Changes of deformational and reservoir properties of arenaceous-argillaceous rocks due to operation of underground gas storage facilities

This paper discusses issues of the decline of the reservoir properties of arenaceous-argillaceous rocks as a result of declining porosity due to long-term operation of underground gas storage facilities. An analysis of the many-year operation of storage facilities, as well as calculation, has revealed that the active capacity of a storage reservoir gradually decreases under certain conditions of underground storage operations. We performed a series of experiments with model specimens in order to support the hypothesis of decreasing reservoir (capacity-filtration) properties because of changes in the value and structure of the pore space. These experiments showed that the cyclic loading and unloading of arenaceous-silty rocks during long-term operation of underground gas storage facilities can significantly decrease the reservoir parameters of reservoirs created within worked out gas-and-gas condensate fields. Laboratory studies of model specimens corresponding to feldspar sandstone in their composition, porosity, and strength proved that porosity considerably decreases in such reservoirs at actually existing values of formation pressure. Tests of sand performed under conditions close to those existing during the development of hydrocarbon fields also showed that their permeability gradually decreases in the process of cyclic changes of effective pressure.     

Ultrahigh pressure macro diamonds from Copeton (New South Wales, Australia), based on Raman spectroscopy of inclusions

Mining of Cenozoic alluvial deposits at Copeton and Bingara (Eastern Australia) has produced two million macrodiamonds (0.25 ct median size). Raman spectroscopy is used to identify included minerals within uncut Copeton diamonds, with sealed chamber remnant pressures of 31.7 to 35.6 kbar for coesite, 13.6 and 22.7 kbar for clinopyroxene, and 7.6 kbar for grossular garnet. Assuming elastic behaviour, these values generate inclusion entrapment PT loci which intersect, restricting diamond formation conditions: from 250 °C, 43 kbar to 800 °C, 52 kbar. Larger than error (± 100 °C and ± 4 kbar), this range shows a systematic variation in inclusion composition with diamond zoning and N properties. Published research shows 1) Copeton and Bingara diamonds are unique, and 2) modern alluvium in the Bingara district carries mantle-formed garnet, captured by post-tectonic alkali basalt from an extensive diamondiferous ultrahigh pressure (UHP) terrane that stalled at depth because it is dominated by mafic eclogite. The combined Raman and geological results indicate two sets of subduction UHP diamond formation conditions/protolith are required, firstly cooler oceanic slab and secondly including higher temperature continental crust. The Copeton and Bingara stones are UHP macrodiamonds, and Carboniferous ⁴⁰Ar/³⁹Ar age dates on clinopyroxene inclusions should be interpreted as ages of crystallisation, representing the termination of subduction. The characteristic features of ruptured inclusions and etched percussion marks on Copeton and Bingara diamond indicate volcanic delivery to the earth's surface. Alluvial deposits elsewhere in Eastern Australia may carry similar diamond along with diamond of different origin.     

Temporal characteristics of aerosol physical properties at Visakhapatnam on the east coast of India during ICARB — Signatures of transport onto Bay of Bengal

Realizing the importance of aerosol physical properties at the adjoining continental and coastal locations in the airmass pathways onto the oceanic region, extensive measurements of aerosol physical properties were made at Visakhapatnam (17.7°N, 83.3°E), an eastern coastal location in peninsular India during the ICARB period. The temporal variations of aerosol optical depth, near surface aerosol mass size distributions and BC mass concentrations show significantly higher aerosol optical depth and near surface mass concentrations during the first and last weeks of April 2007. The mean BC mass fraction in the fine mode aerosol was around 11%. The aerosol back scatter profiles derived from Micro Pulse Lidar indicate a clear airmass subsidence on the days with higher aerosol optical depths and near surface mass fraction. A comparison of the temporal variation of the aerosol properties at Visakhapatnam with the MODIS derived aerosol optical depth along the cruise locations indicates a resemblance in the temporal variation suggesting that the aerosol transport from the eastern coastal regions of peninsular India could significantly affect the aerosol optical properties at the near coastal oceanic regions and that the affect significantly reduced at the farther regions.     

Observations of unusual whistlers during daytime at Jammu

In this paper, we report observations of unusual whistlers recorded at Jammu (geomag. lat. = 22°26′N; L = 1.17), India on March 8, 1999 during the daytime. They are interpreted as one-hop ducted whistlers having propagated along higher L-values in closely spaced narrow ducts from the opposite hemispheres. After leakage from the duct, the waves might have propagated in the earth-ionosphere waveguide towards the equator in surface mode. Tentative explanation of the dynamic spectra of these events is briefly presented.     

内蒙古敖包吐萤石矿床的Sr、Nd、Pb同位素地球化学特征

敖包吐萤石矿床是内蒙古北部苏莫查干地区单一萤石矿集区中的一个代表性矿床,产于早二叠世大石寨组火山-沉积岩与早白垩世敖包吐花岗岩的接触带上。文章通过分析该矿床岩、矿石的微量元素和稀土元素,揭示出萤石的成矿作用可分为2个阶段,即交代作用和充填作用。交代作用过程中大石寨组的结晶灰岩可能为萤石的形成提供了部分Ca来源,萤石矿石的稀土元素配分模式与海水基本类似,具有Ce负异常;成矿作用后期主要表现为充填作用,形成颗粒粗大的萤石,表现为重稀土元素富集的特征,并随着萤石的沉淀析出,稀土元素总量逐渐下降,反映出成矿流体经历了较长期的演化过程。各地层单元、花岗岩体和萤石矿石的Sr、Nd、Pb同位素研究表明,萤石的放射性同位素组成具有壳、幔源混合的特点,成矿物质来源具有多源性。早白垩世敖包吐花岗岩可能是萤石中F的主要来源,而大石寨组的结晶灰岩则可能提供了Ca。另外,Pb、Nd同位素的极大不均一性,有可能是成矿流体在运移过程中对艾力格庙群放射性组分的选择性吸收的结果。萤石成矿作用与钾玄岩的时空关系暗示了萤石的成矿过程可能是中国东部岩石圈减薄和下地壳的置换地质事件的结果。在构造转型的过程中,燕山中期富碱的酸性花岗岩浆的活动分异出富含F的成矿流体,与幔源流体混合,沿区域重新活化的深大断裂和大石寨组的层间破碎带上升,交代其间的灰岩透镜体,从而形成敖包吐中型萤石矿床。     

Asymmetrically zoned reaction rims: assessment of grain boundary diffusivities and growth rates related to natural diffusion-controlled mineral reactions

This study explores garnet coronas around hedenbergite, which were formed by the reaction plagioclase + hedenbergite→garnet + quartz, to derive information about diffusion paths that allowed for material redistribution during reaction progress. Whereas quartz forms disconnected single grains along the garnet/hedenbergite boundaries, garnet forms ～20‐μm‐wide continuous polycrystalline rims along former plagioclase/hedenbergite phase boundaries. Individual garnet crystals are separated by low‐angle grain boundaries, which commonly form a direct link between the reaction interfaces of the plagioclase|garnet|hedenbergite succession. Compositional variations in garnet involve: (i) an overall asymmetric compositional zoning in Ca, Fe²⁺, Fe³⁺ and Al across the garnet layer; and (ii) micron‐scale compositional variations in the near‐grain boundary regions and along plagioclase/garnet phase boundaries. These compositional variations formed during garnet rim growth. Thereby, transfer of the chemical components occurred by a combination of fast‐path diffusion along grain boundaries within the garnet rim, slow diffusion through the interior of the garnet grains, and by fast diffusion along the garnet/plagioclase and the garnet/hedenbergite phase boundaries. Numerical simulation indicates that diffusion of Ca, Al and Fe²⁺ occurred about three to four, four and six to seven orders of magnitude faster along the grain boundaries than through the interior of the garnet grains. Fast‐path diffusion along grain boundaries contributed substantially to the bulk material transfer across the growing garnet rim. Despite the contribution of fast‐path diffusion, bulk diffusion through the garnet rim was too slow to allow for chemical equilibration of the phases involved in garnet rim formation even on a micrometre scale. Based on published garnet volume diffusion data the growth interval of a 20‐μm‐wide garnet rim is estimated at ～10³–10⁴ years at the inferred reaction conditions of 760 ± 50 °C at 7.6 kbar. Using the same parameterization of the growth law, 100‐μm‐ and 1‐mm‐thick garnet rims would grow within 10⁵–10⁶ and 10⁶–10⁷ years respectively.     

Basement–cover relationships of the Kalak Nappe Complex, Arctic Norwegian Caledonides and constraints on Neoproterozoic terrane assembly in the North Atlantic region

The Kalak Nappe Complex (KNC) has been regarded as Baltica passive margin metasediments telescoped eastwards onto the Baltic (Fennoscandian) Shield during the Caledonian Orogeny. Recent studies have questioned this interpretation, instead pointing to a Neoproterozoic exotic origin. In an effort to resolve this controversy we present a Sm–Nd and U–Th–Pb study of gnessic units, traditionally considered as the depositional basement, along with cover rock sediments and intrusives. Late Palaeoproterozoic gneisses now beneath the KNC were deposited after 1948 ± 33 Ma, before intrusion of the Tjukkfjellet Granite at 1796 ± 3 Ma, and were affected by later melting events at 1765 ± 9 and 1727 ± 9 Ma. These gneisses are interpreted as part of the Baltic Shield and underlie the KNC across a tectonic contact. An unconformity between psammites of the KNC and other paragneisses previously considered as its Precambrian basement is reinterpreted as a modified sedimentary contact between Neoproterozoic metasediments. These metasediments have statistically very similar detrital zircon populations with grains as young as 1034 ± 22, 1025 ± 32 and 1014 ± 14 Ma. The results indicate that the KNC sediments were deposited during the Neoproterozoic in basins along the Laurentian margin of eastern Rodinia and were not connected to Baltica via a depositional basement. Dating of the 851 ± 5 Ma Eidvågvatnet and 853 ± 4 Ma Nordneset granites shows that intrusive material associated with the Porsanger Orogeny (c. 850 Ma) affected a considerable region of the upper KNC terrane. Later Neoproterozoic events at 711 ± 6, 687 ± 12 and 617 ± 6 Ma are also recognised the latest of which may be an expression of rifting. Since early Neoproterozoic magmatism (c. 840–690 Ma) is unknown in Baltica, these results support an exotic origin for the KNC terranes.     

Paleomagnetism and Detrital Zircon Geochronology of the Upper Vindhyan Sequence, Son Valley and Rajasthan, India: A ca. 1000 Ma Closure age for the Purana Basins?

The utility of paleomagnetic data gleaned from the Bhander and Rewa Groups of the “Purana-aged” Vindhyanchal Basin has been hampered by the poor age control associated with these units. Ages assigned to the Upper Vindhyan sequence range from Cambrian to the Mesoproterozoic and are derived from a variety of sources, including ⁸⁷Sr/⁸⁶Sr and δ ¹³C correlations with the global curves and Ediacara-like fossil finds in the Lakheri–Bhander limestone. New analyses of the available paleomagnetic data collected from this study and previous work on the 1073 Ma Majhgawan kimberlite, as well as detrital zircon geochronology of the Upper Bhander sandstone and sandstones from the Marwar SuperGroup suggest that the Upper Vindhyan sequence may be up to 500 Ma older than is commonly thought. Paleomagnetic analysis generated from the Bhander and Rewa Groups yields a paleomagnetic pole at 44°N, 214.0°E (A95 = 4.3°). This paleomagnetic pole closely resembles the VGP from the well-dated Majhgawan intrusion (36.8°N, 212.5°E, α₉₅ = 15.3°).Detrital zircon analysis of the Upper Bhander sandstone identifies a youngest age population at 1020 Ma. A comparison between the previously correlated Upper Bhander sandstone and the Marwar sandstone detrital suites shows virtually no similarities in the youngest detrital suite sampled. The main 840–920 Ma peak is absent in the Upper Bhander. This supports our assertion that the Upper Bhander is older than the 750–771 Ma Malani sequence, and is likely close to the age of the 1073 Ma Majhgawan kimberlite on the basis of the paleomagnetic similarities. By setting the age of the Upper Vindhyan at 1000–1070 Ma, several intriguing possibilities arise. The Bhander–Rewa paleomagnetic pole allows for a reconstruction of India at 1000–1070 Ma that overlaps with the 1073 ± 13.7 Majhgawan kimberlite VGP. Comparisons between the composite Upper Vindhyan pole (43.9°N, 210.2°E, α₉₅ = 12.2°) and the Australian 1071 ± 8 Ma Bangamall Basin sills and the 1070 Ma Alcurra dykes suggest that Australia and India were not adjacent at this time period.     

The role of heterogeneous strain in the development and preservation of a polymetamorphic record in high-P granulites, western Canadian Shield

Mafic rocks in the Chipman domain of the Athabasca granulite terrane, western Canadian Shield, provide the first well‐documented record of two distinct high‐P granulite facies events in the same domain in this region. Textural relations and the results of petrological modelling (NCFMASHT system) of mafic granulites are interpreted in terms of a three‐stage tectonometamorphic history. Stage 1 involved development of the assemblage Grt + Cpx + Qtz ± Pl (M₁) from a primary Opx‐bearing igneous precursor at conditions of 1.3 GPa, 850–900 °C. Field and microstructural observations suggest that M₁ developed synchronously with an early S₁ gneissic fabric. Stage 2 is characterized by heterogeneous deformation (D₂) and synkinematic partial retrogression of the peak assemblage to an amphibole‐bearing assemblage (M₂). Stage 3 involved a third phase of deformation and a return to granulite facies conditions marked by the prograde breakdown of amphibole (Amph₂) to produce matrix garnet (Grt_3a) and the coronitic assemblage Cpx_3b + Opx_3b + Ilm_3b + Pl_3b (M_3b) at 1.0 GPa, 800–900 °C. M₁ and M_3b are correlated with 2.55 and 1.9 Ga metamorphic generations of zircon, respectively, which were dated in a separate study. Heterogeneous strain played a crucial role in both the development and preservation of these rare examples of multiple granulite facies events within single samples. Without this fortuitous set of circumstances, the apparent reaction history could have incorrectly led to an interpretation involving a single‐cycle high‐grade event. The detailed P–T–t–D history constructed for these rocks provides the best evidence to date that much of the east Lake Athabasca region experienced long‐term lower crustal residence from 2.55 to 1.9 Ga, and thus the region represents a rare window into the reactivation and ultimate stabilization processes of cratonic lithosphere.     

The effect of extracellular polymers (EPS) on the proton adsorption characteristics of the thermophile Bacillus licheniformis S-86

This study investigated proton adsorption to an extracellular polymeric substance (EPS) producing bacterial strain, Bacillus licheniformis S-86, in order to characterise and quantify the contribution made by EPS to cell surface reactivity. Potentiometric titrations were conducted using both untreated cells and cells from which the EPS layer had been extracted. Surface-complexation modelling indicated the presence of four different functional groups in both untreated and EPS-free cells. These sites are assigned to phosphodiester, (pK_a 3.3–3.4), carboxylic (pK_a 5.3–5.4), phosphoryl/ (pK_a 7.4–7.5) and hydroxyl/amine (pK_a 9.9–10.1) type groups. The pK_a values for the four groups were very similar for untreated and EPS-free cells, indicating no qualitative difference in composition, but site concentrations in the untreated cells were statistically found to be significantly higher than those in the EPS-free cells for the pK_a 3.3–3.4 and pK_a 9.9–10.1 sites. Infrared analysis provided supporting evidence that site 2 is carboxylic in nature but did not reveal any difference in IR absorption between the native and EPS-free cells. Dissolved organic carbon (DOC) analysis conducted during this study indicated that DOC release by cells is significant, and that the EPS layer is the major contributor.