Isotopengeochemische Charakterisierung kohlenwasserstoffbildender organischer Substanzen

Within the framework of a larger research project on contributions of isotope investigations to natural gas and crude oil exploration, the following publication is a first part of research reports from the author's laboratory.

The isotopic composition of carbon in fossil organic matter is primarily determined by the type of biological precursors. The main constituents forming organic matter in sediments are higher plants and microorganisms (algae, bacteria). These precursors contain a great number of organic compounds with corresponding isotope signatures. Hydrocarbons and lignin e.g., are enriched in carbon 13, while lipids in most cases are depleted.

Semi-empirical calculations on a thermodynamic basis are used to precalculate isotopic compositions of components or single compounds, applying the so-called β-factor method. The results are compared with numerous data from references about isotopic compositions of higher plants, algae and plant components. Also environmental conditions of plant growing-including paleoenvironment-have been taken into consideration.

The δ¹³C values of more than 150 types of organic substances in sediments of several geological formations have been measured in our isotope geochemical department.

The results allow a characterization and classification of organic matter: humic and sapropelitic organic substances can in many cases be distinguished by their isotopic signatures taking into account exceptions of e.g., regional origins. Influences of maturity (characterized by vitrinite reflectance) and especially of macerale composition of organic matter on it's isotope values and on the formation of hydrocarbons including their isotopic compositions are elucidated. The interpretation concept is also assured using special examples of drilling sites in Germany. The obtained results and proposed interpretation concept can contribute to further development in the understanding of hydrocarbon formation and natural gas exploration.     

Leaching Behaviour and Solid Phase Fractionation of Selected Metals as Affected by Thermal Treatment of a Polluted Sediment

Abstract

A contaminated dredged sediment was subjected to a thermal treatment at temperatures ranging from 120 to 450°C. The leaching behaviour of selected metals (Cd, Cu, Pb, Zn, Fe, Mn) was studied using NH₄OAc-EDTA extraction. In addition, solid phase fractionation was carried out by means of a sequential extraction procedure.

The NH₄OAc-EDTA extraction showed a sharp increase in metal leachability from sediments treated at intermediate temperatures (120–350°C). The metal fractionation of the solid phases at the different temperatures did not reveal relevant shifts except for Cu. The decrease of the oxidizable Cu fraction was highly correlated (P < 0.001) with the disappearance of organic matter at higher treatment temperatures. It is suggested that binding energy changes within the fractions rather than shifts between chemical forms account for the observed leaching behaviour.     

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.     

生物活动对海床沉积物工程地质特征改造研究

底栖穴居动物是河口潮滩生态系统的重要组成部分,它对沉积物的二次改造作用非常重要。本文以黄河三角洲钓 口区潮滩为研究对象,研究了不同生物密度对沉积物工程地质特征的改造,包括滩面形态、沉积物强度、以及沉积物颗粒大小 的改变。在此基础上探讨了生物活动与滩面凹坑,沉积物强度非均匀性以及研究区浮泥之间的关系。     

Estimation of carbonate concentration and characterization of marine sediments by Fourier Transform Infrared Spectroscopy

Fourier Transform Infrared Spectroscopy (FTIR) is a well established method for the characterization of mineralogical and geochemical properties of marine sediments. Understanding the biogeochemical changes in marine ecosystems is challenging task since it requires adequate analytical techniques and efforts. Biogeochemical characteristics of twenty one marine sediment samples collected off Chennai coast, Bay of Bengal, India were analyzed using FTIR spectroscopy. The FTIR peaks at 1460 cm⁻¹ (stretching vibration) and 880 cm⁻¹ (bending vibration) were used for carbonate determination. To verify the FTIR results, the obtained carbonate data were compared with carbonate values obtained by chemical analyses. The ranges of carbonate in sediments using FTIR and chemical analyses were 4.5–9.6% and 4.8–10%, respectively. The significant positive relationship was obtained between the carbonate results of FTIR and chemical analyses. This study demonstrates that instead of expensive and time consuming chemical methods, FTIR spectroscopic technique is found as a suitable, rapid and effective method for the quantification of carbonate in marine sediments.     

Levels of polycyclic aromatic hydrocarbons,polychlorinated byphenyls,methylmercury and butyltins in the natural UNESCO reserve of the biosphere of Urdaibai (Bay of Biscay,Spain)

Polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), methylmercury (MeHg⁺) and butyltins (mono-, di- and tri-butyltin, MBT, DBT and TBT) were monitored in oysters (Crassostrea sp.) and sediments collected in different sampling points of the UNESCO reserve of the biosphere of Urdaibai (Bay of Biscay) from March 2006 to June 2007. In the case of oyster samples, concentrations in the 290–1814 µg kg^?1 (PAHs), 70–475 µg kg^?1 (PCBs), 75–644 µg kg^?1 (MeHg⁺) and 200–1300 µg kg^?1 (as a sum of the three butyltins) ranges were obtained. In most samples TBT was the most abundant butyltin, followed by DBT and MBT. It should be highlighted that most samples exceeded the highest range (367 µg kg^?1) found in the last mussel watch programme carried out by the National Oceanic and Atmospheric Administration (NOAA) for butyltins in oyster samples. This could be due to the presence of a shipyard in the estuary. Sediment concentrations ranged as follows: total PAHs (856–3495 µg kg^?1) and total PCBs (58–220 µg kg^?1). Organometallic species were always below the limits of detection (LODs) (0.24 µg kg^?1 for MeHg⁺, 0.6 µg kg^?1 for MBT, 0.48 µg kg^?1 for DBT and 1.1 µg kg^?1 for TBT). In both sediment and oyster PAH sources were mostly combustion. In the case of PCBs, 4-6 chlorine-atom congeners were the most abundant ones. Slight differences in the profile of PAHs as well as PCBs can be detected when the matrices were compared with each other. Finally, in the case of PAHs, sediment and water column played the main role in the accumulation pathway into the organisms in all the sampling stations.     

Determination of Trace Metals in Antarctic Sediments from Terra Nova Bay - Ross Sea

Abstract

Trace metals (Cu, Pb, Zn, Cd, Cr, Ni, Co, Mn) and iron concentration were determined in several sediments collected in the Antarctica (Terra Nova Bay—Ross Sea). Samples were analyzed by inductively coupled plasma (ICP-AES) after selective and total extraction. The results are in good agreement with the data previously collected in the same area.     

Analytical methods and problems related to the determination of organotin compounds in marine sediments

The determination of organotin compounds in bottom sediments is a complex process that requires a number of analytical steps, i.e. sample collection, transport and storage; extraction of analytes from sediment; derivatization; extract purification; enrichment; and the final chromatographic measurement. The whole process is time and labour consuming, and subject to securing sample representativeness. In this review the most frequently encountered problems and the examples of possible analytical solutions are presented, which encompass the specific steps of speciation analysis of these toxic compounds.     

Development of the DET technique for high-resolution determination of soluble reactive phosphate profiles in sediment pore waters

The DET (diffusive equilibrium in thin films) technique is developed to measure soluble reactive phosphate (SRP) profiles in sediment pore waters at a millimetre resolution. The analytical procedure includes equilibration of the gels in sediments, section of the gels after retrieval from the sediments, back elution of phosphorus in the gels, and analysis of SRP in the eluents. Recovery of phosphorus is improved from back elution with 0.25?M nitric acid relative to deionised water. SRP concentrations in pore waters of different sediments measured by DET probes agree well with those directly measured by the colorimetric method. Pore water profiles obtained simultaneously using gel probes and other techniques (including Rhizon and dialysis peeper) also show comparability at similar resolutions. The DET probes were used to investigate pore water SRP profiles in the sediments of two contrasting regions (algal-dominated and macrophyte-dominated) in Lake Taihu. An increasingly upward movement of SRP was observed in subsurface pore waters of the algal-dominated region coupled with an increase in water temperature from March to May. Peak-shape distribution of SRP and horizontal heterogeneity was observed in pore waters of the macrophyte-dominated region, which is most likely caused by the activity of submerged macrophyte roots.