A critical evaluation of using bulk sediment instead of fine fraction in environmental marine studies, investigated on example of Rijeka harbor, Croatia

This work tested the preferential use of fine (<63 μm) or bulk sediment (<2 mm) in environmental research of marine sediments in the Eastern Adriatic. Fine fraction sediment containing silt and clay (<63 μm), predominating in the studied area, was examined to evaluate past and present anthropogenic inputs and to test our hypothesis that investigation of bulk sediment should be preferred. Following aqua regia digestion, chemical analyses of 58 elements were performed by ICP/OES, ICP-MS and cold vapor AAS, and statistical analysis was performed. The concentrations of the majority of the analyzed elements increased with age of the sediment, except for Ag and Sn, which had higher concentrations in recent sediments. The previous main sources of metal contamination in Rijeka harbor were now abandoned municipal-sewage outflow and oil refinery, and continuing harbor activities and antifouling paint use. All activities except of antifouling paint use have been decreasing significantly. Anomalies of selected elements were determined by the box-plot method. More anomalies were found in the bulk sediment than in the fine fraction. Results of Q-modality clustering and factor analysis in the fine fraction almost correlate with that applied on bulk sediments. Thus, it can be said that the differences between the element distribution in the bulk and fine fraction are not statistically significant. Our conclusion is that analysis of bulk marine sediment gives a better insight into the state of pollution and supports previous recommendations to use bulk sediment as a chosen media for environmental studies.     

The geochemistry of mafic metavolcanics: implications for the origin of the Devonian massive sulfide deposits at Zlaté Hory,Czechoslovakia

Mafic metavolcanic rocks in the area of the Zlaté Hory massive sulfide deposits are interpreted as convergent plate-margin basalts and basaltic andesites metamorphosed to the greenschist facies. According to the major- and trace-element compositions the metabasites exhibit island-arc tholeiitic to low-K, calc-alkaline composition.Approximately 50% of samples of maifc metavolcanics studied have a salient negative anomaly of Ce in chondrite-normalized REE patterns. The Ce-depleted greenschists are thought to represent hydrothermally altered equivalents of metabasites of island-arc tholeiitic composition. The alteration was accompanied by the sulfide mineralization. That is indicated by enrichment in Ba and S together with correlation of the Ce/Ce* values and CO₂ abundances in the Ce-depleted rocks. The Ce anomaly may be caused by alteraton of ore-forming, seawaterderived solutions. The occurrence of Ce-depleted greenschists supports the hypothesis of the volcanogenic origin of the ore deposits in the Zlaté Hory area.     

High-pressure phase behavior of MnTiO<Subscript>3</Subscript>: decomposition of perovskite into MnO and MnTi<Subscript>2</Subscript>O<Subscript>5</Subscript>

The phase relations and compression behavior of MnTiO₃ perovskite were examined using a laser-heated diamond-anvil cell, X-ray diffraction, and analytical transmission electron microscopy. The results show that MnTiO₃ perovskite becomes unstable and decomposes into MnO and orthorhombic MnTi₂O₅ phases at above 38 GPa and high temperature. This is the first example of ABO₃ perovskite decomposing into AO + AB₂O₅ phases at high pressure. The compression behavior of volume, axes, and the tilting angle of TiO₆ octahedron of MnTiO₃ perovskite are consistent with those of other A²⁺B⁴⁺O₃ perovskites, although no such decomposition was observed in other perovskites. FeTiO₃ is also known to decompose into two phases, instead of transforming into the CaIrO₃-type post-perovskite phase and we argue that one of the reasons for the peculiar behavior of titanate is the weak covalency of the Ti–O chemical bonds.     

Role of Crystal Interlocking on the Strength of Brittle Rocks

Results of an experimental programme on heterogeneous rock-like specimens of dental plaster confirm the pronounced role of tensile microcracks on brittle failure. Microbuckling of very small rock-columns formed amid closely located tensile cracks was observed as the key incident connecting stable phenomenon of tensile cracking to unstable phenomenon of shearing and subsequent macroscopic failure. Using the classical beam and buckling theories and considering geometry of the problem a new failure criterion is proposed. As a novel attempt, this new failure criterion relates the compressive strength of rock to three basic microstructural properties, i.e. degree of crystal interlocking, average Young modulus and average tensile strength of rock forming minerals.     

Hydraulic Conductivity Tests for Evaluating Compatibility of Lateritic Soil—Fly Ash Mixtures with Municipal Waste Leachate

Long term competent performance of liner systems is a critical issue in the design and construction of waste repositories due to adverse interactions associated with leachate generated by wastes. This study was conducted to verify the efficacy of fly ash stabilization in enhancing compatibility between lateritic soil and municipal waste leachate. Applications investigated include soil mixtures containing 0, 5, 10, 15, and 20% fly ash compacted at approximately 2% wet of optimum moisture content with modified proctor energy. Baseline hydraulic conductivity was first established at every level of fly ash content by permeating soil mixtures with tap water before permeation with leachate in a compaction mould permeameter using the falling head test method. Results show that the trend in hydraulic conductivity of specimen containing 0% fly ash was characterized by a gradual but erratic decrease which may suggests partial entry of the leachate cations into the double layer. Conversely, specimens containing fly ash showed a general trend consisting of an initial drop in k (up to an order of magnitude) that was followed by slight decrease sustained until k stabilized and later terminated. Above 10% fly ash content, the relatively high values of k observed was not connected with the reactivity of the soil mixtures with leachate, rather it may be attributed to excessive fly ash content that altered their textural and hydraulic properties. The result of this study is potentially significant in the assessment of fly ash as a compatibility enhancing agent which can be admixed in barrier materials that are susceptible to adverse reactions with the liquid to be contained.     

Helium and argon isotope geochemistry of natural gases in China’s petroliferous basins

The age-accumulation effect of 40Ar in hydrocarbon source rocks was discussed in accordance with the decay law of radioactive elements. In terms of the mean values of 40Ar/36Ar, the old Sinian gas reservoirs (mean values of 40Ar/36Ar: 7009) were definitely distinguished from the Permian gas reservoirs (mean values of 40Ar/36Ar: 1017) in Weiyuan, Sichuan Province, and the gas source of the Permian gas reservoir (mean values of 40Ar/36Ar: 5222) in well Wei-7 with the Weiyuan structure is defined as the Sinian system. Based on the values of 40Ar/36Ar, the coal-type gases (The source rocks are of the C-P system; mean values of 40Ar/36Ar: 1125) are definitely distinguished from the oil-type gases (The source rocks are of the Tertiary system; mean values of 40Ar/36Ar: 590) in the Tertiary reservoirs of the Zhongyuan Oilfield. Besides, 40Ar/36Ar values also have a positive effect on the oil-source correlation of oil reservoirs in ancient hidden mountains. According to the crust-mantle interchange information reflected by 3He/4He values, petroliferous provinces in China can be divided into three major tectonic regions. (1) The eastern active region: The crust-mantle volatile matter exchanges actively, and the 3He/4He values are mainly around 10-6, partly around 10-7. (2) The central stable region: The 3He/4He values are all around 10-8. (3) The western sub-stable region: The 3He/4He values are mainly around 10-8, and around 10-7 on the edges of the basins. Helium contents of some gas wells in China’s eastern petroliferous region reach the industrial abundance (He≈0.05%–0.1%), the 3He/4He values reach 10-6, and the equivalent values for the mantle-source components in helium gas can reach 30%–50%. As viewed from this, a new type of crust-mantle composite helium resources has been proposed. Geneses of some CO2 gas reservoirs in the east of China and some issues concerning mantle-source methane were discussed in the light of the helium and carbon isotopes of CO2 and CH4 in natural gases. In the discussion on helium isotopic characteristics of inclusions in the reservoirs, it was discovered that the 3He/4He values are close to those in natural gases. That is to say, this phenomenon is related to regional tectonism. The 3He/4He, CO2/3He and CH4/3He data were used to discuss the tectonic activities of fault zones in a certain number of regions in China.     

Zircon U-Pb ages and Hf isotopic characteristics of the Dehe biotite monzonitic gneiss pluton in the North Qinling orogen and their geological significance

The Dehe granitic pluton intruded the Xiahe Group which is in the core complex of the North Qinling Orogenic Belt(NQOB).It shows gneissic bedding and possesses typical S-type granite minerals such as muscovite and garnet.LA-ICP-MS U-Pb isotopic dating of the Dehe granite yielded a weighted average age of 925±23 Ma which represents the emplacement age of the pluton.Most of the εHf(t) values are negative,and the two-stage model ages are consistent with the age of the Qinling Group.The isotope data show that the Dehe granite was formed in the following geological setting:in the syn-collision setting of the NQOB in the Neoproterozoic,crustal thickening induced partial melting of materials derived from the Qinling complex,and then the maga upwelled and intruded into the Xiahe Group.The formation of the Dehe S-type granite implied the occurrence of a convergent event in the QOB during the Neoproterozoic.     

Die Kristallstruktur des Minerals Eclarit, (Cu,Fe) Pb9Bi12S28

Zusammenfassung Die Kristallstruktur des zuerst vonPaar, Chen undMeixner beschriebenen neuen Minerals wurde an der Originalprobe bestimmt. Für die prinzipielle Lösung der Struktur war eine Kombination von direkten und Pattersonmethoden erforderlich. Anhand von 2774 kristallographisch unabhängigen Röntgenreflexen (davon 1828 beobachtet) wurde die Struktur bis zu einem gewichtetenR-Wert von 10.7% isotrop verfeinert. Das Mineral ist orthorhombisch, RaumgruppePnma mit den Gitterkonstantena ₀=54.76Å,b ₀=4.030 Å,c ₀=22.74 Å undZ=4. Die Kristallstruktur ist durch galenitähnliche Bereiche, deren [110] Richtung parallel zurb ₀-Achse verläuft, gekennzeichnet. Die gegenseitige Anordnung dieser Bereiche ist teils kobellit-, teils cosalitähnlich. Die galenitähnlichen Bereiche sind vorwiegend wismuthhaltig (Koordination 3+2+1), während die Ph-Atome in einer trigonal-prismatischen Koordination mit 2 zusätzlichen Schwefelatomen vorwiegend als Bindeglieder dazwischen liegen.

---

The crystal structure of eclarite, (Cu,Fe)Pb₉Bi₁₂S₂₈

Summary The crystal structure of the new mineral eclarite, first described byPaar, Chen andMeixner was determined using the original material. It was necessary to apply a combination of direct and Patterson methods. The structure was refined for 2774 independent reflections (1828 observed) with isotropic temperature factors to a weightedR-value of 10.7%. Eclarite crystallizes in the orthorhombic space groupPnma with lattice parametersa ₀=54.76 Å,b ₀=4.030 Å,c ₀=22.75 Å,Z=4. The structure is characterized by galena-like building units with [110] (galena) parallel to theb-axis. These units are linked to each other partly as in kobellite, partly as in cosalite structures. Bi prefers to occupy the metal positions in the galena-like units, coordinated by 3+2+1S, whereas Pb occupies preferably the positions coordinated trigonal prismatic with two additional S. The latter groups serve to connect the galena-like units.

---

---

Mit 3 Abbildungen

---

Herrn Professor Dr.Josef Zemann zum 60. Geburtstag gewidmet.     

Beyond dual-porosity modeling for the simulation of complex flow mechanisms in shale reservoirs

The state of the art of modeling fluid flow in shale reservoirs is dominated by dual-porosity models which divide the reservoirs into matrix blocks that significantly contribute to fluid storage and fracture networks which principally control flow capacity. However, recent extensive microscopic studies reveal that there exist massive micro- and nano-pore systems in shale matrices. Because of this, the actual flow mechanisms in shale reservoirs are considerably more complex than can be simulated by the conventional dual-porosity models and Darcy’s law. Therefore, a model capturing multiple pore scales and flow can provide a better understanding of the complex flow mechanisms occurring in these reservoirs. This paper presents a micro-scale multiple-porosity model for fluid flow in shale reservoirs by capturing the dynamics occurring in three porosity systems: inorganic matter, organic matter (mainly kerogen), and natural fractures. Inorganic and organic portions of shale matrix are treated as sub-blocks with different attributes, such as wettability and pore structures. In kerogen, gas desorption and diffusion are the dominant physics. Since the flow regimes are sensitive to pore size, the effects of nano-pores and micro-pores in kerogen are incorporated into the simulator. The multiple-porosity model is built upon a unique tool for simulating general multiple-porosity systems in which several porosity systems may be tied to each other through arbitrary connectivities. This new model allows us to better understand complex flow mechanisms and eventually is extended into the reservoir scale through upscaling techniques. Sensitivity studies on the contributions of the different flow mechanisms and kerogen properties give some insight as to their importance. Results also include a comparison of the conventional dual-porosity treatment and show that significant differences in fluid distributions and dynamics are obtained with the improved multiple-porosity simulation.