Diagenesis of Ordovician carbonates from the north-east Michigan Basin, Manitoulin Island area, Ontario: evidence from petrography, stable isotopes and fluid inclusions

Middle to Late Ordovician subtidal carbonates in the Manitoulin Island area of Ontario are predominantly limestone in composition, but non-ferroan and ferroan dolomite is a common cement as well as a selective or locally pervasive replacement phase. Integration of field, petrographic, geochemical (δ¹³C, δ¹⁸O) and fluid inclusion data indicates that lithification of these carbonates occurred during burial diagenesis, with much of the alteration controlled by regional fracturing and hydrothermal influences. Aqueous (type 1) fluid inclusions in early calcite (pre-dolomite) and dolomite are saline (> 29 wt% NaCl eq.) solutions with Ca and/or Mg in excess of Na and display homogenization temperatures with modes of 95 and 101°C, respectively. These temperatures can be explained by significantly more burial than can be accounted for either by the available stratigraphic information or by an unusually high palaeogeothermal gradient, which also is not well supported. The fluid inclusion temperatures are interpreted to have resulted from hydrothermal fluids which circulated during the burial diagenesis of these strata. Type 1 inclusions in late (post-dolomite) calcite are less saline (<19 wt% NaCl eq.) and have a bimodal distribution of homogenization temperatures with a relatively well defined low temperature peak similar to those in early calcite and dolomite and a broad higher temperature grouping with a mode at 183°C. A small proportion of methane and light hydrocarbon-bearing fluid inclusions (type 2) are present in all stages of carbonate. Dolomitizing fluids were derived from burial compaction of argillaceous sediments in the more central parts of the Michigan Basin and the updip migration of these brines along fractures to the basin margin where the carbonates of the Manitoulin Island area were dolomitized. Alternatively, migration of dolomitizing brines downward from the overlying pervasively dolomitized Silurian sequence into fractures in the Ordovician carbonates may have occurred. Integration of the aqueous fluid inclusion data into the diagenetic history of these carbonates remains equivocal because most of the inclusions are secondary or indeterminate in origin. Nevertheless, high salinities resulting from interaction with evaporitic strata and hydrothermal effects are clearly implicated although the origin of the latter remains unclear. The alteration styles of the Ordovician carbonates in the Manitoulin area are similar to those of Ordovician hydrocarbon reservoirs described from other parts of the Michigan Basin. They indicate that fracture-related diagenesis occurred on a basin-wide scale and that hydrothermal effects were important.     

Natrolite,part I: Refinement of high-order data,separation of internal and external vibrational amplitudes from displacement parameters

A single crystal of natrolite, Na₂Al₂Si₃O₁₀·2H₂O, was studied by X-ray diffraction methods at room temperature. The intensities were measured with MoKα radiation (λ = 0.7107 Å) in a complete sphere of reflection up to sin θ/λ = 0.903 Å^?1. The structure was refined in the orthorhombic space group Fdd2 with a = 18.2929 (7) Å, b = 18.6407(9) Å, c = 6.5871(6) Å, V = 2246 ų, Z = 8. A refinement of high-order diffraction data yielded reliability factors of R(F) = 0.9%, R _w(F) = 0.8%, GoF = 1.40 for 1856 high-angle reflections (0.7 ?in θ/λ <0.903 Å^?1) and R(F) = 1.0%, R _W(F) = 1.2%, GoF = 3.07 for all 3471 independent reflections in the complete sphere of reflection. The T-O distances as well as the T-O-T angles were found to be strongly influenced by the different bond strengths received by the individual oxygen atoms. The T O distances calculated using Baur's extended valence rule agree on average within 0.003 Å with the observed values. An analysis of the mean square displacement amplitudes allowed a separation of the external and internal vibrational amplitudes along the T-O bonds as well as along the Na O and H₂O-O bond directions and the calculation of force constants. The internal vibrational amplitudes (ΔU) of the T-O vibrations are in the range of 5 to 11 × 10^-4 Ų, that is about one order of magnitude smaller than the mean square displacement amplitudes of the external vibrations. The corresponding force constants are F = 354 to 824 Nm^?1. The values of the force constants of the motion of the Na-ion and the water molecule against the framework oxygen atoms lie in the range between F = 57 and 293 Nm^?1. This is the first instance where displacement amplitudes from a zeolite structure refinement could be apportioned between contributions from internal and external vibrations for individual bonds.     

The Catoca kimberlite pipe, Republic of Angola: A paleovolcanological model

The Catoca kimberlite pipe is among the world’s largest primary diamond deposits. The Catoca volcanic edifice is only slightly eroded. Kimberlitic rocks of various facies compose a crater of about 1 km in diameter and a diatreme. The structure of the pipe and mining conditions of the deposit are complicated by intense intrapipe tectonic processes related to large-amplitude subsidence. Based on geological data, we propose a structural model of the deposit and a paleovolcanological model of the Catoca pipe formed during a full cycle beginning with a stage of active volcanism and completed by stages of gradually waning volcanic activity and sedimentation. It is suggested that the banded tuffisitic kimberlite of the crater zone was deposited at the stage of active volcanic eruption from specific pyroclastic suspension as a low-viscosity mixture of crystals and aqueous sol rich in serpentine.     

Removal of dyes by adsorption on magnetically modified activated sludge

The ability of magnetically modified activated sludge affected by thermal treatment to remove water-soluble organic dyes was examined. Twelve different dyes were tested. Based on the results of the initial sorption study, four dyes (namely aniline blue, Nile blue, Bismarck brown Y and safranin O) were chosen for further experiments due to their promising binding onto magnetic activated sludge. Significant factors influencing adsorption efficiency such as dependence of contact time, initial pH or temperature were studied in detail. The adsorption process was very fast; more than 88 % of dye content (55 mg/L) was adsorbed within 15 min under experimental conditions used. The equilibrium adsorption data were analyzed by Freundlich, Langmuir and Sips adsorption isotherm models, and the fitting of each isotherm model to experimental data was assessed on the basis of error functions. The maximum adsorption capacities of magnetic activated sludge were 768.2, 246.9, 515.1 and 326.8 mg/g for aniline blue, Bismarck brown Y, Nile blue and safranin O, respectively. The kinetic studies indicated that adsorption of all selected dyes could be well described by the pseudo-second-order kinetic model, and the thermodynamic data suggested the spontaneous and endothermic process.     

Rb-Sr dating of Paleozoic glauconite from the Llano region,central Texas

Glauconite from eight stratigraphic horizons (Cambrian to Pennsylvanian) in the Llano Uplift, central Texas and two Cretaceous glauconites were analyzed by the Rb-Sr method. Only two untreated samples provide ages in agreement with those anticipated from current best estimates of the geologic time scale. With one exception all the other apparent ages fall short of the estimated age of deposition by as much as 22%. Low ages, the pattern customarily observed, are attributed to postdepositional loss of radiogenic ⁸⁷Sr from expandable layers by weathering or during diagenesis.Detailed leaching experiments using a variety of reagents were performed to characterize the behavior of glauconite. The most promising treatment, which we recommend as standard procedure in all future studies, is with ammonium acetate which is able to purge the mineral of loosely-bound Rb and Sr while leaving tightly-bound components intact. After appropriate leach, three other Rb-Sr ages were brought into coincidence with their estimated ages of deposition.In contrast an Upper Cambrian glauconite was found to be extremely resistant to further alteration by chemical attack′, providing an age of 429 ± 17 M yr. Although 17% short of the age of deposition, this age is interpreted as the time of a real event: diagenetic recrystallization induced by burial. Comparison of data from four samples indicates that for Paleozoic glauconite, conditions exist in which the Rb-Sr system is less susceptible to mild disturbance than is the K-Ar system.     

Dauphiné twinning and texture memory in polycrystalline quartz. Part 3: texture memory during phase transformation

Samples of quartz-bearing rocks were heated above the α (trigonal)–β (hexagonal) phase transformation of quartz (625–950°C) to explore changes in preferred orientation patterns. Textures were measured both in situ and ex situ with neutron, synchrotron X-ray and electron backscatter diffraction. The trigonal–hexagonal phase transformation does not change the orientation of c- and a-axes, but positive and negative rhombs become equal in the hexagonal β-phase. In naturally deformed quartzites measured by neutron diffraction a perfect texture memory was observed, i.e. crystals returned to the same trigonal orientation they started from, with no evidence of twin boundaries. Samples measured by electron back-scattered diffraction on surfaces show considerable twinning and memory loss after the phase transformation. In experimentally deformed quartz rocks, where twinning was induced mechanically before heating, the orientation memory is lost. A mechanical model can explain the memory loss but so far it does not account for the persistence of the memory in quartzites. Stresses imposed by neighboring grains remain a likely cause of texture memory in this mineral with a very high elastic anisotropy. If stresses are imposed experimentally the internal stresses are released during the phase transformation and the material returns to its original state prior to deformation. Similarly, on surfaces there are no tractions and thus texture memory is partially lost.     

Hydrogeochemical prospecting for porphyry copper deposits in the tropical-marine climate of Puerto Rico

A hydrogeochemical survey utilizing waters from streams and springs was conducted in the area of two known porphyry copper deposits in the tropical-marine climate of westcentral Puerto Rico. The most important pathfinder for regional hydrogeochemical surveys is sulfate which reflects the associated pyrite mineralization. Because of increased mobility due to intense chemical weathering and the low pH environment, dissolved copper can also be used as a pathfinder for regional surveys and has the advantage of distinguishing barren pyrite from pyrite associated with copper mineralization. For follow-up surveys, the most important pathfinders are copper, sulfate, pH, zinc, and fluoride. High concentrations of dissolved copper and moderate concentrations of sulfate is a diagnostic indication of nearby sources of copper minerals.An understanding of the geochemical processes taking place in the streambeds and the weathering environment, such as the precipitation of secondary copper minerals, contributes to the interpretation of the geochemical data and the selection of the most favorable areas for further exploration.     

Heavy metals in sediments of the Tecate River, Mexico

Ten sites along the Tecate River, Mexico were sampled to evaluate the cadmium, lead, nickel and chromium concentrations in sediments. The result shows contamination for cadmium in most of the sites, where two sites were class 4 (polluted to strongly polluted) according to geoaccumulation index proposed by Muller. Two sites were found polluted for all the heavy metals analyzed (Cr, Cd, Pb and Ni), indicating the effect of anthropogenic activities. A correlation between Ni and Cd concentration had been found indicating a common source. These metals are usually used in electroplating industry. The results of this study can be used for decision makers to prioritize measures to control the pollution for these metals.     

Fractal Analysis of the Complexity of United States Coastlines

Coastlines have long been used as a principal example of a natural feature that exhibits fractal structure. With the advent of large digitized databases, it has become possible to examine in detail large regions of coast and to examine differences in complexity, as measured by the fractal dimension, among regions. In this study, we have determined the fractal dimension of the Atlantic and Pacific coastlines of the conterminous United States. The traditional divider method was used in obtaining the fractal dimension of each coastline arc from the NOAA Medium-Resolution Shoreline Data Set. On average, the Atlantic coast has much higher fractal dimension than the Pacific coast. The results also indicate that the complexity of the Atlantic coast increases toward low latitudes. These results have implications for the interpretation of species distributions and diversity patterns along the coast and for the understanding of the dynamics of biotic recovery from mass extinctions.