Beiträge zur Isotopengeochemie von Erdgasen

It is the proper aim of geochemical investigations regarding natural gas to describe the processes of generation, migration and accumulation of gaseous compounds. By this way our research results should contribute to knowledge about the gas generating potential of organic matter and about the expected gas volumes in natural gas deposits.

The main topics in the authors' research project are

- isotopic characterization of hydrocarbon forming organic matter

- simulation of the generation of natural gas components by coalification processes (model experiments including also radiolytic gas formation from organic matter)

- investigation of various separation processes (diffusion, adsorption, solubility, mixing of gases. oxidation of natural gas components) affecting chemical compositions and isotopic signatures

- elucidation of pressure and temperature dependence of separation processes and especially of the elementary isotope separation cofficients in systems gas/sorbent

- as the main result, an interpretation concept for natural gas samples is proposed which is based on chemical and isotopic compositions of methane and ethane in the samples and which takes into consideration also separation processes.

Following this summarizing publication some of the most important results of our research work will be presented in more detail in three separate parts.     

Isotopengeochemische Untersuchungen an organischen Substanzen aus Sedimenten der Hilsmulde (Nordwestdeutschland)

Abstract

Model coalification experiments have been carried out using organic matter in sediments from the Hils syncline. In the experiments we wanted to elucidate, to what extent different facies situations can be observed in the investigated region and which conclusions can be drawn regarding the type of originating substances for hydrocarbons adsorbed in drilling cores. As a result of chemical and isotope analyses the organic substances should be characterized not only as pure sapropelites but show in different degree the participation of humic organic matter.

The obtained data of the several evaluation methods used for the characterization of organic matter are in good agreement for the particular samples.     

Stable Sulfur Isotope Effects Related to Local Intense Sulfate Reduction in a Tidal Sandflat (Southern North Sea): Results from Loading Experiments

Abstract

Anoxic sediment surfaces coloured black by iron monosulfides (“black spots”) evolve in tidal sandflats of the Wadden Sea (southern North Sea) as a result of the degradation of buried organic matter. To follow the short- and long-term effects of organic matter burial on pore water and sediment isotopic biogeochemistry, formation of artificial black spots was initiated on the Groninger Plate (site RP63) in the backbarrier tidal flats of Spiekeroog island. Changes in concentrations (DOC, TA, TOC, sulfate, sulfide, TRS, Fe) and isotopic compositions (sulfate, sulfide, TRS, pyrite, TOC) were followed for up to 12 months and compared to reference areas. 13°C ratios of TOC clearly mirror the early diagenetic degradation of organic matter. At least temporarily closed system sulfate reduction is inferred for the artificial black spot from the variation of sulfate concentrations and stable sulfur isotope partitioning, In the interstitial waters of the black spot, 34S/32S values of coexisting dissolved sulfate and sulfide yield fractionation degrees between ?5 and ?25%. On the reference area, 34S/32S are fractionated by ?32 to ?42% as calculated from the isotope composition of solid phase reduced sulfur and pore water sulfate. Sulfur isotope fractionation seems to increase with decreasing sulfate reduction rate. Limiting factor seems to be the availability of DOC. Between the pyrite pool and the dissolved sulfide in the black spot, no significant isotope exchange is observed within 12 months.     

Effects of high pressure and temperature on carbon isotope compositions of some acyclic alkanes and preservation of organic matter

The effects of high pressure and temperature on carbon isotopic compositions of acyclic alkanes and the stability of the acyclic alkanes were experimentally investigated. The pyrolysis of lignite with water in a closed system was conducted at 400–700°C and 1–3 GPa. The carbon isotope data, variations of peak carbon and evident odd–even predominance of acyclic alkanes indicated that: (1) the high pressure retarded the maturation of organic matter and destruction of hydrocarbons, (2) n-C₁₂₊ hydrocarbons from biogenic sources could be preserved in the cool slab subducted into the upper mantle, and (3) some organic compounds might preserve the carbon isotope signals inherited from biogenic sources. The results favor tracing the origins of organic matter in mantle rocks and extraterrestrial organic matter in meteorites and the process of deep carbon cycle.     

Gas Forming Processes within Lignite Mining Dumps

Abstract

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‰, which is typical for humous materials. The carbonates are found to be of marine origin (δ¹³C: +0.5 to ?1.1‰). 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.     

PB- Und Sr-Isotopensignaturen AlS Herkunftsindikatoren Für Anthropogene Und Geogene Kontaminationen

Abstract

In isotope geochemistry, natural differences in isotope abundance ratios of heavy elements (e.g. Sr, Nd, Pb) allow the use of specific isotopic signatures as tracers for these and genetically related elements. Examples of such applications in the field of anthropogeochemistry will be presented for lead and strontium.     

Rechnergestützte Auswertung experimenteller Inkohlungsuntersuchungen

Model investigations, carried out as laboratory coalification reactions with humous and sapropelitic sediments of different maturation degree, showed that conclusions can be drawn about the character of the parent rock of a natural gas using data of the chemical and isotopic composition of the organic substance in sediments and its coalification products.

Several examples demonstrate, that the following parameters have proved as suitable fades- and in part as maturity criteria: CH₄/Σ HKW; C₂H₆/CH₄, i-/n-C₄H₁₀, ¹³C-abundance of organic substance, ¹³C-abundance of methane.

For a complex interpretation all results obtained from coalification experiments over some years were stored in a data file. By means of cluster analysis all samples were classified in groups corresponding to their characteristics represented by the above mentioned five criteria. Four clusters resulted depending on maceral composition of the tested organic sediments. The differentiating criteria of these clusters are discussed.     

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.     

Insights from stable isotopes of water and hydrochemistry to the evolutionary processes of groundwater in the Subei lake basin,Ordos energy base,Northwestern China

ABSTRACT

Changes in groundwater evolutionary processes due to aquifer overexploitation show a world-wide increase and have been of growing concern in recent years. The study aimed to improve the knowledge of groundwater evolutionary processes by means of stable water isotopes and hydrochemistry in a representative lake basin, Ordos energy base. Groundwater, precipitation, and lake water collected during four campaigns were analysed by stable isotopes and chemical compositions. Results showed that temperature effect predominated the isotope fractionation in precipitation, while evaporation and inadequate groundwater recharge were the key factors explaining high salinity and isotopic enrichment in lake water. Additionally, the Kuisheng Lake was a preferential area of groundwater recharge, while the Subei Lake received less sources from underlying aquifer due to the combined effects of low permeable zone and upstream groundwater captured by the production wells. The homogeneous isotope signatures of groundwater may be ascribed to the closely vertical hydraulic connectivity between the unconfined and the confined aquifers. Isotopically enriched groundwater pumping from well field probably promoted isotopic depletion in groundwater depression cone. These findings not only provide the conceptual framework for the inland basin, but also have important implications for sustainable groundwater management in other groundwater discharge basins with arid climate.     

Limitations of the Quantification of Organic Carbon in Sediment from C–H Stretching Vibrations in DRIFT Spectra

Abstract

The limitations of quantifying organic carbon (OC) or various organic substances in sediment from the integration of infrared C–H stretching bands using diffuse reflectance infrared Fourier transform (DRIFT) spectra are pointed out, both from theoretical arguments and by presenting experimental data. Such determinations are inaccurate and imprecise because (i) the band at 2930 cm^?1 is not exclusively due to CH₂ groups; (ii) there is a spectral interference from CO₃ ^2? absorption; and (iii) the proportion of CH₂ groups in organic matter varies for different sediments. The measurement of aliphatic C–H stretching band areas only provides an approximate measurement of aliphatic carbon bonded to hydrogen, which turns out to be a factor of about 3 to 3.5 times smaller than the OC content for Hong Kong marine sediments, depending on their nature and origin.     

Isotope variations of hydrogen,carbon and nitrogen in florae from the Schirmacher Oasis,East Antarctica

Comparative biochemical and isotope-chemical investigations of cosmopolitical plants open up ways of obtaining parameters from different parts of the Earth which are characterised by variations in the habitat due to different environments. As an Antarctic oasis, the Schirmacher Oasis disposes of adequate favourable ecological conditions for the growth of lower plants.

In the present paper, results of isotope studies of lichens, mosses and algae of the Schirmacher Oasis are given and peculiarities of the habitats which influence the isotope contents of the plants are discussed.     

Sulfur Isotope Fractionation in the Biogeochemical Sulfur Cycle of Marine Sediments

Abstract

The sulfur isotopic record of sedimentary sulfides (mainly pyrite) and sulfates shows considerable variations in time and plays an important role in the biological and geochemical interpretation, e.g., of the evolution of life and the oxygen partial pressure of Earth's atmosphere (e.g. [1]). From a comparison of experimental results with Desulfovibrio spp. it can be inferred that the S isotope fractionation during reduction of sulfur compounds is controlled by the number of electrons transferred (Fig. 1). Sulfur isotope discrimination in the sulfur cycle of marine sediments is dominated by dissimilatory bacterial sulfate reduction (BSR), and [2] used laboratory experiments with mesophilic bacteria to postulate that high sulfate reduction rates with abundant sulfate at enhanced temperature dominated the Ocean water chemistry during early Archean time. Experiments with pure cultures of thermophilic sulfate reducers [3] and natural hydrothermally influenced communities [4], however, demonstrated that isotope discrimination is close to average fractionation by mesophiles and that temperature is not directly influencing isotope discrimination during BSR.     

Variations of δ15N-Values and Hydrolyzable Amino Acids in Settling Particles in the Ocean

Abstract

The modification of nitrogen isotopic signals during particle sedimentation in the sea is of great interest for the use of sedimentary δ¹⁵N-values as a paleoceanographic tool. The effect of organic matter degradation on such modification was studied by analyzing nitrogen, hydrolyzable amino acids (THAA) and δ¹⁵N-values in a suit of marine settling particles collected from the Bay of Bengal, Indian Ocean, by using time-series sediment traps, and in underlying sediments. The flux of settling particles showed temporal variations which are related to the monsoons, the major climatic feature of this marine region. During high flux periods settling particles are enriched in nitrogenous material that is less degraded and exhibit higher δ¹⁵N-values than particles showing characteristics of degradation. At the sediment surface more than 95% of the settling particulate nitrogen is lost and the δ¹⁵N-values of the residual sedimentary nitrogen are higher than those of settling particles. The observed increase is interpreted to be due to fractionation during degradation of organic matter.     

Expression of maternal isotopes in offspring: implications for interpreting ontogenetic shifts in isotopic composition of consumer tissues

When evaluating ontogenetic shifts in isotopic composition of consumer tissues within the context of a dietary analysis, the isotopic starting point of consumers in the population should not be ignored. Neonate isotopic composition may be different from that of juveniles and adults; in general, neonate tissues are built from maternal resources rather than food resources. Thus, the range of isotope values observed within a population of consumers may be significantly impacted by consumer isotope ratios at birth. Long-term goals of my research involve the use of stable isotopes to assess the role diet plays in driving population level differences in life history and demography observed among three pigmy rattlesnake (Sistrurus miliarius; family Viperidae) populations. For meaningful interpretation of field-collected data, it was important to determine starting (i.e., at birth) isotopic compositions of rattlesnakes from the study populations. We quantified isotopic composition of pregnant pigmy rattlesnake scale tissue, isotopic composition of neonate scale tissue and the degree that neonate scale tissue isotopic composition reflected the isotopic composition of maternal scale tissue. Collectively, neonate isotopic composition was highly variable among-litters; average litter delta(13)C values spanned 7 per thousand and average litter delta(15)N values spanned 2.8 per thousand. Over 95 % of the variation in offspring isotopic composition was expressed among litters. Thus, high levels of among-litter isotopic variation were largely due to the retention of a maternal signal. Results of the enclosure study suggest that highly variable isotopic signatures in young animals within field populations could easily reflect the retention of a maternal signal rather than differences in resource utilisation among younger snakes.     

Using Stable Isotope Analyses to Identify Allochthonous Inputs to Lake Naivasha Mediated via the Hippopotamus Gut

Abstract

The hippopotamus grazes nocturnally on land and resides in water during the day. Much of the ingested material must therefore be defecated directly into the aquatic system and can thus be considered an allochthonous resource available to aquatic consumers. The utility of stable isotope analyses of carbon and nitrogen to distinguish hippo faecal matter from other potential basal resources was tested at Lake Naivasha, Kenya. Hippopotami proved faithful to a short grass diet although supplementary grazing of aquatic macrophytes was observed. The typical isotopic ratios of C4 grasses ingested were not altered substantially by gut processes, and were clearly distinct from algal and aquatic macrophyte isotopic ratios. However, marginal plants such as Cyperus papyrus exhibit C4 ratios, and so the technique is suitable only for use in localities where ‘contamination’ from such sources is negligible.     

Stable isotope deltas: tiny,yet robust signatures in nature

Although most of them are relatively small, stable isotope deltas of naturally occurring substances are robust and enable workers in anthropology, atmospheric sciences, biology, chemistry, environmental sciences, food and drug authentication, forensic science, geochemistry, geology, oceanography, and paleoclimatology to study a variety of topics. Two fundamental processes explain the stable isotope deltas measured in most terrestrial systems: isotopic fractionation and isotope mixing. Isotopic fractionation is the result of equilibrium or kinetic physicochemical processes that fractionate isotopes because of small differences in physical or chemical properties of molecular species having different isotopes. It is shown that the mixing of radioactive and stable isotope end members can be modelled to provide information on many natural processes, including ¹⁴C abundances in the modern atmosphere and the stable hydrogen and oxygen isotopic compositions of the oceans during glacial and interglacial times. The calculation of mixing fractions using isotope balance equations with isotope deltas can be substantially in error when substances with high concentrations of heavy isotopes (e.g. ¹³C, ²H, and ¹⁸O ) are mixed. In such cases, calculations using mole fractions are preferred as they produce accurate mixing fractions. Isotope deltas are dimensionless quantities. In the International System of Units (SI), these quantities have the unit 1 and the usual list of prefixes is not applicable. To overcome traditional limitations with expressing orders of magnitude differences in isotope deltas, we propose the term urey (symbol Ur), after Harold C. Urey, for the unit 1. In such a manner, an isotope delta value expressed traditionally as?25 per mil can be written as?25 mUr (or?2.5 cUr or?0.25 dUr; the use of any SI prefix is possible). Likewise, very small isotopic differences often expressed in per meg ‘units’ are easily included (e.g. either+0.015 ‰ or+15 per meg can be written as+15 μUr.     

Metabolite Pools and Metabolic Branching as Factors of in-vivo Isotope Discriminations by Kinetic Isotope Effects

Abstract

Inter- and intra-molecular non-statistical isotope distributions do not only require the existence of a kinetic isotope effect on a defined enzyme catalyzed reaction, but also the prerequisite that this reaction is located at a metabolic branching point. Furthermore a metabolic and isotopic balance demand that the extent of the isotopic shift is reciprocal to the products' yields. On this base the ¹³C-enrichment of L-ascorbic acid in position C-1 and the depletion of glycerol in C-1 are interpreted. The ¹³C-pattern of natural malic acid is discussed as a consequence of isotope effects on the carboxylation of pyruvate and PEP and on the pyruvate dehydrogenase reaction. The patterns of natural products synthezised by transfer of “active acetaldehyde” is proposed to be due to an isotope effect on the thiamine pyrophosphate containing lyase reaction. An isotope effect on the reduction of “active formaldehyde” to “active methyl” and the existence of corresponding pools is responsible for ¹³C-enrichments and depletions of natural products in positions bearing these intermediates. Finally a model for the main nitrogen pools and for isotope discriminations between α-amino, ω-amino-N and amide pools in plants is proposed.     

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.     

Comparison of δ81Br and δ37Cl composition of volatiles,salt precipitates,and associated water in terrestrial evaporative saline lake systems

This study provides the first characterization of the variability of bromine and chlorine stable isotopic composition in evaporites, associated residual brines, and shoreline gases in terrestrial evaporative saline lakes. The lakes investigated here are groundwater discharge locations, and include both potash-rich alkaline lakes and sodic-dominated neutral pH lakes at a variety of salinities and evaporative stages. The chlorine and bromine isotope systems behave consistently different during evaporative salt precipitation, with ³⁷Cl more enriched in the salt than in the fluid, but ⁸¹Br more enriched in the fluid compared with the precipitated salt. The ⁸¹Br concentration of shore off-gassing was even smaller than mineral precipitate compositions. The trends observed for bromine isotopes are surprising compared with published laboratory studies, indicating that a process besides inorganic mineral precipitation is affecting δ⁸¹Br. Additional processes explored include diffusion, salt deflation, microbial and photolytic conversion to the gas phase, and oxidative bromination of organic matter.

Dedicated to Professor Peter Fritz on the occasion of his 80th birthday     

Isotope Geochemical Studies on Carbonates of Quaternary Glacio-Lacustrine Lake Sediments as indicators of Paleoenvironment

Selected silty “summer” and argillaceous “winter” layers of profiles of the rhythmically bedded glacio-lacustrine ice-marginal lake sediment of the Dehlitz-Leipzig varved clay (Leipziger Tieflandsbucht, Central Germany) have been examined for isotope composition (¹⁸O/¹⁶O, ¹³C/¹²C) of carbonate and organic fraction. In addition, mineralogical and grain size compositions were determined. The results show 1) a change in source of carbonate sediment (provenance) through time; 2) the oxygen isotope ratios differed between the “summer” and “winter” layers of varves couplets due to different rates of sedimentation; 3) anoxic events occurred in the lake; 4) carbon isotope ratios suggest organics in lake sediments which were derived from land and the primary productivity was low in the lake itself. In the study of cold-climatic lake sediments, isotope investigations can efficiently be used as additional paleosedimentological and facies indicators.