 per thousand for delta18O) with respect to the Danube water because of their catchment effects. Hydrogen and oxygen stable isotope values were used in combination with measured physico-chemical and biological parameters to trace hydrological and transport processes in these river systems. The mixing relationships between the Danube main stream and its tributaries were estimated using the mass balance for isotopic composition and electrical conductivity as conservative parameters. Evidence of an incomplete mixing process at the Centa location, 8 km below the confluence of the Tisza river, with its participation of 88% was shown by its oxygen-18 content. The correlations between river water isotope composition and physico-chemical and biological parameters are discussed.     

13C discriminations of Pinus sylvestris vs. Pinus ponderosa at a dry site in Brandenburg (eastern Germany): 100-year growth comparison

The carbon isotope composition (delta(13)C, per thousand) and discrimination (Delta, per thousand) of old grown North American Pinus ponderosa Dougl. Ex P. et C. Laws. and European Pinus sylvestris L. were determined using trees grown under almost identical growing conditions in a mixed stand in Bralitz, Northeast Germany. Single-tree delta(13)C analyses of tree-ring cellulose of both species were carried out at a yearly resolution for the period 1901-2001 and the results compared with growth (basal area increment). Annual mean delta(13)C values for P. ponderosa ranged from-21.6 per thousand to-25.2 per thousand and for P. sylvestris from-21.4 per thousand to-24.4 per thousand. Accordingly, (13)C discrimination (Delta) showed higher values for P. ponderosa throughout the investigation period. Five characteristic periods of Delta were identified for both the tree species, reflecting positive and negative influences of environmental factors. Good growing conditions such as after-thinning events had a positive effect on Delta, reflecting higher values, while poor conditions like aridity and air pollution had a negative influence, reflecting lower values. The dynamics of Delta were likewise reflected in the growth (basal area increment, BAI). Higher (13)C discrimination values of P. ponderosa led to higher BAIs of P. ponderosa in comparison with P. sylvestris. Correlation function analyses confirmed that P. sylvestris was more dependent on precipitation than P. ponderosa, which showed a closer relationship with temperature. The results confirm that under predominantly dry growing conditions, P. ponderosa showed better growth performance than P. sylvestris, indicating better common intrinsic water-use efficiency and, therefore, higher rates of net photosynthesis at a given transpiration. In view of the prospect of climate change, the results are very significant for assessing both trees' physiological properties and, hence, their potential for coping with future growing conditions.     

Fertilizer nitrogen isotope signatures

There has been considerable recent interest in the potential application of nitrogen isotope analysis in discriminating between organically and conventionally grown crops. A prerequisite of this approach is that there is a difference in the nitrogen isotope compositions of the fertilizers used in organic and conventional agriculture. We report new measurements of delta15N values for synthetic nitrogen fertilizers and present a compilation of the new data with existing literature nitrogen isotope data. Nitrogen isotope values for fertilizers that may be permitted in organic cultivation systems are also reported (manures, composts, bloodmeal, bonemeal, hoof and horn, fishmeal and seaweed based fertilizers). The delta15N values of the synthetic fertilizers in the compiled dataset fall within a narrow range close to 0 per thousand with 80% of samples lying between-2 and 2 per thousand and 98.5% of the data having delta15N values of less than 4 per thousand (mean=0.2 per thousand n=153). The fertilizers that may be permitted in organic systems have a higher mean delta15N value of 8.5 per thousand and exhibit a broader range in delta15N values from 0.6 to 36.7 per thousand (n=83). The possible application of the nitrogen isotope approach in discriminating between organically and conventionally grown crops is discussed in light of the fertilizer data presented here and with regard to other factors that are also important in determining crop nitrogen isotope values.     

Gas forming processes within lignite mining dumps

Gas analyses of the soil atmosphere of lignite mining dumps yielded increased contents of carbon dioxide. To get information about the potential sources and the carbon dioxide releasing capacity of the dumps, samples of dump material were investigated for their contents and isotopic compositions of organic and inorganic carbon as well as the carbon dioxide in the soil atmosphere. The contents of organic and inorganic carbon were found to vary depending on type of dump material. The isotopic composition of the organic carbon ranges between -24.5 and -26.5 per thousand, which is typical for humous materials. The carbonates are found to be of marine origin (delta13C: +0.5 to -1.1 per thousand). By means of the isotope investigations it could be shown that the carbon dioxide in the lignite mining dump arises from these two different sources. Mixing ratios can be calculated using the isotope balance equation. Both reaction paths are associated with oxygen consumption and do not result in an increased gas pressure within the dump.     

Isotope variations in white-tailed kites from various habitats in California: possible limitations in assessing prey utilization and population dynamics

White-tailed kite (Elanus leucurus) populations in the 1930s were close to extirpation in the United States. But by the 1940s, an upward trend towards recovery was apparent and continued to their current stable population levels. These dramatic fluctuations in kite numbers may have been related to changes in rodent prey populations due to the conversion of native habitats to agriculture. To address this question, we evaluated the use of stable isotope analysis in determining if a shift in diet could be isotopically differentiated in current and historic kite populations. We first compared delta13C, delta15N, and delta34S values from present-day kite flight feathers and prey fur samples from four locations in California. The total ranges of isotope values for kite and their rodent prey were similar within each site. Carbon isotope values ranged from -27.1 to -22.2 per thousand in Arcata, -26.1 to -16.9 per thousand in Davis, -27.0 to -15.0 per thousand in Cosumnes, and -28.2 to -11.6 per thousand in Santa Barbara. Nitrogen isotope values ranged from 3.2 to 15.7 per thousand in Arcata, 2.8 to 12.7 per thousand in Davis, 4.0 to 15.7 per thousand in Cosumnes, and 1.7 to 20.0 per thousand in Santa Barbara. Sulfur isotope values ranged from -7.8 to 12.4 per thousand in Arcata, -1.1 to 9.2 per thousand in Davis, 0.7 to 10.9 per thousand in Cosumnes, and -8.6 to 15.6 per thousand in Santa Barbara. Carbon, nitrogen, and sulfur isotope values at each site reflect typical trophic enrichments due to physiological processes. At each site, delta13C and delta15N values reflected the influence of a predominantly C3 or a mixed C3/C4 plant community. Sulfur isotope values reflect the influence of predominant marine or terrestrial sulfur sources at each site. However, variability in isotope values may limit the usefulness of such analyses for addressing prey utilization and population dynamics.     

The fate of organic matter in a papyrus (Cyperus papyrus L.) dominated tropical wetland ecosystem in Nyanza Gulf (Lake Victoria, Kenya) inferred from delta13C and delta15N analysis

Papyrus swamps usually form at the interface between river inlet and open lake. From one such wetland ecosystem (the Kibos system located in the Nyanza Gulf, Lake Victoria, Kenya), three sediment cores were recovered using piston corer in order to determine the fate of organic matter derived from papyrus and possible nutrient pathways in this system. The coring represented a transect from the river through the floating papyrus mat to the lake. Two short cores were retrieved from the lake and river. One long core (2 m) was recovered on a floating papyrus mat. The C:N ratio showed similar trends down core from the three locations. This may possibly be due to diagenic processes such as autolysis, dissolution and microbial mineralisation occurring in the sediments. Statistical analysis through one-way ANOVA revealed no significant differences in the C:N ratios between stations. Results of the stable carbon isotope ratios revealed that the delta(13)C of the river and lake samples were persistently more negative than -20 per thousand over the whole profile indicating possible contribution from terrestrial derived carbon. Regarding the floating mat core, the delta(13)C values ranged from -18.99 per thousand on the top of the floating mat but gradually increased to -16.82 per thousand towards the bottom of the core indicating possible contribution of carbon from Cyperus papyrus that has a delta(13)C value of -13.45+/-0.62 per thousand. Statistical analysis through one-way ANOVA revealed significant differences in the delta(13)C values between stations. The stable nitrogen isotope values were highly positive both in the river and in the lake station (delta(15)N > 10 per thousand), indicating possible contamination from sewage wastes. Values in the swamp were less positive suggesting first, the formation of ammonium depleted in (15)N from intense organic matter mineralisation, secondly indicating the delta(15)N signal of papyrus and, finally that nitrogen fixation processes were possibly occurring in the swamp. Statistical analysis through one-way ANOVA revealed significant differences in the delta(15)N values between stations. The stable isotope findings suggested that carbon derived from papyrus is retained in the swamp. Impoverished oxygen concentration in the swamp suggests high mineralisation of organic matter in the swamp indicating that the retained papyrus-derived carbon is largely respired. We conclude that further studies should be undertaken to determine the respiration rates in the wetland.     

Characteristics of suspended matter in the River Sava watershed, Slovenia

A combination of C/N ratios, delta(13)C and delta(15)N values in suspended matter was used to examine the seasonal (late summer 2004 and spring 2005) relationship with hydrological characteristics of the River Sava watershed in Slovenia. The values of C/N ratios range from 1.2 to 19.1, delta(13)C values range from-29.2 to-23.0 per thousand and delta(15)N values from 0.5 to 16.7 per thousand and indicate that the samples are a mixture of two end members: modern soils and plant litter. A simple mixing model was used to indicate that soil organic carbon prevails over plant litter and contributes more than 50% of suspended material. The calculated annual particulate organic carbon flux is estimated as 5.2x10(10) g C/year, the annual particulate nitrogen flux 8.5x10(9) g N/year and the total suspended solid flux is estimated to be 1.3x10(12) g/year. Anthropogenic impact was detected only in a tributary stream of the River Sava, which is located in an agriculture-industrial area and is reflected in higher delta(15)N values in suspended matter and high nitrate concentrations in the late summer season.     

Millimeter scale variations in the isotopic composition of vein sulphide minerals in the Kupferschiefer deposits, Lubin area, SW Poland

A slice of black shale rock cut by various metal sulphide veins of different generations from the Kupferschiefer deposits of Lubin, Poland was subjected to bombardment in a Laser Microprobe Combustion Reactor to produce SO2 for S-isotope analyses. The delta34S values ranged from-22 to-29 per thousand consistent with previous findings using conventional IRMS and attributable to primary generation of H2S by bacterial sulphate reduction. Systematic trends in delta34S values of a few per mil over distances of the order of mm attest to low temperatures of mineralization with accompanying change in the isotope composition of the fluids due to kinetic or equilibrium isotope fractionation.     

A laser extraction/combustion technique for in situ delta(13)C analysis of organic and inorganic materials

A CO(2) laser extraction system is described for in situ delta(13)C analysis of organic and inorganic materials. Carbonaceous compounds volatilized by the laser are quantitatively converted to CO(2) gas by a combustion furnace mounted after the sample chamber. Gases produced by the laser and combustion processes are swept by helium carrier gas and separated by a packed gas chromatography column prior to their introduction to an isotope ratio monitoring mass spectrometer. A sample of lentil bean was analyzed at a spatial resolution of 200 μm and yielded delta(13)C values with precision of +/- 0.3 per thousand. The accuracy of delta(13)C measurements was better than +/- 0.5 per thousand from NBS 22 (mineral oil), USGS 24 (graphite), and IAEA CO-1 (calcium carbonate). Copyright 1999 John Wiley & Sons, Ltd.     

Isotopic characteristics of meteoric waters in the Belgrade region

The stable isotope composition of hydrogen (delta(2)H) and oxygen (delta(18)O) in monthly precipitation and river water (Sava River and Danube) samples in the Belgrade area gathered between 1992 and 2005 are determined. The local meteoric water line delta(2)H=7.8 (+/-0.2) delta(18)O+7.3(+/-1.6) (r(2)=0.98, n=60, sigma=0.52) for the whole period of observation is close to the global meteoric water line. The amount-weighted mean delta(2)H and delta(18)O values of precipitation were-65+/-27 per thousand and-9.4+/-3.4 per thousand, respectively. Good correlation between delta(18)O values (r approximately >0.67) and ambient temperature and relative humidity was obtained. Stream-water data ranged from-94 to-60 per thousand for delta(2)H and from-11.0 to approximately 5.7 per thousand for delta(18)O with highly statistically significant difference (p>0.01) between the Sava River and the Danube. In addition, the isotopic compositions of local precipitation and adjacent river water at monitoring sites were compared. Obtained data will give an opportunity to improve the knowledge of mixing stream water and local groundwater, and assessment of potential groundwater risks and pressures in the Belgrade basin.     

Isotope characteristics of vegetables and wheat from conventional and organic production

Multielement isotope ratio analysis was checked for its suitability as a means for the discrimination between agricultural products from integrated/conventional or organic production, respectively. Differences were mainly found for delta15N-values. Paprika and tomatoes from organic production in greenhouses showed delta15N-values above+7 per thousand, whereas corresponding products from conventional cultivation had delta15N-values near 0 per thousand. Lettuce, onions, cabbage and Chinese cabbage from field production had delta15N-values in the range of+5 to+6 and+5.5 to+7.5 per thousand, respectively (conventional and organic production); these overlapping differences do not permit a reliable discrimination. The same is true for wheat, showing average delta15N-values of+2.3+/-1.0 and+3.6+/-1.6 per thousand, respectively. The unexpected relative high 15N-enrichments of vegetables from integrated production are discussed as originating, at least partially, from 15N-enrichment in the soil by NH3 evaporation and denitrification.     

Isotopic assessment of sources and processes affecting sulfate and nitrate in surface water and groundwater of Luxembourg

Surface water and deep and shallow groundwater samples were taken from selected parts of the Grand-Duchy of Luxembourg to determine the isotopic composition of nitrate and sulfate, in order to identify sources and/or processes affecting these solutes. Deep groundwater had sulfate concentrations between 20 and 40 mg/L, delta34S(sulfate) values between -3.0 and -20.0 per thousand, and delta18O(sulfate) values between +1.5 and +5.0 per thousand; nitrate was characterized by concentrations varying between < 0.5 and 10 mg/L, delta15N(nitrate) values of approximately -0.5 per thousand, and delta18O(nitrate) values approximately +3.0 per thousand. In the shallow groundwater, sulfate concentrations ranged from 25 to 30 mg/L, delta34S(sulfate) values from -20.0 to +4.5 per thousand, and delta18O(sulfate) values from approximately +0.5 to +4.5 per thousand; nitrate concentrations varied between approximately 10 and 75 mg/L, delta15N(nitrate) values between +2.5 and +10.0 per thousand, and delta18O(nitrate) values between +1.0 and +3.0 per thousand. In surface water, sulfate concentrations ranged from 10 to 210 mg/L, delta34S(sulfate) values varied between -9.3 and +10.9 per thousand, and delta18O(sulfate) values between +3.0 and +10.7 per thousand were observed. Nitrate concentrations ranged from 10 to 40 mg/L, delta15N(nitrate) values from +6.5 to +12.0 per thousand, and delta18O(nitrate) values from -0.4 to +4.0 per thousand. Based on these data, three sulfate sources were identified controlling the riverine sulfate load. These are soil sulfate, dissolution of evaporites, and oxidation of reduced S minerals in the bedrock. Both groundwater types were predominantly influenced by sulfate from the two latter lithogenic S sources. The deep groundwater and a couple shallow groundwater samples had nitrate derived mainly from soil nitrification. All other sampling sites were influenced by nitrate originating from sewage and/or manure. A decrease in nitrate concentration observed along one of the rivers was attributed to denitrification. It appears that sulfate within Luxembourg's aquatic ecosystem is mainly of lithogenic origin, whereas nitrate is often derived from anthropogenic activities.     

Independence of alpine meadow plants from soil organic matter for nitrogen supply: evidence from stable nitrogen isotopes

Stable nitrogen isotope signatures of major sources of mineral nitrogen (mineralization of soil organic nitrogen, biological N(2) fixation by legumes, annual precipitation and plant litter decomposition) were measured to relatively define their individual contribution to grass assimilation at the Haibei Alpine Meadow Ecosystem, Qinghai, China. The results indicated that delta(15)N values (-2.40 per thousand to 0.97 per thousand) of all grasses were much lower than those of soil organic matter (3.4+/-0.18 per thousand) and mineral nitrogen (ammonium and nitrate together, 7.8+/-0.57 per thousand). Based on the patterns of stable nitrogen isotopes, soil organic matter (3.4+/-0.18 per thousand), biological N(2) fixation (0 per thousand), and precipitation (-6.34+/-0.24 per thousand) only contributed to a small fraction of nitrogen requirements of grasses, but plant litter decomposition (-1.31+/-1.01 per thousand) accounted for 67 %.     

Determination of delta13 CV-PDB and delta15NAIR values of cocaine from a big seizure in Germany by stable isotope ratio mass spectrometry

In this study, delta(13)C(V- PDB) and delta(15)N(AIR) values of 132 cocaine samples from a big seizure in Germany in 2002 were determined using elemental analyser isotope ratio mass spectrometry. The 1.2 tons of cocaine were packed in 1 kg packages and the cocaine bricks inside these packages showed certain logos. Twenty different logos could be identified. Results show a large variability among some samples, for delta(15)N(AIR) values ranging from-17 to -2 per thousand. Furthermore, the possibility of linking samples with the same logo was checked. The results show that, in general, there is no relationship between the determined isotope ratio and a certain logo.     

Flooding of lignite mines: isotope variations and processes in a system influenced by saline groundwater

The quality of both groundwaters and surface waters that arise during flooding of abandoned lignite open pits are influenced by regional and local factors. A typical regional factor is due to oxidised sedimentary sulfides. A more local factor is the interaction of shallow water with highly saline groundwater, which is important in Merseburg-Ost (Germany). Investigation of this system is aided by the use of many environmental isotope tracers but special problems can arise. In order to reveal processes in the mine environment (shallow groundwater, lake water) and to characterise mixtures with saline groundwater results are described using the tracers deltaD, delta18O, delta13C, delta34S, 87Sr/86Sr, 3H, 14C, 39Ar, and 222Rn. Deep highly saline groundwater had a radiocarbon concentration typically below 10 pMC. The values of delta13C(DIC) are around-5 per thousand. As delta13C of the aquifer rock samples (Permian, Zechstein carbonates) was in the range of-6...+5 per thousand, residence time corrections based on delta13C are questionable. Additional checks with 39Ar, as well as results from the variationof delta18O (or deltaD) with respect to the salinity, emphasise a Holocene age; as is also the case for most mineralised groundwaters and also for water having a low delta18O (and deltaD). For saline groundwater residing in the Zechstein aquifer the measured delta34S values of about 12 per thousand are close to those expected from the literature. In contrast, the 87Sr/86Sr ratio of dissolved strontium is far from the values anticipated for the aquifer rocks despite there being proportionality between the chloride concentration and the strontium concentration. Furthermore, the proportionality is not valid in lower mineralised water. The 87Sr/86Sr ratio can, therefore, hardly be used as a tracer for the distribution of ascending saline water. The amount of salt-water coming from below into the residual quarry basins is an essential contribution to the lake inventories. Therefore, 222Rn was used to assist in determining the renewal of salt-water layers that formed in deep lake locations. In the deep zones 222Rn concentrations up to 6 Bq/l were measured but were dominantly in equilibrium with 226Ra, which was found in all higher mineralised groundwater samples. Excess radon was limited to just a few decimetres above the lake sediment surface but does not appear to be caused by continuous groundwater discharge.Hydrochemical investigations of groundwater from the Quaternary aquifer were carried out over the last six years before flooding was complete. Apart from a slight downward shift of the average sulfate concentration, other changes showed virtually no trends. An increase of the sulfate concentration was mostly correlated with a decrease of delta34S for individual sites only, but not for the whole ensemble of sampling locations. Sulfate from pyrite oxidation plays an important role but cannot be attributed unequivocally to coal mining. There are hints that the conditions closer to the basin edges may differ from those remoter parts of the flood plain.     

On-line delta(18)O measurement of organic and inorganic substances

A method for the automated sample conversion and on-line oxygen isotope ratio (delta(18)O) determination for organic and inorganic substances is presented. The samples are pyrolytically decomposed at 1400 degrees C in the presence of nickelized graphite. With the system presented organic as well as inorganic samples such as nitrates, sulphates and phosphates of 50-100 &mgr;g O can be analyzed for their delta(18)O values with a standard deviation usually better than 0.5 per thousand. Additionally, carbon isotope ratios of organic substances and nitrogen isotope ratios of inorganic nitrogenous compounds are available in the same sample run. Data for international and some inter-laboratory reference materials are presented to show the accuracy and reliability of the method. The effect of some additives on the CO yield was checked for substances which do not pyrolyze completely. Copyright 1999 John Wiley & Sons, Ltd.     

Isotopic composition of sulphates from meteoric precipitation as an indicator of pollutant origin in Wrocław (SW Poland)

This paper describes the results of isotopic analyses of (i) hydrogen and oxygen in water (delta DH2O and delta18OH2O ) and (ii) sulphur and oxygen in sulphates (delta34Ssulphate and delta18Osulphate) from atmospheric precipitation collected within a one-year period between 25 May 2004 and 25 May 2005 in Wroc?aw (SW Poland). The resulting equation of Local Meteoric Water Line for Wroc?aw is delta D=6.373xdelta18O-0.047, (r2=0.97, n=32). The delta34Ssulphate varies from 1.1 to 4.2 per thousand (with an average of 2.5 per thousand), delta18Osulphate varies from 9.0 to 16.7 per thousand (with an average of 13.8 per thousand) and delta18OH2O varies from-0.8 to-16.3 per thousand (with an average of-8.2 per thousand). The above results indicate two main sources of sulphates in Wroc?aw precipitation: (i) low-temperature secondary sulphates forming in situ in Wroc?aw from the atmospheric SO2 as well as precipitation water (heterogeneous and homogeneous pathways oxidation) and (ii) high-temperature primary sulphates forming in rapid high-temperature hydratation of SO3- in an immediate proximity of industrial chimneys. We hypothesise that the secondary low-temperature type of sulphates is probably formed from the local sulphur and oxygen reservoirs, whereas the primary high-temperature type is allochthonous and it is probably transported from industrial areas located outside of Wroc?aw.     

Chlorine isotope fractionation associated with volcanic activity at the Kusatsu-Bandaiko hot spring in Japan

Stable chlorine isotope compositions (delta(37)Cl, per-mil: per thousand, vs. a standard sample of sea water) of Kusatsu-bandaiko hot water samples, taken regularly in the years between 1974 and 1995 in the Kusatsu-Shirane volcanic region, Japan, were measured mass-spectrometrically. The results show that the delta(37)Cl values of the waters taken before 1984 were at around-0.12 per thousand, whereas those after 1984 were at around+0.18 per thousand. The delta(37)Cl values are thus distinct across 1984, which is consistent with the classification by the Cl to S molar ratio (Cl/S): the higher the Cl/S ratio, the larger the delta(37)Cl value. The delta(37)Cl value increased as much as 0.30 per thousand during 5 years between 1980 and 1984. This isotopic enrichment is likely correlated with increasing Cl/S ratios, suggesting that the heavier isotope ((37)Cl) may have preferentially increased in the original Cl source of the hot spring across 1984 when volcanic activity likely increased at Mt Kusatsu-Shirane.     

Effects of natural environmental factors on delta13C of lichens

This preliminary study was designed to determine the extent to which the carbon isotope ratio in four species of lichens was influenced by such features as humidity, rainfall, radioactivity, and air quality. The sampling sites were selected to be at a great distance from any pollution. At the time of sampling, field data (temperature, relative humidity, average monthly precipitation, and radioactivity) were recorded. delta(13)C in whole lichen specimens were determined using standard mass spectrometric techniques with a standard deviation of+/-0.3 per thousand. We have found a weak but negative correlation between delta(13)C and relative humidity, and a positive correlation between delta(13)C and average monthly precipitation at the studied sites. The effects were minor, of the order of 1.5 per thousand for all the lichens. We have examined the correlation between (137)Cs activity concentration of the studied lichens and delta(13)C of these lichens, and we have suggested that fixation of radiocesium does not alter photosynthesis rate. There was a delta(13)C variation with the altitude gradient with less negative delta(13)C values at higher altitude. It is possible that this difference is caused by the ozone and occurred at the high elevations.     

Molecular insight into soil carbon turnover

Curie-point pyrolysis-gas chromatography coupled on-line to mass spectrometry (Py-GC/MS) and isotope ratio mass spectrometry (Py-GC/IRMS) were used to determine the individual turnover rate of specific carbohydrates, lignin, lipids and N-containing compounds from French arable soils. The analysed soils were cultivated, either continuously with a C3 plant (wheat delta(13)C-value = -25.2 per thousand), or transferred to a C4 plant (maize delta(13)C-value = -11.4 per thousand) cropping 23 years ago. Most pyrolysis products identified were related to carbohydrates (furans), lipids (hydrocarbons and derivatives of benzene), proteins (nitriles and pyrrole) and lignins (phenols). The relative yield of all individual pyrolysis products was similar in the samples from the maize and control wheat soil. The isotopic enrichment between identical pyrolysis products from the two soils varied from 1 to 12 delta (delta) units, indicating that after 23 years of cultivation 7 to 90% of their C was derived from maize. This suggests a slow mean turnover time varying from 9 to 220 years. Based on the differences in isotopic enrichment of chemical structures after vegetation change the pyrolysis products could be divided into three groups: (i) pyrolysis products with a nearly complete C4 signal, e. g. phenol, derived from lignin degradation products, (ii) pyrolysis products with an intermediate isotopic enrichment of 6-8 per thousand, most likely to be a composite of remaining (possibly physically protected) fragments derived from both maize and native wheat, and (iii) pyrolysis products showing only low enrichments in (13)C of 1-3 per thousand. Most of their precursors were found to be proteinaceaous materials. This indicates that proteins or peptides are indeed preserved during decomposition and humification processes occurring in the soil. Our study highlights the potential of Py-GC/MS-C-IRMS to further novel insights into the dynamics of soil organic constituents. Copyright 1999 John Wiley & Sons, Ltd.