Influences of heterotrophic and autotrophic resource use on carbon and hydrogen isotopic compositions of tropical tree leaves.

The delta13C and SD values of newly emerging to senescing tree leaves produced during a rainy season were obtained in dry seasonal and moist forest in Panamá. Newly emerging leaves had less negative delta13C values than older leaves yet instantaneous pi/pa was never lowest in the youngest leaves. Furthermore, isotopic enrichment during early growth may have a detectable influence on the delta13C values of mature leaves. The deltaD values of cellulose nitrate were only related to deltaD values of leaf water if leaf age was also considered so that, for a given deltaD of leaf water, deltaD values were highest in the youngest leaves (R2 = 98%). There was no correlation between leaf age and deltaD values of leaf water. Investment of translocated organic carbon is a factor likely to be associated with both 13C and deuterium enrichment effects in new leaves. A coarse, mass balance approach can estimate the proportional heterotrophic investment in leaf growth and improve estimates of integrated pi/pa by approximating delta13C for the most autotrophic phase of leaf growth. Delta13C values of the predominantly sucrose mobile organic fraction in new leaves were less negative than in older leaves, thereby suggesting that the enrichment did not occur at the original site of production of the substrate for new leaf growth. Although the delta values of early leaf growth must be influenced by inputs of translocated organic carbon, enrichment effects, per se, are apparently caused by other mechanisms such as, for carbon, de novo sucrose synthesis and anaplerotic replenishment. Better recognition of metabolic causes of isotopic enrichment in leaves promises to increase the power and accuracy of inferences about carbon and water use of tropical trees from delta analyses.     

Diurnal variations in the photosynthesis-respiration activity of a cyanobacterial bloom in a freshwater dam reservoir: an isotopic study

The stable isotopic analyses of molecular oxygen dissolved in water (delta18O(DO)) and dissolved inorganic carbon (delta13C(DIC)), supplemented with basic chemical measurements, have been carried out on a diurnal basis to better understand the dynamics of photosynthesis and respiration in freshwater systems. Our observations have been carried out in a lowland dam reservoir, the Sulejow Lake (central Poland), during the summer cyanobacterial bloom. All data obtained, isotopic, hydrochemical, and biological, show a high mutual consistency. Namely, the lowest delta18O(DO) values, obtained at 10:00 and 14:00 (16.0 and 15.5 per thousand, respectively), correspond to the highest amount of cyanobacterial cells observed (66 and 63 mg dm(-3), respectively), whereas the minimum delta13C(DIC) (-10.6 per thousand) obtained at 22:00 corresponds to the maximum content of organic matter (110 mg dm(-3)). This evidence suggests that isotopic assays of delta18O(DO) and delta13C(DIC) are a reliable tool for the quantitative study of biochemical processes in freshwater systems.     

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.     

Stable isotope ratios and uric acid preservation in termites belonging to three feeding habits in Thailand

Nitrogen and carbon stable isotope ratios and uric acid concentrations in termites sampled from a dry evergreen forest in Thailand, were determined across three kinds of feeding habits. Feeding habits of Microcerotermes crassus, which is an abundant wood-feeder, and Dicuspiditermes makhamensis, a common soil-feeding termite, were confirmed by isotopic signatures. Lichen feeding termites (Hospitalitermes birmanicus, H. bicolor and H. ataramensis) were characterized by low delta15N values, suggesting that they assimilated nitrogen deposited from the atmosphere. There was also a significant difference in uric acid concentrations between termites representing different feeding habits. No significant relationships were found between uric acid concentrations and delta15N or delta13C in Hospitalitermes. However, delta15N values were correlated with C/N ratios in H. birmanicus, except in one colony of H. ataramensis. delta13C values in both species were negatively correlated with C/N ratios.     

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.     

Potential for assessing long-term dynamics in soil nitrogen availability from variations in delta15N of tree rings

Numerous researchers have used the isotopic signatures of C, H, and O in tree rings to provide a long-term record of changes in the physiological status, climate, or water-source use of trees. The frequently limiting element N is also found in tree rings, and variation in its isotopic signature may provide insight into long-term changes in soil N availability of a site. However, research has suggested that N is readily translocated among tree ring of different years; such infidelity between the isotopic compositions of the N taken up from the soil and the N contained in the ring of that growth year would obscure the long-term N isotopic record. We used a 15-year 15N-tracer study to assess the degree of N translocation among tree rings in ponderosa pine (Pinus ponderosa) trees growing in a young, mixed-conifer plantation. We also measured delta13C and delta15N values in unlabeled trees to assess the degree of their covariance in wood tissue, and to explore the potential for a biological linkage between them. We found that the maximum delta15N values in rings from the labeled trees occurred in the ring formed one-year after the 15N was applied to the roots. The delta15N value of rings from labeled trees declined exponentially and bidirectionally from this maximum peak, toward younger and older rings. The unlabeled trees showed considerable interannual variation in the delta15N values of their rings (up to 3 and 5 per thousand), but these values correlated poorly between trees over time and differed by as much as 6 per thousand. Removal of extractives from the wood reduced their delta15N value, but the change was fairly small and consistent among unlabeled trees. The delta13C and delta15N values of tree rings were correlated over time in only one of the unlabeled trees. Across all trees, both delta13C values of tree rings and annual stem wood production were well correlated with annual precipitation, suggesting that soil water balance is an important environmental factor controlling both net C gain and transpirational water loss at this site. Our results suggest that interannual translocation of N among tree rings is substantial, but may be predictable enough to remove this source of variation from the tree-ring record, potentially allowing the assessment of long-term changes in soil N availability of a site.     

Continuous field measurements of delta(13)C-CO(2) and trace gases by FTIR spectroscopy

Continuous analysis of the (13)C/(12)C ratio of atmospheric CO(2) (delta(13)C-CO(2)) is a powerful tool to quantify CO(2) flux strengths of the two major ecosystem processes assimilation and respiration. Traditional laboratory techniques such as isotope ratio mass spectrometry (IRMS) in combination with flask sampling are subject to technical limitations that do not allow to fully characterising variations of atmospheric delta(13)C-CO(2) at all relevant timescales. In our study, we demonstrate the strength of Fourier transform infrared (FTIR) spectroscopy in combination with a PLS-based calibration strategy for online analysis of delta(13)C-CO(2) in ambient air. The ability of the instrument to measure delta(13)C-CO(2) was tested on a grassland field-site and compared with standard laboratory-based IRMS measurements made on field-collected flask samples. Both methods were in excellent agreement, with an average difference of 0.4 per thousand (n=81). Simultaneously, other important trace gases such as CO, N(2)O and CH(4) were analysed by FTIR spectroscopy.     

Stable carbon isotopic composition of tree rings from a pine tree from Augustów Wilderness, Poland, as a temperature and local environment conditions indicator

Tree rings can be used as archives of climatic and environmental data with annual resolution. Tree rings widths, maximum late wood density and other parameters as stable composition in tree rings can be used for the reconstruction of past climatic and environmental changes. Stable carbon isotope ratios in tree rings may provide valuable information on past climatic conditions. 13C/12C ratios of plant organic matter can reflect corresponding 13C/12C ratio of atmospheric CO2 during formation of the rings. Investigations of isotopic carbon composition in tree rings from in the ecologically clean the Augustów Wilderness region in the north-eastern part of Poland (22 degrees 58'E, 53 degrees 51'N) (nowadays a sanctuary) were undertaken. Series of delta13C in alpha-cellulose and in wholewood were acquired. Those measurements constituted a part of more complex investigations of carbon isotope composition in tree rings including the measurements of radiocarbon concentration and tree ring widths. This article presents preliminary results. It is argued that contrary to the tree ring widths and delta13C in wholewood that do not reveal significant correlation with temperature, the variation of delta13C in the latewood alpha-cellulose is correlated with combined July and August temperatures.     

Stable isotopic analysis of pyrogenic organic matter in soils by liquid chromatography-isotope-ratio mass spectrometry of benzene polycarboxylic acids

Pyrogenic organic matter (PyOM), the incomplete combustion product of organic materials, is considered stable in soils and represents a potentially important terrestrial sink for atmospheric carbon dioxide. One well-established method of measuring PyOM in the environment is as benzene polycarboxylic acids (BPCAs), a compound-specific method, which allows both qualitative and quantitative estimation of PyOM. Until now, stable isotope measurement of PyOM carbon involved measurement of the trimethylsilyl (TMS) or methyl (Me) polycarboxylic acid derivatives by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). However, BPCA derivatives can contain as much as 150% derivative carbon, necessitating post-analysis correction for the accurate measurement of δ13C values, leading to increased measurement error. Here, we describe a method for δ13C isotope ratio measurement and quantification of BPCAs from soil-derived PyOM, based on ion-exchange chromatography (IEC-IRMS). The reproducibility of the δ13C measurement of individual BPCAs by IEC-IRMS was better than 0.35‰ (1σ). The δ13C-BPCA analysis of PyOM in soils, including at natural and artificially enriched 13C-abundance, produced accurate and precise δ13C measurements. Analysis of samples that differed in δ13C by as much as 900‰ revealed carryover of <1‰ between samples. The weighted sum of individual δ13C-BPCA measurements was correlated with previous isotopic measurements of whole PyOM, providing complementary information for bulk isotopic measurements. We discuss potential applications of δ13C-BPCA measurements, including the study of turnover rates of PyOM in soils and the partitioning of PyOM sources based on photosynthetic pathways.     

13C and 15N distributions in three spodic dystric cambisols under beech and spruce

The study of natural isotopic abundance signatures is useful to gain further insights in the processes resulting in depthwise changes in the composition of soil organic matter (SOM). Objectives were to describe the delta 13C and delta 15N abundances of SOM with depth in soils from a 153-year old beech (B1), a 119-year old spruce (F1) and a 61-year old spruce (F2) stand at Solling, north-west Germany, and to study, how podzolisation affects the isotopic abundances of 13C and 15N in the SOM. The degree of podzolisation decreased in the order F1 > B1 > F2. At the surface of the humus layer of all three sites, delta 13C values are approximately 1 to 4/1000 higher than in the leaves and needles, probably mainly due to the discrimination of 13C by microbial decomposition. 13C abundances in the organic layers of B1 and F2 increased only slightly from -27.6/1000 PDB (B1, L) to -27.2/1000 PDB (B1, Oh) and from -26.3/1000 PDB (F2, L) to -25.9/1000 PDB (F2, Oh), suggesting that biotic activity resulted in mixing of organic matter. At F1, however, 13C abundance increased from -27.5/1000 PDB (L) to -26.0/1000 PDB (Oh) which reflects the lack of mixing by animals. In the upper 2-4 cm of the mineral soil, i.e., in the eluvial horizons Aeh, 13C values showed a minimum at the spruce sites which was presumably related to a translocation of 13C enriched fulvic acids. Depthwise changes in delta 15N values were not related to podzolisation processes. At all three sites, a 13N enrichment with depth occurred in the mineral soil which is the result of the discrimination of 15N by microbial decomposition.     

Direct evidence for the existence of dairying farms in prehistoric Central Europe (4th millennium BC)

The molecular and isotopic chemistry of organic residues from archaeological potsherds was used to obtain further insight into the dietary trends and economies at the Constance lake-shore Neolithic settlements. The archaeological organic residues from the Early Late Neolithic (3922-3902 BC) site Hornstaad-Hornle IA/Germany are, at present, the oldest archaeological samples analysed at the Institute of Mineralogy and Geochemistry of the University of Lausanne. The approach includes 13C/12C and 15N/14N ratios of the bulk organic residues, fatty acids distribution and 13C/12C ratios of individual fatty acids. The results are compared with those obtained from the over 500 years younger Neolithic (3384-3370 BC) settlement of Arbon Bleiche 3/Switzerland and with samples of modern vegetable oils and fat of animals that have been fed exclusively on C3 forage grasses. The overall fatty acid composition (C9 to C24 range, maximizing at C14 and C16), the bulk 13C/12C and 15N/14N ratios (delta13C, delta15N) and the 13C/12C ratios of palmitic (C16:0), stearic (C18:0) and oleic acids (C18:1) of the organic residues indicate that most of the studied samples (25 from 47 samples and 5 from 41 in the delta13C18:0 vs. delta13C16:0 and delta13C18:0 vs. delta13C18:1 diagrams, respectively) from Hornstaad-Hornle IA and Arbon Bleiche 3 sherds contain fat residues of pre-industrial ruminant milk, and young suckling calf/lamb adipose. These data provide direct proof of milk and meat (mainly from young suckling calves) consumption and farming practices for a sustainable dairying in Neolithic villages in central Europe around 4000 BC.dagger.     

Contribution of collagen stable isotope biogeochemistry to the paleobiology of extinct endemic vertebrates from Tenerife (Canary Islands, Spain)

The paleodiet and paleoenvironmental context of two extinct species from Tenerife island, one giant rat Canariomys bravoi and one giant lizard Gallotia goliath, have been investigated using carbon and nitrogen isotopic compositions of fossil bone collagen. Preliminary to this study, a calibration of the isotopic variations of bone collagen from modern Rat Rattus rattus, Rabbit Oryctolagus cuniculus and Lizard Gallotia galotti relative to environmental conditions on Tenerife Islands has been attempted. No clear relationship could be found between collagen delta13C and delta15N values and aridity; the only relevant factors seem to be seashore proximity for rat, and the relative amount of C3 and CAM plants. It seems that anthropic activities have interfered with the expected relationships between collagen isotopic compositions and environmental conditions. Most fossil specimens yielded well preserved collagen. The isotopic composition of giant rat and giant lizard collagen suggest a purely C3 environment, possibly more humid than today on Tenerife. Large ranges of nitrogen isotopic compositions, especially within giant rats, may be due to local environmental conditions. Further work is needed in order to provide more valuable paleobiological information in order to better understand the role of environmental factors in the evolution and extinction of insular endemic species on Tenerife.     

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 (delta13Ccell and delta18Ocell) 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 delta13Ccell showed an extraordinary increase in the period 1945-1990 and a rapid decrease after 1990, whereas delta18Ocell remained nearly constant. The increase of delta13Ccell 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 delta18Ocell. Furthermore, a significant positive correlation between the year-to-year variations of carbon and oxygen isotope ratios (delta13Cresid and delta18Oresid) has been found for all sites. The slopes of the relationship between delta13Cresid and delta18Oresid differ insignificantly. It is concluded that this relationship is not influenced by soil water availability but by climatic variables.     

Environmental isotopes as a useful tool for studies at mixed uranium mill tailings sites

Groundwaters in the area of a mixed landfill (domestic waste above uranium mill tailings) in Dresden (Saxony, Germany) were investigated for their isotope signatures to distinguish between different groundwater types. To determine between the two contamination sources (waste and uranium mill tailings) a multi parameter interpretation was done using both, the main hydrochemical parameters the radionuclides 234U, 238U, 226Ra and 222Rn as well as the environmental isotopes of the elements hydrogen, oxygen, sulphur and carbon. The seepage water from the landfill shows higher delta34S, delta18O and tritium values as the inflow. The tritium values give an idea about water movement in the dump and mean residence time of the groundwater. The water in the dump shows varying delta13C values which indicate different processes occurring in the dump.     

A robust and fast method of sampling and analysis of delta13C of dissolved inorganic carbon in ground waters

The stable carbon isotopic composition of dissolved inorganic carbon (delta13C(DIC)) is traditionally determined using either direct precipitation or gas evolution methods in conjunction with offline gas preparation and measurement in a dual-inlet isotope ratio mass spectrometer. A gas evolution method based on continuous-flow technology is described here, which is easy to use and robust. Water samples (100-1500 microl depending on the carbonate alkalinity) are injected into He-filled autosampler vials in the field and analysed on an automated continuous-flow gas preparation system interfaced to an isotope ratio mass spectrometer. Sample analysis time including online preparation is 10 min and overall precision is 0.1 per thousand. This method is thus fast and can easily be automated for handling large sample batches.     

Stable isotope study of precipitation and cave drip water in Florida (USA): implications for speleothem-based paleoclimate studies

Stable isotopes of hydrogen and oxygen were used to examine how the isotopic signal of meteoric water is modified as it travels through soil and epikarst into two caves in Florida. Surface and cave water samples were collected every week from February 2006 until March 2007. The isotopic composition of precipitation at the investigated sites is highly variable and shows little seasonal control. The delta18O vs. delta2H plot shows a mixing line having a slope of 5.63, suggesting evaporation effects dominate the isotopic composition of most rainfall events of less than 8 cm/day, as indicated by their low d-excess values. The delta18O values of the drip water show little variability (<0.6 per thousand), which is loosely tied to local variations in the seasonal amount of precipitation. This is only seen during wintertime at the Florida Caverns site. The lag time of over two months and the lack of any relationship between rainfall amount and the increase in drip rate indicate a dominance of matrix flow relative to fracture/conduit flow at each site. The long residence time of the vadose seepage waters allows for an effective isotopic homogenisation of individual and seasonal rainfall events. We find no correlation between rainfall and drip water delta18O at any site. The isotopic composition of drip water in both caves consistently tends to resemble the amount-weighted monthly mean rainfall input. This implies that the delta18O of speleothems from these two caves in Florida cannot record seasonal cycle in rainfall delta18O, but are suitable for paleoclimate reconstructions at inter-annual time scales.dagger.     

Microcombustion of ng Amounts of Carbon in Non-Volatile Materials for isotope Ratio Evaluation

Abstract A novel microcombustion technique for carbon isotopic analysis of nanogram amounts of carbon in non-volatile materials based on isotope ratio monitoring (irm) mass spectrometry is described. Liquid or solid samples placed in a quartz sleeve are combusted at 1000°C in a continuous stream of helium and oxygen. CO(2) removed from the carrier gas stream by cryogenic trapping is transferred onto a GC column. Following GC separation, the CO(2) is transferred via an open split to the ion source of a gas isotope ratio mass spectrometer. Reproducibility for samples >25 nmol carbon is <1‰. Problems associated with blanks from various sources and with reproducible deposition of small sample amounts led to variable accuracy, which was dependent on the compound class being analysed. Minimum sample size was in the range from 5 to 10 nmol carbon. Measurements of dissolved organic carbon (DOC) of groundwater from Germany yielded consistent values of δ(13)C = -28.8‰.     

Effect of different lipid extraction methods on delta13C of lipid and lipid-free fractions of fish and different fish feeds

For many ecological applications of stable carbon isotope techniques, it is necessary to separate the lipid and lipid-free fractions. The effect of different lipid extraction methods on the isotope signature of the remaining lipid-free matter as well as the lipid fraction was tested. A hot extraction form of the Soxhlet method using petrol-ether was compared with two liquid-liquid extraction methods for lipid determination described by Bligh and Dyer and Smedes. Solid samples of fish and different natural food items were subjected to extraction and the carbon isotope ratios in lipid and lipid-free matter determined by IRMS. All methods were suitable for lipid extraction from all samples analysed here and did not cause biologically relevant differences (> 1%) in carbon isotopic ratios, except the Bligh and Dyer extraction method using chloroform which caused systematic errors for delta13C when applied to diatoms.     

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.