Geochemical, zircon U�CPb dating and Sr�CNd�CHf isotopic constraints on the age and petrogenesis of an Early Cretaceous volcanic-intrusive complex at Xiangshan, Southeast China

The Late Mesozoic geology of Southeast China is characterized by extensive Jurassic to Cretaceous magmatism consisting predominantly of granites and rhyolites and subordinate mafic rocks, forming a belt of volcanic-intrusive complexes. The Xiangshan volcanic-intrusive complex is located in the NW region of the belt and mainly contains the following lithologies: rhyodacite and rhyodacitic porphyry, porphyritic lava, granite porphyry with mafic microgranular enclaves, quartz monzonitic porphyry, and lamprophyre dyke. Major and trace-element compositions, zircon U?CPb dating, and Sr?CNd?CHf isotopic compositions have been investigated for these rocks. The precise SHRIMP and LA?CICP?CMS zircon U?CPb dating shows that the emplacement of various magmatic units at Xiangshan took place within a short time period of less than 2?Myrs. The stratigraphically oldest rhyodacite yielded a zircon U?CPb age of 135?±?1?Ma and the overlying rhyodacitic porphyry has an age of 135?±?1?Ma. Three porphyritic lava samples yielded zircon U?CPb ages of 136?±?1?Ma, 132?±?1?Ma, and 135?±?1?Ma, respectively. Two subvolcanic rocks (granite porphyry) yielded zircon U?CPb ages of 137?±?1?Ma and 137?±?1?Ma. A quartz monzonitic porphyry dyke, which represented the final stage of magmatism at Xiangshan, also yielded a zircon U?CPb age of 136?±?1?Ma. All these newly obtained precise U?CPb ages demonstrate that the entire magmatic activity at Xiangshan was rapid and possibly took place at the peak of extensional tectonics in SE China. The geochemical data indicate that all these samples from the volcanic-intrusive complex have an A-type affinity. Sr?CNd?CHf isotopic data suggest that the Xiangshan volcanic-intrusive complex derived mainly from remelting of Paleo-Mesoproterozoic crust without significant additions of mantle-derived magma. However, the quartz monzonitic porphyry, which has zircon Hf model ages older than the whole-rock Nd model ages, and which has ??_Nd(T) value higher than the other rocks, may indicate involvement of a subordinate younger mantle-derived magma in its origin. Geochemical data indicate that the various rocks show variable REE patterns and negative anomalies of Ba, Nb, Sr, P, Eu and Ti in the trace element spidergrams, suggesting that these rocks may have undergone advanced fractional crystallization with separation of plagioclase, K-feldspar and accessory minerals such as allanite. We suggest that this Cretaceous volcanic-intrusive complex formed in an extensional environment, and the formation of the Xiangshan mafic microgranular enclaves can be explained by the injection of mafic magma from a deeper seated mantle magma chamber into a hypabyssal felsic magma chamber at the crustal emplacement levels.     

Asymptotic Dykstra�CParsons Distribution, Estimates and Confidence Intervals

The sample Dykstra?CParsons (DP) coefficient, the most popular heterogeneity static measure among petroleum engineers, may exhibit significant sampling errors. Moreover, approximations of its probability distributions (uncertainty estimates) are only available for specific families of permeability models (e.g., log-normal). The cited probability distributions allow for the specification of confidence intervals and other inferences for the theoretical DP, which will be useful for reservoir screening purposes, or to establish if a more detailed study is justified. This paper presents the development of an asymptotic approximation of the distribution of the sample Dykstra?CParsons coefficient, which is independent of the permeability probability distribution. The effectiveness (bias and confidence intervals) of the proposed approach is demonstrated using analytical and field case studies and by comparing the results gleaned with those obtained using a well-known parametric approximation, under different scenarios of reservoir maturity levels (i.e., number of wells) and different degrees of deviation from the log-normal probability density function assumption. The results show that, in the vast majority of the case studies, the proposed approach outperformed the parametric approximation; in particular, our approach resulted in a significant reduction of the bias and the confidence intervals always including the theoretical DP coefficient. In addition, an excellent agreement was observed between the asymptotic cumulative distribution of the DP coefficient and the corresponding empirical distribution for sample sizes as small as one hundred, which suggests that high success rates can be obtained when reservoirs are classified according to the asymptotic DP coefficient.     

Equivalent granular state parameter and undrained behaviour of sand�Cfines mixtures

State parameter defined using void ratio, e, and the steady-state line has been shown to be effective in predicting the undrained behaviour of sand. However, steady-state line for sand with fines is dependent on fines content. To overcome this problem, the concept of equivalent granular void ratio, e*, has been well investigated. However, the conversion from e to e* has been essentially a back-analysis process. A methodology for converting e to e* without the need of a back-analysis process was first presented. The concept of equivalent granular state parameter, ψ*, defined in terms of e*, and equivalent granular steady-state line was then developed. An extensive experimental study was conducted to investigate whether ψ* can capture the effects of fines content, and thus can be used to correlate undrained behaviour of sand–fines mixtures without the need of separately considering the effects of fines content. This study suggested that the effective stress path and deviatoric stress–strain responses in undrained shearing can be correlated with the ψ* value at the start of undrained shearing irrespective of fines content.     

EPR investigation of NO2 and CO2 − and other radicals in beryl

A number of different impurities are located in the open channels of natural beryl crystals. The rare Maxixe beryl contains an unusual amount of NO₂. The isoelectronic CO₂ ⁻ radical is found in the irradiated Maxixe-type beryl. The NO₂ radicals are distributed in the Be–Al plane of the crystal, with the nitrogen atom close to the oxygens of the beryl cavity wall. These oxygens repel the negative CO₂ ⁻ radical, which is located at the center of the beryl cavity and rotates around its O–O axis, which is parallel to the crystal c-axis. When there is a nearby alkali ion at the center of the beryl channel, it reorients the CO₂ ⁻ radical so that its bisector is parallel to the c-axis and points toward the positive ion. Different signals are analyzed for Li⁺, Na⁺, and another counter-ion, which probably is Cs⁺. The related NO₃ and CO₃ ⁻ radicals are the color centers in the investigated deep blue beryls. The slow decay of the color, which makes these beryls useless as gem stones, is related to the decay of the hydrogen atoms which are present in these crystals. Evidence is given that NO₃ is created in Maxixe beryl by a natural process, while CO₃ ⁻ in Maxixe-type beryl has been created by irradiation. The temperature dependence of the EPR signals of these two radicals was investigated, but a definitive proof that they rotate at the center of the beryl cavity could not be given. EPR signals from some other radicals in beryl have been observed and described.     

Land–sea carbon and nutrient fluxes and coastal ocean CO2 exchange and acidification: Past,present, and future

Epochs of changing atmospheric CO₂ and seawater CO₂–carbonic acid system chemistry and acidification have occurred during the Phanerozoic at various time scales. On the longer geologic time scale, as sea level rose and fell and continental free board decreased and increased, respectively, the riverine fluxes of Ca, Mg, DIC, and total alkalinity to the coastal ocean varied and helped regulate the C chemistry of seawater, but nevertheless there were major epochs of ocean acidification (OA). On the shorter glacial–interglacial time scale from the Last Glacial Maximum (LGM) to late preindustrial time, riverine fluxes of DIC, total alkalinity, and N and P nutrients increased and along with rising sea level, atmospheric PCO₂ and temperature led, among other changes, to a slightly deceasing pH of coastal and open ocean waters, and to increasing net ecosystem calcification and decreasing net heterotrophy in coastal ocean waters. From late preindustrial time to the present and projected into the 21st century, human activities, such as fossil fuel and land-use emissions of CO₂ to the atmosphere, increasing application of N and P nutrient subsidies and combustion N to the landscape, and sewage discharges of C, N, P have led, and will continue to lead, to significant modifications of coastal ocean waters. The changes include a rapid decline in pH and carbonate saturation state (modern problem of ocean acidification), a shift toward dissolution of carbonate substrates exceeding production, potentially leading to the “demise” of the coral reefs, reversal of the direction of the sea-to-air flux of CO₂ and enhanced biological production and burial of organic C, a small sink of anthropogenic CO₂, accompanied by a continuous trend toward increasing autotrophy in coastal waters.     

Reactions between olivine and CO2-rich seawater at 300 °C: Implications for H2 generation and CO2 sequestration on the early Earth

To understand the influence of fluid CO₂ on ultramafic rock-hosted seafloor hydrothermal systems on the early Earth, we monitored the reaction between San Carlos olivine and a CO₂-rich NaCl fluid at 300 °C and 500 bars. During the experiments, the total carbonic acid concentration (ΣCO₂) in the fluid decreased from approximately 65 to 9 mmol/kg. Carbonate minerals, magnesite, and subordinate amount of dolomite were formed via the water-rock interaction. The H₂ concentration in the fluid reached approximately 39 mmol/kg within 2736 h, which is relatively lower than the concentration generated by the reaction between olivine and a CO₂-free NaCl solution at the same temperature. As seen in previous hydrothermal experiments using komatiite, ferrous iron incorporation into Mg-bearing carbonate minerals likely limited iron oxidation in the fluids and the resulting H₂ generation during the olivine alteration. Considering carbonate mineralogy over the temperature range of natural hydrothermal fields, H₂ generation is likely suppressed at temperatures below approximately 300 °C due to the formation of the Mg-bearing carbonates. Nevertheless, H₂ concentration in fluid at 300 °C could be still high due to the temperature dependency of magnetite stability in ultramafic systems. Moreover, the Mg-bearing carbonates may play a key role in the ocean-atmosphere system on the early Earth. Recent studies suggest that the subduction of carbonated ultramafic rocks may transport surface CO₂ species into the deep mantle. This process may have reduced the huge initial amount of CO₂ on the surface of the early Earth. Our approximate calculations demonstrate that the subduction of the Mg-bearing carbonates formed in komatiite likely played a crucial role as one of the CO₂ carriers from the surface to the deep mantle, even in hot subduction zones.     

A multi-methodological approach to determine CO2 and CH4 fluxes and concentrations in solid waste disposal

The municipal solid waste （MSW） landfills are the significant sources of atmospheric contamination, due to biogas production by anaerobic decomposition of organic matter via bacterial activity. Biogas released from landfills is commonly composed of a mixture of methane （55%-60%） and carbon dioxide （40%-45%）, with minor contents of N2, H2, CO and traces of toxic and bad smelling inorganic and organic compounds. Particular attention has to be paid to CH4 and CO2 because of their liability for the greenhouse effect. Presently, the U.S. methane emission from landfills is considered to be about 25% of the total methane released to the atmosphere. Accordingly, field measurements should be planned in order to verify and, eventually, optimize the amount of gases released from waste disposals to the atmosphere. Simultaneous measurements of methane and carbon dioxide fluxes are an effective tool to better evaluate： （1） the amount of biogas released, （2） the real efficiency of the impervious cover, and （3） the presence of anomalous degassing zones or of newly formed fractures. Static closed-chamber methods for CH4 and CO2 flux measurements have been developed and used in both natural and artificial systems. Furthermore, portable gas-chromatographers equipped with flame ionization detector （FID） and accumulation chamber connected to infrared detectors （IR） .have been utilized for measuring CH4 and CO2 fluxes, respectively. This paper deals with a detailed investigation that combines （1） CH4 and CO2 flux measurements from solid waste disposal and surrounding areas （determined by an accumulation chamber equipped with two IR detectors, respectively）, （2） chemical composition of soil and piezometer gases （collected in pre-evacuated glass tubes and analyzed by gas-chromatography）, and （3） CO2 linear concentration measurements on optical air paths with IR laser devices. This multi-methodological approach was successfully applied to an active MSW in Tuscany （Central Italy）. The analytical results have shown that the CO2/CH4 ratios of the piezometer gases have large variations, likely related to the different stage of decomposition processes affecting the heterogeneous solid material of the waste landfill. Significant contents of light hydrocarbons and BTX were also detected.     

Chemical and physical studies of type 3 chondrites—VIII: Thermoluminescence and metamorphism in the CO chondrites

The thermoluminescence properties of nine CO chondrites have been measured. With the exception of Colony and Allan Hills A77307 (ALHA 77307), whose maximum induced TL emission is at approximately 350°C, CO chondrites exhibit two TL peaks, one at 124 ± 7°C (130°C peak) and one at 252 ± 7°C (250°C peak). The 130°C peak shows a 100-fold range in TL sensitivity (0.99 ± 0.21 for Isna to 0.010 ± 0.004 for Colony), and correlates with various metamorphism-related phenomena, such as silicate heterogeneity, metal composition and McSween's metamorphic subtypes. The peak at 250°C does not show these correlations and, Colony excepted, varies little throughout the class (0.3 to 0.07, Colony 0.018 ± 0.004). Mineral separation experiments, and a series of annealing experiments on Isna, suggest that the TL properties for CO chondrites reflect the presence of feldspar in two forms, (1) a form produced during metamorphism, and analogous to the dominant form of feldspar in type 3 ordinary chondrites, and (2) a primary, metamorphism-independent form, perhaps associated with the amoeboid inclusions. If this interpretation is correct, then the CO chondrites have not experienced temperatures above the order/disorder temperature for feldspar (500–600°C) and they cooled more slowly than comparable (i.e. type <3.5) type 3 ordinary chondrites. Colony and ALHA 77307 have atypical TL properties, including very low TL sensitivity, suggesting that phosphors other than feldspar are important. They have apparently experienced less metamorphism than the others, and may have also been aqueously altered.     

Conditions of formation of the Mavrokoryfi high-sulfidation epithermal Cu�CAg�CAu�CTe mineralization (Petrota Graben, NE Greece)

The Mavrokoryfi Cu?CAg?CAu?CTe prospect, northeastern Greece, consists of atypical, high-sulfidation mineralization where precious metals were introduced contemporaneously with advanced argillic alteration from magmatic vapors. It occurs as veins of massive sulfides in zones of silicic and advanced argillic alteration spatially associated with an andesitic lava dome and hyaloclastites. Mineralogical data demonstrate an unusual ore and gangue mineralogy that is compatible with formation under very oxidizing conditions (logfO₂ values of >?31.8) at temperatures of 200°C to 250°C. Oxidizing conditions favored the formation of hypogene lead sulfates (anglesite and barian celestite) instead of galena. Selenian acanthite, cadmian freibergite, and argentian goldfieldite are the main carriers of silver in the deposit and are reported in Greece for the first time. They were deposited at logfS₂ of ?9 to ?7 and logfTe₂ values of ?9 to ?12.5 (250°C). Ag-poor goldfieldite at Mavrokoryfi has up to 3.7 apfu Te and is the most Te-rich goldfieldite yet reported. The mineralization is accompanied by aluminum?Cphosphate?Csulfate minerals of magmatic-hydrothermal origin and an unusual Pb-enrichment. Ore-forming components were likely derived from andesite porphyries.     

The transpressional connection between Dom Feliciano and Kaoko Belts at 580�C550?Ma

A new U?CPb SHRIMP age of 551?±?4?Ma on a mylonitic porphyry that intruded into the Sierra Ballena Shear Zone (Southernmost Dom Feliciano Belt, Uruguay) and a review of relevant published data make possible a more refined correlation and reconstruction of Brasiliano/Pan-African transpressional events. Paleogeographic reconstruction, kinematics and timing of events indicate a connection between the shear systems of the Dom Feliciano and Kaoko Belts at 580?C550?Ma. Sinistral transpression recorded in shear zones accommodates deformation subsequent to collision between the Congo and Río de la Plata Cratons. The correlation is strengthened by the similarity of magmatic and metamorphic ages in the Coastal Terrane of the Kaoko Belt and the Punta del Este Terrane of the Dom Feliciano Belt. This post-collisional sinistral transpression brought these units near to their final position in Gondwana and explains the different evolution at 550?C530?Ma. While in the Kaoko Belt, an extensional episode resulted in exhumation as a consequence of collision in the Damara Belt, in the Dom Feliciano Belt, sinistral transpression occurred associated with the closure of the southern Adamastor Ocean due to Kalahari-Río de la Plata collision.     

Dissolution kinetics of selected natural minerals relevant to potential CO2-injection sites – Part 2: Dissolution and alteration of carbonates and feldspars in CO2-bearing brines

Chemical interaction processes among injected CO₂, saline fluids and potential reservoir materials are experimentally simulated to derive dissolution rates of natural materials (minerals) that can be used as input parameters for modeling of CO₂ storage in deep saline formations and risk analyses. In order to study dissolution processes, mineral aliquots were exposed to CO₂-bearing brines at elevated temperature (60, 100, 150 °C) and pressure (85 bar) and at various run durations. Several potential reservoir rocks include carbonates as cement. Calcite and dolomite grains were therefore mainly used as solid starting material. Experiments with the two feldspar varieties alkali feldspar and almost pure anorthite were performed in addition. Grain sizes of the mineral starting materials varied between <63 μm and 500 μm with most experiments performed at grain size fractions of 160 – 250 μm and 250 – 500 μm. All experiments run with a complex synthetic brine (total dissolved solids: ∼156 g/l) according to a natural upper cretaceous formation water. Dry ice was used as CO₂-source. All experiments were done in closed batch reactors. These reactors allow mimicking reservoir conditions far from the injection site as well as reservoir conditions after finishing the CO₂ injection. The concentration changes during the experiment were monitored by ICP-OES measurements of the initial and the post-run fluids. Dissolution rates were derived based on the concentration changes of the brine.Most of the studied experimental variables and parameters (temperature, run duration, grain size, brine composition – expressed as pH-value and ionic strength) impact alteration of the reacting agents, i.e. they change the chemical composition of the brine, change the surfaces of the mineral aliquots exposed to the CO₂-bearing brine, and induce formation of secondary minerals. Hence, all influencing parameters on dissolution processes have to be considered and time-resolved changes of the dissolution behavior have to be implemented in numerical simulations of processes at CO₂ injection sites and CO₂ storage reservoirs.     

大气CO研究进展

当下大气CO的研究内容和关注焦点主要包括CO的大气化学特性、CO对气候环境的间接影响、环境污染监测及源汇研究、CO全球分布特点及传输变化规律等。为了更好地了解大气CO的研究现状,回顾了大量国内外研究成果,对大气CO的研究方法进行了初步总结,以期对未来加强我国三极地区大气CO观测和完善大气化学模式等方面提出合理建议。     

Interactions between basalts and oil source rocks in rift basins： CO2 generation

Basalts interbedded with oil source rocks are discovered frequently in rift basins of eastern China, where CO2 is found in reservoirs around or within basalts, for example in the Binnan reservoir of the Dongying Depression. In the reservoirs, CO2 with heavy carbon isotopic composition (δ13C>-10‰ PDB) is in most cases accounts for 40% of the total gas reserve, and is believed to have resulted from degassing of basaltic magma from the mantle. In their investigations of the Binnan reservoir, the authors suggested that the CO2 would result from interactions between the source rocks and basalts. As the source rocks around basalts are rich in carbonate minerals, volcanic minerals, transition metals and organic matter, during their burial history some of the transition metals were catalyzed on the thermal degradation of organic matter into hydrocarbons and on the decomposition of carbonate minerals into CO2, which was reproduced in thermal simulations of the source rocks with the transition metals (Ni and Co). This kind of CO2 accounts for 55%-85% of the total gas reserve generated in the process of thermal simulation, and its δ13C values range from -11‰- -7.2‰ PDB, which are very similar to those of CO2 found in the Binnan reservoir. The co-generation of CO2 and hydrocarbon gases makes it possible their accumulation together in one trap. In other words, if the CO2 resulted directly from degassing of basaltic magma or was derived from the mantle, it could not be accumulated with hydrocarbon gases because it came into the basin much earlier than hydrocarbon generation and much earlier than trap formation. Therefore, the source rocks around basalts generated hydrocarbons and CO2 simultaneously through catalysis of Co and Ni transition metals, which is useful for the explanation of co-accumulation of hydrocarbon gases and CO2 in rift basins in eastern China.     

Seasonal and annual variability of days with strong winds and wind damage in Krakow (Poland) during the period 2000�C2007

The study analyses the numbers of days with strong winds in Krakow during the period 2000?C2007 using anemometric records and fire department data. Patterns are identified in the seasonal and annual variation of strong winds. Particular attention is devoted to extreme events. Based on measurements, the study finds that strong winds mostly occurred in winter. Fire department call-out data show that repair of damage caused by strong winds and gusts of wind was needed equally as frequently in summertime. Strong winds accompanying summer storms are often of a local nature and are not always recorded by weather stations. Wind damage was mapped using requests for fire department assistance.     

Irish peat slides 2006�C2010

The purpose of this paper is to present a review of peat landslide events in Ireland since 2003, when two significant events occurred. Since 2003, there have been at least 13 such events. Several of these events included more than one slide. It is also likely that there have been unrecorded slides. It seems that there is an increasing incidence of such events, but they seem to occur in clusters with intervening quiet periods. These clusters coincide with periods of intense rainfall. For many slides, at least two causal factors can be identified. Primarily these comprised intense rainfall but human activities such as road construction and peat cutting also contributed to the slides. Detailed geotechnical testing of the peat, including laboratory direct simple shear tests (DSS), is reported for two of the slides. Back-analysis of these two failures suggests that the mobilised strength of the material in the failure surface is similar to that measured in the DSS tests. However, conventional geotechnical analyses need to be treated with caution as they fail to account for the complex interactions in the sliding surface and in particular the lubricating role of water.