Stable isotope mass balances versus concentration differences of dissolved inorganic carbon – implications for tracing carbon turnover in reservoirs

The aim of this study was to identify sources of carbon turnover using stable isotope mass balances. For this purpose, two pre-reservoirs in the Harz Mountains (Germany) were investigated for their dissolved and particulate carbon contents (dissolved inorganic carbon (DIC), dissolved organic carbon, particulate organic carbon) together with their stable carbon isotope ratios. DIC concentration depth profiles from March 2012 had an average of 0.33 mmol L^–1. Increases in DIC concentrations later on in the year often corresponded with decreases in its carbon isotope composition (δ¹³C_DIC) with the most negative value of –18.4?‰ in September. This led to a carbon isotope mass balance with carbon isotope inputs of ?28.5?‰ from DOC and ?23.4, ?31.8 and ?30.7?‰ from algae, terrestrial and sedimentary matter, respectively. Best matches between calculated and measured DIC gains were achieved when using the isotope composition of algae. This shows that this type of organic material is most likely responsible for carbon additions to the DIC pool when its concentrations and δ¹³C_DIC values correlate negatively. The presented isotope mass balance is transferable to other surface water and groundwater systems for quantification of organic matter turnover.     

Isotopic Assessment of Sources and Processes Affecting Sulfate and Nitrate in Surface Water and Groundwater of Luxembourg

Abstract

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 40mg/L, δ³⁴S_sulfate values between ?3.0 and ?20.0‰, and δ¹⁸O_sulfate values between +1.5 and +5.0‰ nitrate was characterized by concentrations varying between <0.5 and 10mg/L, δ¹⁵N_nitrate values of ～?0.5‰, and δ¹⁸O_nitrate values ～+3.0‰. In the shallow groundwater, sulfate concentrations ranged from 25 to 30mg/L, δ³⁴S_sulfate values from ?20.0 to +4.5‰, and δ¹⁸O_sulfate values from ～+0.5 to +4.5‰ nitrate concentrations varied between ～10 and 75mg/L, δ¹⁵N_nitrate values between +2.5 and +10.0‰, and δ¹⁸O_nitrate values between +1.0 and +3.0‰. In surface water, sulfate concentrations ranged from 10 to 210mg/L, δ³⁴S_sulfate values varied between ?9.3 and +10.9‰, and δ¹⁸O_sulfate values between +3.0 and +10.7‰ were observed. Nitrate concentrations ranged from 10 to 40mg/L, δ¹⁵N_nitrate values from +6.5 to +12.0‰, and δ¹⁸O_nitrate values from ?0.4 to +4.0‰. 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.     

Degradation pathways of dissolved carbon in landfill leachate traced with compound-specific 13C analysis of DOC

The isotopic compositions of carbon compounds in landfill leachate provide insights into the biodegradation pathways that dominate the different stages of waste decomposition. In this study, the carbon geochemistry of different carbon pools, environmental stable isotopes and compound-specific isotope analysis (CSIA) of leachate dissolved organic carbon (DOC) fractions and gases show distinctions in leachate biogeochemistry and methane production between the young area of active waste emplacement and the old area of historical emplacement at the Trail Road Landfill (TRL).

The active area leachate has low DOC concentrations (<200 mg l^?1) dominated by fulvic acid (FA=160 mg l^?1), and produces CH₄ dominantly by CO₂ reduction (D? excess=20.6‰). Leachate generated in the area of older waste has high DOC (>4770 mg l^?1) dominated by FA (4482 mg l^?1) and simple fatty acids (acetic=1008 mg l^?1 and propionic=608 mg l^?1), and produces CH₄ by the acetate fermentation pathway (D? excess=9.8‰). CSIA shows an advanced degradation and a progressive accumulation of ¹³C of fatty acids in leachate from the older area. The enriched ¹³C value of FA (?20 and?26‰ for the older and active parts, respectively,) and of low molecular weight DOC (?8 and?27‰) as well as of the bulk DOC (?21 and?25‰) shows more advanced degradation in the older part of the landfill, which is consistent with the shift in the humic/FA ratios (0.05 and 0.18). The ¹³C enrichment of acetate (?12‰) above the ¹³C of DOC (?21‰) and of propionic acid (?19‰), in older leachate, suggests that this acetate has not evolved from the simple degradation of larger organic molecules, but by homoacetogenesis from the enriched dissolved inorganic carbon (DIC) pool (8‰) and H_2, which produce a more enriched ¹³C of acetate. In contrast, the ¹³C of the minor acetate in the active area (?17‰) indicates that CO₂-reducing bacteria must be the primary consumers of H₂, which has resulted in enriched ¹³C_DIC (10‰) and depleted ¹³C_CH4 (?58‰).     

Isotope-Ratio-Monitoring Liquid Chromatography Mass Spectrometry (IRM-LCMS): First Results from a Moving Wire Interface System

Abstract

A Liquid Chromatography-Combustion (LC-C) Interface, based on a moving wire technique, has been built and tested. The LC effluent is deposited onto a transport wire, which carries the sample through solvent evaporation and combustion ovens. CO₂ from the combustion step is analysed in an isotope ratio mass spectrometer. Performance of the interface was tested by loop injections of sucrose and glucose into a liquid flow of methanol/water (80/20). Accuracy and precision of δ¹³C_PDB < 1‰ was achieved for sample concentrations > 500 ng/ul (5μl loop), sufficient for studies at natural isotope ratios. In case of ¹³C tracer applications the detection limit was determined to be about 20 pg carbon tracer (on wire).     

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. CO₂ removed from the carrier gas stream by cryogenic trapping is transferred onto a GC column. Following GC separation, the CO₂ 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 δ¹³C = -28.8‰.     

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.     

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.     

Stable Carbon Isotope Fractionation in Lower Plants from the Schirmacher and Untersee Oases (Central Dronning Maud Land,East Antarctica)

Abstract

Lower plants (algae, lichens, mosses) from the Antarctic continent have been analysed for their stable carbon isotope composition. In contrast to lichens and mosses which exhibit quite normal δ¹³C-values the studied microbial benthos is characterized by an extremely low carbon isotope fractionation (δ¹³C-values up to ?1.4‰. vs. PDB). Limited CO₂ availability and bicarbonate uptake are probably the main factors responsible for this phenomenon.     

Temporal diet changes recorded by stable isotopes in Asiatic black bear (Ursus thibetanus) hair

Carbon and nitrogen stable isotope ratios were measured in hair samples of the Asiatic black bear (Ursus thibetanus) inhabiting the Northern Japanese Alps (NJA) (n?=?20) and the periphery of Nagano City (NC) (n?=?6), in Nagano Prefecture, Japan. The hair of NJA bears, which did not have access to anthropogenic foods, showed lower values of δ¹³C and δ¹⁵N than that of NC bears which had access to garbage and corn fields, especially during the summer. These results reflect somewhat differing diets between the NJA and NC bears. We attempted to assess the feeding history during the hair growth cycle using the growth section analysis method. Each hair sample had been cut into 3?mm lengths from root to tip, labeled, and analyzed along the hair growth. We measured the carbon and nitrogen stable isotope ratios of each 3?mm length of hair sample from one NC bear which had been killed while raiding a corn field. The sections showed wide ranges of isotope ratios, from ?23.2‰ to ?14.6‰ for δ¹³C, and from 0.3‰ to 4.6‰ for δ¹⁵N. It was shown that the diet of this bear shifted dramatically from principally C₃ plants to more C₄ plants and to foods of animal origin. An analysis of the whole hair reflects just the average feeding habit during hair growth, but the present method can trace its diet history. This method can contribute to obtain precise ecological information of wildlife.     

Determination of δ13 CV−PDB and δ15NAIR values of cocaine from a big seizure in Germany by stable isotope ratio mass spectrometry†

In this study, δ¹³C_{V? PDB} and δ¹⁵N_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 δ¹⁵N_AIR values ranging from?17 to ?2 ‰. 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.     

Isotope-Ratio-Monitoring Liquid Chromatography Mass Spectrometry (IRM-LCMS): First Results from a Moving Wire Interface System

Abstract A Liquid Chromatography-Combustion (LC-C) Interface, based on a moving wire technique, has been built and tested. The LC effluent is deposited onto a transport wire, which carries the sample through solvent evaporation and combustion ovens. CO(2) from the combustion step is analysed in an isotope ratio mass spectrometer. Performance of the interface was tested by loop injections of sucrose and glucose into a liquid flow of methanol/water (80/20). Accuracy and precision of δ(13)C(PDB) < 1‰ was achieved for sample concentrations > 500 ng/ul (5μl loop), sufficient for studies at natural isotope ratios. In case of (13)C tracer applications the detection limit was determined to be about 20 pg carbon tracer (on wire).     

Evaluation of the Sulfate Dynamics in Groundwater by Means of Environmental Isotopes

Abstract

Elevated sulfate concentrations and their heterogeneous distribution in the drinking water catchment area Torgau-Mockritz (Germany) were investigated by means of multiple isotope signatures such as δ³⁴S, δ¹⁸O-H₂O, δD, tritium, and ⁸⁵Kr. δ³⁴S values of the groundwater sulfate vary between -19…+ 37‰ CDT. No simple correlation exists between sulfate concentrations and δ³⁴S. Superimposition of different sulfur sources and mobilization processes combined with a complicated groundwater movement create a complex distribution pattern. The oxidation of reduced sedimentary sulfur has to be regarded as a main source of dissolved sulfate at least regionally. Tritium and ¹⁴C data revealed that old groundwater can be excluded as source for high sulfate contents. Correlated temporal variations in the concentrations of tritium and sulfate are observed in deeper sampling positions. Highly variable δ¹⁸O and δD, as detected in parts of the catchment area, indicate local influences of surface water infiltration into the aquifer. The spatial distribution of isotope signatures enables the identification of zones with descending younger water or hindered groundwater movement and hence provides useful hints for flow modeling.     

Reliability of stable carbon and oxygen isotope compositions of pedogenic needle fibre calcite as environmental indicators: examples from Western Europe

Stable carbon and oxygen isotope analyses were conducted on pedogenic needle fibre calcite (NFC) from seven sites in areas with roughly similar temperate climates in Western Europe, including the Swiss Jura Mountains, eastern and southern France, northern Wales, and north-eastern Spain. The δ¹³C values (?12.5 to?6.8 ‰ Vienna Pee Dee Belemnite (VPDB)) record the predominant C₃ vegetation cover at the sites. A good correlation was found between mean monthly climatic parameters (air temperature, number of frost days, humidity, and precipitation) and δ¹⁸O values (?7.8 to?3.4‰ VPDB) of all the NFC. Similar seasonal variations of δ¹⁸O values for monthly NFC samples from the Swiss sites and those of mean monthly δ¹⁸O values of local precipitation and meteorological data point out precipitation and preferential growth/or recrystallisation of the pedogenic needle calcite during dry seasons. These covariations indicate the potential of stable isotope compositions of preserved NFC in fossil soil horizons as a promising tool for palaeoenvironmental reconstructions.     

Using the 13C/12C carbon isotope ratio to characterise the emission sources of airborne particulate matter: a review of literature

ABSTRACT

Particulate matter (PM) from atmospheric aerosols contains carbons that are harmful for living organisms and the environment. PM can originate from vehicle emissions, wearing of vehicle components, and dust. Size and composition determine PM transport and penetration depth into the respiratory system. Understanding PM emission characteristics is essential for developing strategies to improve air quality. The number of studies on carbon isotope composition (¹³C/¹²C) of PM samples to characterise emission factors has increased. The goal of this review is to integrate and interpret the findings from ¹³C/¹²C carbon isotope ratio (δ¹³C, ‰) analyses for the most common types of emission sources. The review integrates data from 25 studies in 13 countries. The range of δ¹³C of PM from vehicle emissions was from ?28.3 to ?24.5?‰ and for non-vehicle anthropogenic emissions from ?27.4 to ?23.3?‰. In contrast, PM ranges for δ¹³C from biomass burning sources differed markedly. For C₃ plants, δ¹³C ranged from ?34.7 to ?25.4?‰ and for C₄ plants from ?22.2 to ?13.0?‰. The ¹³C/¹²C isotope analysis of PM is valuable for understanding the sources of pollutants and distinguishing vehicle emissions from biomass burning. However, additional markers are needed to further distinguish other anthropogenic sources.     

Seasonal variation in natural abundance of δ13C and 15N in Salicornia brachiata Roxb. populations from a coastal area of India

High and fluctuating salinity is characteristic for coastal salt marshes, which strongly affect the physiology of halophytes consequently resulting in changes in stable isotope distribution. The natural abundance of stable isotopes (δ¹³C and δ¹⁵N) of the halophyte plant Salicornia brachiata and physico-chemical characteristics of soils were analysed in order to investigate the relationship of stable isotope distribution in different populations in a growing period in the coastal area of Gujarat, India. Aboveground and belowground biomass of S. brachiata was collected from six different populations at five times (September 2014, November 2014, January 2015, March 2015 and May 2015). The δ¹³C values in aboveground (?30.8 to ?23.6?‰, average: ?26.6?±?0.4?‰) and belowground biomass (?30.0 to ?23.1?‰, average: ?26.3?±?0.4?‰) were similar. The δ¹³C values were positively correlated with soil salinity and Na concentration, and negatively correlated with soil mineral nitrogen. The δ¹⁵N values of aboveground (6.7–16.1?‰, average: 9.6?±?0.4?‰) were comparatively higher than belowground biomass (5.4–13.2?‰, average: 7.8?±?0.3?‰). The δ¹⁵N values were negatively correlated with soil available P. We conclude that the variation in δ¹³C values of S. brachiata was possibly caused by soil salinity (associated Na content) and N limitation which demonstrates the potential of δ¹³C as an indicator of stress in plants.     

Untersuchungen zur Isotopensignatur von Methan und Kohlendioxid aus biogenen Gasen unterschiedlicher Quellen

Abstract

The isotopic compositions of biogenic carbon dioxide and methane from different sites were investigated. The δ¹³C values of methane vary mainly between ?55‰ and ?75‰ whereas δ¹³C values of carbon dioxide were found from about + 11‰ to ?23‰. Especially the latter ones are not so typical for microbial gases. The different sites don't vary over the whole scales but form certain groups. Secondary effects like diffusion change the δ values of both components in an even more negative direction, while oxidation processes near the surface result in more positive δ¹³C values for methane and very negative δ¹³C values for carbon dioxide.     

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.     

Pleistocene age paleo-groundwater inferred from water-stable isotope values in the central part of the Baltic Artesian Basin

A new data set of δ²H and δ¹⁸O in the groundwater from the central part of the Baltic Artesian Basin is presented. The hydrogeological section is subdivided into stagnation, slow exchange and active exchange zones. Na–Ca–Cl brine found at the deepest part – the stagnation zone – is characterized by δ¹⁸O values above ?5?‰ and δ²H values approaching ?40?‰ with respect to Vienna Standard Mean Ocean Water. The slow exchange zone where waters of mostly intermediate salinity reside is characterized by δ¹⁸O values around ?11.7?‰ and δ²H values around ?85.3?‰. Mean δ¹⁸O and δ²H values of the fresh groundwater in the active water exchange zone are ?11.1 and ?79.9?‰, respectively. Characteristically, the groundwater in the active and slow exchange zone is isotopically more depleted compared with the precipitation values observed, and the depletion increases with depth down to the level where strongly enriched brines are encountered.     

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‰.     

Natural abundances of 15N and 13C in leaves of some N2-fixing and non-N2-fixing trees and shrubs in Syria

A survey study was conducted on man-made plantations located at two different areas in the arid region of Syria to determine the variations in natural abundances of the ¹⁵N and ¹³C isotopes in leaves of several woody legume and non-legume species, and to better understand the consequence of such variations on nitrogen fixation and carbon assimilation. In the first study area (non-saline soil), the δ¹⁵N values in four legume species (Acacia cyanophylla,?1.73 ‰ Acacia farnesiana,?0.55 ‰ Prosopis juliflora,?1.64 ‰; and Medicago arborea,+1.6 \textperthousand) and one actinorhizal plant (Elaeagnus angustifolia,?0.46 to?2.1 ‰) were found to be close to that of the atmospheric value pointing to a major contribution of N₂ fixing in these species; whereas, δ¹⁵N values of the non-fixing plant species were highly positive. δ¹³C ‰; in leaves of the C3 plants were found to be affected by plant species, ranging from a minimum of?28.67 ‰; to a maximum of?23 ‰. However, they were relatively similar within each plant species although they were grown at different sites. In the second study area (salt affected soil), a higher carbon discrimination value (Δ¹³C ‰) was exhibited by P. juliflora, indicating that the latter is a salt tolerant species; however, its δ¹⁵N was highly positive (+7.03 ‰) suggesting a negligible contribution of the fixed N₂. Hence, it was concluded that the enhancement of N₂ fixation might be achieved by selection of salt-tolerant Rhizobium strains.