The system: Two alkali feldspars-KCl-NaCl-H2O at moderate to high temperatures and low pressures

Because of frequent discrepancies between the available experimental data and the measured composition of alkali chloride aqueous solutions coexisting with two alkali feldspars in high temperatures-low pressures natural systems, a systematic investigation of the system KAlSi₃O₈-NaAlSi₃O₈-KCl-NaCl-H₂O has been undertaken.Experiments have been carried out at temperatures from 300 °C to 660 °C, pressures from 0.2 to 2 kbar and total chloride concentrations ranging from 0.05 to 14 moles/kg H₂O.No effect of pressure on the feldspars solvus could be detected. Smoothing the experimental data on the basis of the regular assymetric solid solution model yields a critical temperature of 661°C and a critical composition of Or_0.36Ab_0.64.The equilibrium constant C = m _KCl/m _NaCl does not depend on total chloride molality, as long as the aqueous solution is homogeneous. But, in the miscibility gap (liquid+vapour) of the fluid, C is always lower in the vapour than in the liquid. The higher the temperature and the lower the pressure, the more striking this effect. For instance, at 500 ° C C _vaqour/C _liquid = 1 above 1 kb, 0.9 at 600 bars, 0.8 at 500 bars, 0.7 at 400–450 bars.The effect of pressure can be neglected in homogeneous fluids and in the liquid phase of unmixed fluids, but it is very important in the vapour phase (dilute solutions at low pressure).The selected values of C _max are (±0.01) 300 ° C0.083; 400 ° C0.139; 500 ° C0.200; 600 ° C0.264; 650 ° C0.298Such a behaviour of the fluid at low pressures explains the abnormally low values of m _KCl/m _NaCl measured in many natural hydrothermal systems. A new mechanism of alkali metasomatism (especially potassic alterations) is also proposed, taking into account the unmixing of alkali chloride aqueous solutions. This model seems particularly interesting in late magmatic hydrothermal processes, such as those occuring in porphyry type deposits.     

The depositional environment of Mauddud limestone,Greater Burgan oil field,Kuwait

Six microfacies are defined on quantitative petrographic data in a carbonate/clastic sequence from the subsurface, oil producing Mauddud Formation of early Middle Cretaceous age. These are, in descending order of importance and abundance: (1) biomicritic wackestone-packstone, (2) argillaceous mudstone, (3) micritic mudstone, (4) glauconitic sandstone, (5)Orhitolina pelsparitic grainstone, and (6) argillaceous dolomite.Sedimentation took place during a marine transgression onto a very shallow, intertidal, restricted marine shelf lagoons. Facies variations appear to be related to depth and energy changes and proximity to areas of clastic deposition. These changes may have been controlled by slight tectonic events in the hinterland and changes in the rate of basin subsidence.

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Zusammenfassung Auf der Grundlage quantitativer petrographischer Daten werden sechs Mikrofazies in einer karbonat/klastischen Folge aus der unter der ErdoberflÄche liegenden, ölliefernden Mauddud-Formation der frühen Mittelkreide definiert. In absteigender Reihenfolge der Bedeutung und HÄufigkeit sind dieses: (1) biomikritischer wackestone-packstone, (2) toniger Schlickstein, (3) unkritischer Schlickstein, (4) glaukonitischer Sandstein, (5) Orbitolina-führender pelsparitischer Grainstone und (6) toniger Dolomit.Die Sedimentation erfolgte wÄhrend einer marinen Transgression auf sehr flache, intertidale Lagunen eines begrenzten marinen Schelfs. Die Fazies-Variationen scheinen mit den Wechseln in Wassertiefe und Energie sowie der mit NÄhe von Gebieten mit klastischer Sedimentation zusammenzuhÄngen.Diese Wechsel könnten durch kleinere tektonische Ereignisse im Hinterland und durch VerÄnderungen der Absenkungsrate des Beckens ausgelöst worden sein.

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Résumé Des données pétrographiques quantitatives permettent de définir six microfacies dans une série clasto-carbonatée d'âge crétacé inférieur du sous-sol de la région pé trolifère de Mauddud. Ce sont par ordre décroissant d'importance et d'abondance: (1) des wacstones-pacstone biomicritiques; (2) des argilites; (3) des argilites micritiques; (4) des grès glauconitiques; (5) des grainstone pelsparitiques à orbitolines; (6) des dolomies argileuses.La sédimentation se produisit au cours d'une transgression marine dans des lagunes très plates, intercotidales, d'une plate-forme continentale de faible étendue. Les variations de facies semblent Être dues à des changements de profondeur et d'énergie, ainsi qu'à la proximité de régions à sédimentation clastique.Ces changements pourraient résulter de légers mouvements tectoniques dans l'arrière-pays et de variations dans le degré de subsidence du bassin de sédimentation.

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Carbon,oxygen and sulphur isotope variations in concretions from the Upper Lias of N.E. England

Carbon, oxygen and sulphur isotope data for transects across two pyrite-bearmg carbonate concretions, and their host sediments, from the Upper Lias of N.E. England show symmetrical zonation. δ¹³C_PDB values of the calcite cement (?12.9 to ?15.4%.) indicate that most of it originated from organic matter by bacterial reduction of sulphate, augmented with marine and, to a lesser extent, fermentation derived carbonate. Organic carbon (δ¹³C_PDB = ?26.1 to ?37.0%.). reflects the admixture of allochtho-nous terrestrial organic matter with marine material and the selective preservation of isotopically light organic material through microbiological degradation.Two phases of pyrite are present in each concretion. The earlier framboidal pyrite formed throughout the sediment prior to concretionary growth and has δ³⁴S_CD values of ?22 to ?26%. indicating formation by open system sulphate reduction. The later euhedral phase is more abundant and reaches values of ? 2.5 to ? 5.5%. at concretion margins. This phase of sulphate reduction provided the carbonate source for concretionary growth and occurred in a partially closed system. The δ¹³C and δ³⁴S data are consistent with mineralogical and chemical evidence which suggest that both concretions formed close to the sediment surface. The δ₁₈O values of the calcite in one concretion (δ¹⁸O_PDB = 2.3 to ?4.8%.) indicate precipitation in pore waters whose temperature and isotopic composition was close to that of overlying seawater. The other concretion is isotopically much lighter (δ¹⁸O_PDB?8.9 to ?9.9%.) and large δ¹⁸O differences between concretions in closely-spaced horizons imply that local factors control the isotopic composition of pore waters.     

An internal variable model for the creep of rocksalt

Summary The creep strain rate of rocksalt, like that of other ductile crystalline materials, can be described by a power law equation of the type ( ) ⁿ , where the active stress is the difference between the total deviatoric applied stress and an internal stress _i . In this paper, the origin and the nature of this internal stress, which develops during inelastic deformation of the material, are discussed. It is shown that this internal stress can serve as an internal (or state) variable in the constitutive model of rocksalt, which reflects the microstructure evolution of the material under the competitive action of hardening and recovery mechanisms.An analysis of experimental data, both our own and those taken from the literature, demonstrates that such a law is able to correctly reproduce rocksalt creep test results in the steady-state domain. The proposed model is in accordance with the macroscopic and microscopic behavior of salt, and with direct measurements of the internal stresses made by others on this material.     

An examination of the use of the logratio transformation for the testing of endmember hypotheses

Given a compositional dataset in the absence of any prior information on any mixing process which may have formed it, a complete analysis of mixtures determines three distinct types of estimates in order. These are: (i) the estimate of the number of endmembers or fixed source compositions, of which all the sample compositions of the dataset must be approximate mixtures; (ii) the estimated compositions for each of these chosen number of endmembers; and (iii) the estimated contributions of each of these endmember estimates to each sample. Traditionally, the estimate for the number of endmembers has been assessed either by mapping or by inspection of the coefficients of determination between the observed and estimated variables. Mapping entails the plotting on a map of the region from which the samples were taken, either the contours of the contributions of each endmember to each sample, or some other portrayal of the distribution of endmember abundances. Because it requires the complete analysis, assessment by this method is too elaborate except for final confirmation and display. Alternatively, choosing a number of endmembers, which result in suitability high coefficients of determination for all or most variables, may account for elements which are not part of the conjectured mixing process or, worse, may result in the identification of endmembers which may never in fact have existed. Such an error is similar to overspecifying a multiple regression model. So, the obvious starting point from which to assess the validity, or otherwise choice of endmember numbers, is to examine the matrix of residuals. The differences between the logratio-transformed observed and estimated data form an array of residual logratios. A linear combination of these may be formed for each sample, which, under a random perturbation assumption, should follow a univariate normal distribution. Whether or not this scalar is normal can be readily tested. It can also be examined graphically for such desirable qualities as symmetry when the test for normality may be too severe. This procedure is employed to assess the decompositions of the U.S.G.S. Mid-Pacific data and the Nazca Plate Surface sediments.This paper was presented at the 18th Geochautauqua, Newark, Delaware, 13–14 October 1989.     

An Example of Island-Arc Petrogenesis: Geochemistry and Petrology of the Southern Luzon Arc, Philippines

Volcanism throughout the Luzon arc is associated with eastwardsubduction of the South China Sea floor along the Manila Trench.The southern section of the arc, the focus of this study, extendsfrom the Lingayen-Dingalan fault to the small islands just southof Luzon. Two segments appear to exist along this section ofthe arc the northern Bataan and southern Mindoro segments whichare separated by the Macolod Corridor. The volcanic rocks have typical arc phenocryst mineralogies:olivine, clinopyroxene, plagioclase, and titanomagnetite inthe most mafic rocks and clinopyroxene, plagioclase, orthopyroxene,titanomagnetite, ? amphibole in the more felsic samples. Complexzoning, sieve textures, and decoupling of incompatible traceelements suggest that processes such as assimilation have takenplace. The rocks from the study area range from basalts to rhyolitesand show typical calc-alkaline features. The rocks of the MacolodCorridor and Mindoro segment are particularly enriched in largeion lithophile elements (LILE), light rare earth elements (LREE),and radiogenic Sr compared with the Bataan segment. The datafall within the mantle array on Sr-Nd isotopic diagrams andgrade toward higher Sr and lower Nd isotopic values from northto south. A likely source for the volcanics of this study is either amid-ocean ridge basalt (MORB)-type mantle that undergoes higherdegrees of partial melting than regions involved in MORB generationor a previously depleted source. We suggest that the high fieldstrength element (HFSE) anomalies have been derived throughdifferential element partitioning during fluid transport fromthe subducted lithosphere to the mantle wedge. Continental crustal material seems to play a significant roleparticularly in the Macolod Corridor and the Mindoro segment,based on the high LILE, La/Sm ratios, radiogenic Sr isotopes,and ¹⁸O values. The Macolod Corridor and the Mindoro segmenthave undergone source contamination by crustal material fromthe North Palawan-Mindoro crustal block either during the collisionof this block with the Manila Trench or by subduction of sedimentsrich in this crustal material. A similar component has alsobeen detected in the Bataan segment but in minor amounts. Thetrace element and isotopic differences between the northernand southern sections of the arc are interpreted in terms ofvariable composition (i. e., variable amounts of a crustal componentintroduced from the Palawan-Mindoro crustal terrain) of themetasomatic fluids released into the source.     

The diagenesis of the late Dinantian Derbyshire-East Midland carbonate shelf, central England

Carbonate cements in late Dinantian (Asbian and Brigantian) limestones of the Derbyshire carbonate platform record a diagenetic history starting with early vadose meteoric cementation and finishing with burial and localized mineral and oil emplacement. The sequence is documented using cement petrography, cathodoluminescence, trace element geochemistry and C and O isotopes. The earliest cements (Pre-Zone 1) are locally developed non-luminescent brown sparry calcite below intrastratal palaeokarsts and calcretes. They contain negligible Fe, Mn and Sr but up to 1000 ppm Mg. Their isotopic compositions centre around δ¹⁸O =?8.5‰, δ¹³C=?5.0‰. Calcretes contain less ¹³C. Subsequent cements are widespread as inclusion-free, low-Mg, low-Fe crinoid overgrowths and are described as having a‘dead-bright-dull’cathodoluminescence. The‘dead’cements (Zone 1) are mostly non-luminescent but contain dissolution hiatuses overlain by finely detailed bright subzones that correlate over several kilometres. Across‘dead'/bright subzones there is a clear trend in Mg (500–900 ppm), Mn (100–450 ppm) and Fe (80-230 ppm). Zone 1 cements have isotopic compositions centred around δ¹⁸O =?8.0‰ and δ¹³C=?2.5‰. Zone 2 cement is bright, thin and complexly subzoned. It is geochemically similar to bright subzones of Zone 1 cements. Dull Zone 3 cement pre-dates pressure dissolution and fills 70% or more of the pore space. It generally contains little Mn, Fe and Sr but can have more than 1000 ppm Mg, increasing stratigraphically upwards. The δ¹⁸O compositions range from ?5.5 to ?15‰ and the δ¹³C range is ?1 to + 3.2^0/00. Zone 4 fills veins and stylolite seams in addition to pores. It is synchronous with Pb, Ba, F ore mineralization and oil migration. Zone 4 is ferroan with around 500 ppm Fe, up to 2500 ppm Mg and up to 1500 ppm Mn. Isotopic compositions range widely; δ¹⁵O =?2.7 to ?9‰ and δ¹³C=?3.8 to+2.50‰. Unaltered marine brachiopods suggest a Dinantian seawater composition around δ¹⁵O = 0‰ (SMOW), but vital isotopic effects probably mask the original δ¹³C (PDB) value. Pre-Zone 1 calcites are meteoric vadose cements with light soil-derived δ¹³C and light meteoric δ¹⁸O. An unusually fractionated‘pluvial’δ¹⁵O(SMOW) value of around — 6‰ is indicated for local Dinantian meteoric water. Calcrete δ¹⁸O values are heavier through evaporation. Zone 1 textures and geochemistry indicate a meteoric phreatic environment. Fe and Mn trends in the bright subzones indicate stagnation, and precipitation occurred in increments from widespread cyclically developed shallow meteoric water bodies. Meteoric alteration of the rock body was pervasive by the end of Zone 1 with a general resetting of isotopic values. Zone 3 is volumetrically important and external sources of water and carbonate are required. Emplacement was during the Namurian-early Westphalian by meteoric water sourced at a karst landscape on the uplifted eastern edge of the Derbyshire-East Midland shelf. The light δ¹⁸O values mainly reflect burial temperatures and an unusually high local heat flow, but an input of highly fractionated hinterland-derived meteoric water at the unconformity is also likely. Relatively heavy δ¹³C values reflect the less-altered state of the source carbonate and aquifer. Zone 4 is partly vein fed and spans burial down to 2000 m and the onset of tectonism. Light organic-matter-derived δ¹³C and heavy δ¹⁸O values suggest basin-derived formation water. Combined with textural evidence of geopressures, this relates to local high-temperature ore mineralization and oil migration. Low water-to-rock ratios with host-rock buffering probably affected the final isotopic compositions of Zone 4, masking extremes both of temperature and organic-matter-derived CO₂.     

The major‐ and trace‐element whole‐rock fingerprints of Egyptian basalts and the provenance of Egyptian artefacts

Discrimination diagrams have been developed that source Egyptian basaltic artefacts using whole‐rock major element geochemistry. These include K₂O versus SiO₂, TiO₂ and P₂O₅ against MgO/Fe₂O₃^t (total Fe as Fe₂O₃), and a discriminant analysis diagram using SiO₂, Fe₂O₃^t, CaO, and MnO. A complementary set of diagrams uses easily obtained trace element data (Nb/Y versus Zr/Nb; Zr [ppm] versus Rb/Sr; TiO₂ [wt % volatile free] versus V; and Cr [ppm] versus Zr/Y) to determine the bedrock sources. These diagrams have been applied to seven First Dynasty basalt vessels (Abydos), two Fourth Dynasty basalt paving stones (Khufu's funerary temple, Giza), and two Fifth Dynasty paving stones (Sahure's complex, Abu Sir). They show that the bedrock source for all the artefacts was the Haddadin flow in northern Egypt. Multidimensional scaling and cluster analysis applied to the whole‐rock data (major elements and trace elements together) and previously published mineral fingerprinting studies confirm these results. Comparing mineral versus whole‐rock fingerprinting techniques, a major advantage of the former is the small sample size required (0.001 g compared to ≥ 0.1 g). Analytical costs are similar for both methods assuming that a comparison (bedrock) database can be assembled from the literature. For most archaeological problems, a whole‐rock bedrock database is more likely to exist than a mineral database, and whole‐rock analyses on artefacts will generally be easier to obtain than mineral analyses. Whole‐rock fingerprinting may be more sensitive than mineral‐based fingerprinting. Thus, if sample quantity is not an issue, whole‐rock analysis may have a slight cost, convenience, and technical advantage over mineral‐based methods. Our results also emphasize that the Egyptians cherished their Haddadin basalt flow and used it extensively and exclusively for manufacturing basalt vessels and paving stones for at least 600 years (∼3150 B.C. to 2500 B.C., approximate ages of the vessels and Abu Sir paving stones, respectively). © 2001 John Wiley & Sons, Inc.     

Geologic sources and geographic distribution of sand tempers in prehistoric potsherds from the Mariana Islands

Temper sands in prehistoric potsherds of the Mariana Islands include terrigenous detritus derived from Paleogene volcanic bedrock and calcareous grains derived chiefly from modern fringing reefs, but also in part from uplifted Neogene limestones overlying volcanic bedrock. Calcareous sands are nondiagnostic of island of origin, but volcanic sands and the terrigenous component of hybrid sands composed of mixed terrigenous and calcareous grain types can be traced to geologic sources on Saipan and Guam, the only occupied islands where volcanic bedrock is extensively exposed. Quartzose tempers of several types were derived exclusively from dacitic volcanic rocks on Saipan. Nonquartzose tempers of andesitic parentage derive from both Saipan and Guam, but abundance of orthopyroxene as well as clinopyroxene is diagnostic of Saipan andesitic tempers, the presence of olivine is diagnostic of selected tempers from Guam, and placer temper sands rich in heavy ferromagnesian minerals occur only in sherds on Guam. Temper analysis documents widespread ceramic transfer from Saipan to other islands throughout Mariana prehistory, and more restricted ceramic transfer from Guam to nearby Rota, although the origin of some andesitic temper types is petrographically indeterminate. © 2001 John Wiley & Sons, Inc.