Estimating intra-seasonal photosynthetic discrimination and water use efficiency using delta C-13 of leaf sucrose in Scots pine

Comparison of assimilate delta C-13 values estimated from different leaf carbon pools, Picarro measurements, and modelled data demonstrates the potential for misinterpretation arising from bulk organic matter delta C-13 analysis.Sucrose has a unique role in recording environmental and physiological signals during photosynthesis in its carbon isotope composition (delta C-13) and transport of the signal to tree rings. Yet, instead of sucrose, total organic matter (TOM) or water-soluble carbohydrates (WSC) are typically analysed in studies that follow delta C-13 signals within trees. To study how the choice of organic material may bias the interpretation of delta C-13 records, we used mature field-grown Scots pine (Pinus sylvestris) to compare for the first time delta C-13 of different leaf carbon pools with delta C-13 of assimilates estimated by a chamber-Picarro system (delta C-13(A_Picarro)), and a photosynthetic discrimination model (delta C-13(A_model)). Compared with sucrose, the other tested carbon pools, such as TOM and WSC, poorly recorded the seasonal trends or absolute values of delta C-13(A_Picarro) and delta C-13(A_model). Consequently, in comparison with the other carbon pools, sucrose delta C-13 was superior for reconstructing changes in intrinsic water use efficiency (iWUE), agreeing in both absolute values and intra-seasonal variations with iWUE estimated from gas exchange. Thus, deriving iWUE and environmental signals from delta C-13 of bulk organic matter can lead to misinterpretation. Our findings underscore the advantage of using sucrose delta C-13 to understand plant physiological responses in depth.Peer reviewe

Plume mapping and isotopic characterisation of anthropogenic methane sources

Methane stable isotope analysis, coupled with mole fraction measurement, has been used to link isotopic signature to methane emissions from landfill sites, coal mines and gas leaks in the United Kingdom. A mobile Picarro G2301 CRDS (Cavity Ring-Down Spectroscopy) analyser was installed on a vehicle, together with an anemometer and GPS receiver, to measure atmospheric methane mole fractions and their relative location while driving at speeds up to 80 kph. In targeted areas, when the methane plume was intercepted, air samples were collected in Tedlar bags, for delta C-13-CH4 isotopic analysis by CF-GC-IRMS (Continuous Flow Gas Chromatography-Isotope Ratio Mass Spectrometry). This method provides high precision isotopic values, determining delta C-13-CH4 to +/- 0.05 per mil. The bulk signature of the methane plume into the atmosphere from the whole source area was obtained by Keeling plot analysis, and a delta C-13 -CH4 signature, with the relative uncertainty, allocated to each methane source investigated. Both landfill and natural gas emissions in SE England have tightly constrained isotopic signatures. The averaged delta C-13-CH4 for landfill sites is -58 +/- 3%o. The delta C-13-CH4 signature for gas leaks is also fairly constant around -36 +/- 2 parts per thousand, a value characteristic of homogenised North Sea supply. In contrast, signatures for coal mines in N. England and Wales fall in a range of -51.2 +/- 0.3 parts per thousand to 30.9 +/- 1.4 parts per thousand, but can be tightly constrained by region. The study demonstrates that CRDS-based mobile methane measurement coupled with off-line high precision isotopic analysis of plume samples is an efficient way of characterising methane sources. It shows that iiotopic measurements allow type identification, and possible location of previously unknown methane sources. In modelling studies this measurement provides an independent constraint to determine the contributions of different sources to the regional methane budget and in the verification of inventory source distribution. (C) 2015 Elsevier Ltd. All rights reserved

Chemostratigraphy of Neoproterozoic carbonates: implications for 'blind dating'

The delta C-13(carb) and Sr-87/Sr-86 secular variations in Neoproteozoic seawater have been used for the purpose of 'isotope stratigraphy' but there are a number of problems that can preclude its routine use. In particular, it cannot be used with confidence for 'blind dating'. The compilation of isotopic data on carbonate rocks reveals a high level of inconsistency between various carbon isotope age curves constructed for Neoproteozoic seawater, caused by a relatively high frequency of both global and local delta C-13(carb) fluctuations combined with few reliable age determinations. Further complication is caused by the unresolved problem as to whether two or four glaciations, and associated negative delta C-13(carb) excursions, can be reliably documented. Carbon isotope stratigraphy cannot be used alone for geological correlation and 'blind dating'. Strontium isotope stratigraphy is a more reliable and precise tool for stratigraphic correlations and indirect age determinations. Combining strontium and carbon isotope stratigraphy, several discrete ages within the 590-544 Myr interval, and two age-groups at 660-610 and 740-690 Myr can be resolved

Tracing Carbon Sources through Aquatic and Terrestrial Food Webs Using Amino Acid Stable Isotope Fingerprinting

Tracing the origin of nutrients is a fundamental goal of food web research but methodological issues associated with current research techniques such as using stable isotope ratios of bulk tissue can lead to confounding results. We investigated whether naturally occurring delta C-13 patterns among amino acids (delta C-13(AA)) could distinguish between multiple aquatic and terrestrial primary production sources. We found that delta C-13(AA) patterns in contrast to bulk delta C-13 values distinguished between carbon derived from algae, seagrass, terrestrial plants, bacteria and fungi. Furthermore, we showed for two aquatic producers that their delta C-13(AA) patterns were largely unaffected by different environmental conditions despite substantial shifts in bulk delta C-13 values. The potential of assessing the major carbon sources at the base of the food web was demonstrated for freshwater, pelagic, and estuarine consumers; consumer delta C-13 patterns of essential amino acids largely matched those of the dominant primary producers in each system. Since amino acids make up about half of organismal carbon, source diagnostic isotope fingerprints can be used as a new complementary approach to overcome some of the limitations of variable source bulk isotope values commonly encountered in estuarine areas and other complex environments with mixed aquatic and terrestrial inputs

Inferring Phytoplankton, Terrestrial Plant and Bacteria Bulk delta C-13 Values from Compound Specific Analyses of Lipids and Fatty Acids

Stable isotope mixing models in aquatic ecology require delta C-13 values for food web end members such as phytoplankton and bacteria, however it is rarely possible to measure these directly. Hence there is a critical need for improved methods for estimating the delta C-13 ratios of phytoplankton, bacteria and terrestrial detritus from within mixed seston. We determined the delta C-13 values of lipids, phospholipids and biomarker fatty acids and used these to calculate isotopic differences compared to the whole-cell delta C-13 values for eight phytoplankton classes, five bacterial taxa, and three types of terrestrial organic matter (two trees and one grass). The lipid content was higher amongst the phytoplankton (9.5 +/- 4.0%) than bacteria (7.3 +/- 0.8%) or terrestrial matter (3.9 +/- 1.7%). Our measurements revealed that the delta C-13 values of lipids followed phylogenetic classification among phytoplankton (78.2% of variance was explained by class), bacteria and terrestrial matter, and there was a strong correlation between the delta C-13 values of total lipids, phospholipids and individual fatty acids. Amongst the phytoplankton, the isotopic difference between biomarker fatty acids and bulk biomass averaged -10.7 +/- 1.1 parts per thousand for Chlorophyceae and Cyanophyceae, and -6.1 +/- 1.7 parts per thousand for Cryptophyceae, Chrysophyceae and Diatomophyceae. For heterotrophic bacteria and for type I and type II methane-oxidizing bacteria our results showed a -1.3 +/- 1.3 parts per thousand, -8.0 +/- 4.4 parts per thousand, and -3.4 +/- 1.4 parts per thousand delta C-13 difference, respectively, between biomarker fatty acids and bulk biomass. For terrestrial matter the isotopic difference averaged -6.6 +/- 1.2 parts per thousand. Based on these results, the delta C-13 values of total lipids and biomarker fatty acids can be used to determine the delta C-13 values of bulk phytoplankton, bacteria or terrestrial matter with +/- 1.4 parts per thousand uncertainty (i.e., the pooled SD of the isotopic difference for all samples). We conclude that when compound-specific stable isotope analyses become more widely available, the determination of delta C-13 values for selected biomarker fatty acids coupled with established isotopic differences, offers a promising way to determine taxa-specific bulk delta C-13 values for the phytoplankton, bacteria, and terrestrial detritus embedded within mixed seston.Peer reviewe

Combining a Quantum Cascade Laser Spectrometer with an Automated Closed-Chamber System for δ13C Measurements of Forest Soil, Tree Stem and Tree Root CO2 Fluxes

Recent advances in laser spectroscopy have allowed for real-time measurements of the C-13/C-12 isotopic ratio in CO2, thereby providing new ways to investigate carbon cycling in natural ecosystems. In this study, we combined an Aerodyne quantum cascade laser spectrometer for CO2 isotopes with a LI-COR LI-8100A/8150 automated chamber system to measure the delta C-13 of CO2 during automated closed-chamber measurements. The isotopic composition of the CO2 flux was determined for each chamber measurement by applying the Keeling plot method. We found that the delta C-13 measured by the laser spectrometer was influenced by water vapour and CO2 concentration of the sample air and we developed a method to correct for these effects to yield accurate measurements of delta C-13. Overall, correcting for the CO2 concentration increased the delta C-13 determined from the Keeling plots by 3.4 parts per thousand compared to 2.1 parts per thousand for the water vapour correction. We used the combined system to measure delta C-13 of the CO2 fluxes automatically every two hours from intact soil, trenched soil, tree stems and coarse roots during a two-month campaign in a Danish beech forest. The mean delta C-13 was -29.8 +/- 0.32 parts per thousand for the intact soil plots, which was similar to the mean delta C-13 of -29.8 +/- 1.2 parts per thousand for the trenched soil plots. The lowest delta C-13 was found for the root plots with a mean of -32.6 +/- 0.78 parts per thousand. The mean delta C-13 of the stems was -30.2 +/- 0.74 parts per thousand, similar to the mean delta C-13 of the soil plots. In conclusion, the study showed the potential of using a quantum cascade laser spectrometer to measure delta C-13 of CO2 during automated closed-chamber measurements, thereby allowing for measurements of isotopic ecosystem CO2 fluxes at a high temporal resolution. It also highlighted the importance of proper correction for cross-sensitivity with water vapour and CO2 concentration of the sample air to get accurate measurements of delta C-13.Danish Ministry for Research, Innovation and Higher Education; Danish Council for Independent Research [DFF-1323-00182]Open Access JournalThis item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]

Landscape-scale assessments of stable carbon isotopes in soil under diverse vegetation classes in East Africa : application of near-infrared spectroscopy

Stable carbon isotopes are important tracers used to understand ecological food web processes and vegetation shifts over time. However, gaps exist in understanding soil and plant processes that influence delta C-13 values, particularly across smallholder farming systems in sub-Saharan Africa. This study aimed to develop predictive models for delta C-13 values in soil using near infrared spectroscopy (NIRS) to increase overall sample size. In addition, this study aimed to assess the delta C-13 values between five vegetation classes. The Land Degradation Surveillance Framework (LDSF) was used to collect a stratified random set of soil samples and to classify vegetation. A total of 154 topsoil and 186 subsoil samples were collected and analyzed using NIRS, organic carbon (OC) and stable carbon isotopes. Forested plots had the most negative average delta C-13 values, -26.1aEuro degrees; followed by woodland, -21.9aEuro degrees; cropland, -19.0aEuro degrees; shrubland, -16.5aEuro degrees; and grassland, -13.9aEuro degrees. Prediction models were developed for delta C-13 using partial least squares (PLS) regression and random forest (RF) models. Model performance was acceptable and similar with both models. The root mean square error of prediction (RMSEP) values for the three independent validation runs for delta C-13 using PLS ranged from 1.91 to 2.03 compared to 1.52 to 1.98 using RF. This model performance indicates that NIR can be used to predict delta C-13 in soil, which will allow for landscape-scale assessments to better understand carbon dynamics

Palaeoproterozoic magnesite: lithological and isotopic evidence for playa/sabkha environments

Magnesite forms a series of 1- to 15-m-thick beds within the approximate to2.0 Ga (Palaeoproterozoic) Tulomozerskaya Formation, NW Fennoscandian Shield, Russia. Drillcore material together with natural exposures reveal that the 680-m-thick formation is composed of a stromatolite-dolomite-'red bed' sequence formed in a complex combination of shallow-marine and non-marine, evaporitic environments. Dolomite-collapse breccia, stromatolitic and micritic dolostones and sparry allochemical dolostones are the principal rocks hosting the magnesite beds. All dolomite lithologies are marked by delta C-13 values from +7.1 parts per thousand to +11.6 parts per thousand (V-PDB) and delta O-18 ranging from 17.4 parts per thousand to 26.3 parts per thousand (V-SMOW). Magnesite occurs in different forms: finely laminated micritic; stromatolitic magnesite; and structureless micritic, crystalline and coarsely crystalline magnesite. All varieties exhibit anomalously high delta C-13 values ranging from +9.0 parts per thousand to +11.6 parts per thousand and delta O-18 values of 20.0-25.7 parts per thousand. Laminated and structureless micritic magnesite forms as a secondary phase replacing dolomite during early diagenesis, and replaced dolomite before the major phase of burial. Crystalline and coarsely crystalline magnesite replacing micritic magnesite formed late in the diagenetic/metamorphic history. Magnesite apparently precipitated from sea water-derived brine, diluted by meteoric fluids. Magnesitization was accomplished under evaporitic conditions (sabkha to playa lake environment) proposed to be similar to the Coorong or Lake Walyungup coastal playa magnesite. Magnesite and host dolostones formed in evaporative and partly restricted environments; consequently, extremely high delta C-13 values reflect a combined contribution from both global and local carbon reservoirs. A C- 13-rich global carbon reservoir (delta C-13 at around +5 parts per thousand) is related to the perturbation of the carbon cycle at 2.0 Ga, whereas the local enhancement in C-13 (up to +12 parts per thousand) is associated with evaporative and restricted environments with high bioproductivity

Tree organ growth and carbon allocation dynamics impact the magnitude and δ13C signal of stem and soil CO2 fluxes

Incomplete knowledge of carbon (C) allocation dynamics in trees hinders accurate modeling and future predictions of tree growth. We studied C allocation dynamics in a mature Pinus sylvestris L. dominated forest with a novel analytical approach, allowing the first comparison of: (i) magnitude and delta C-13 of shoot, stem and soil CO2 fluxes (A(shoot), R-stem and R-soil), (ii) concentration and delta C-13 of compound-specific and/or bulk non-structural carbohydrates (NSCs) in phloem and roots and (iii) growth of stem and fine roots. Results showed a significant effect of phloem NSC concentrations on tracheid growth, and both variables significantly impacted R-stem. Also, concentrations of root NSCs, especially starch, had a significant effect on fine root growth, although no effect of root NSC concentrations or root growth was detected on R-soil. Time series analysis between delta C-13 of A(shoot) and delta C-13 of R-stem or delta C-13 of R-soil revealed strengthened C allocation to stem or roots under high C demands. Furthermore, we detected a significant correlation between delta C-13 of R-stem and delta C-13 of phloem sucrose and glucose, but not for starch or water-soluble carbohydrates. Our results indicate the need to include C allocation dynamics into tree growth models. We recommend using compound-specific concentration and delta C-13 analysis to reveal C allocation processes that may not be detected by the conventional approach that utilizes bulk organic matter.Peer reviewe

Response of carbon isotopic compositions of Early-Middle Permian coals in North China to palaeo-climate change

To investigate the magnitude to which the carbon isotopic ratio (delta C-13) varies in coals in response to their contemporary terrestrial environment, the Early-Middle Permian Huainan coals (including coals from the Shanxi Formation, Lower Shihezi Formation and Upper Shihezi Formation) in North China were systematically sampled. A 2.5 parts per thousand variation range of delta C-13 values (-25.15%o to -22.65%o) was observed in Huainan coals, with an average value of -24.06 parts per thousand. As coal diagenesis exerts little influence on carbon isotope fractionation, delta C-13 values in coals were mainly imparted by those of coal -forming flora assemblages which were linked to the contemporary climate. The delta C-13 values in coals from the Shanxi and Lower Shihezi Formations are variable, reflecting unstable climatic oscillations. Heavy carbon isotope is enriched in coals of the Capitanian Upper Shihezi Formation, implying a shift to high positive delta C-13 values of coeval atmospheric CO2. Notably, our study provides evidence of the Kamura event in the terrestrial environment for the first time