Origin and history of waters associated with coalbed methane: I, Cl, and stable isotope results from the Fruitland Formation, CO and NM

The Fruitland Formation of the San Juan Basin was deposited during the late Cretaceous and is associated with significant reservoirs of coalbed methane (CBM). The purpose of this study is to determine the origin and history of waters associated with the formation, using long-lived cosmogenic and stable isotope systems. Ratios of ¹²⁹I/I and stable isotope values (δD and δ¹⁸O) were determined in waters from close to 100 wells, ³⁶Cl/Cl ratios for a subset of these samples. A significant group of samples has ¹²⁹I/I ratios between 100 × 10⁻¹⁵ and 200 × 10⁻¹⁵, indicating minimum iodine ages close to 60 Ma. If these ages are corrected for the addition of fissiogenic ¹²⁹I, they are compatible with the depositional age of the Fruitland Formation (Late Cretaceous).Several sets of waters are clearly present within the data. A group dominated by infiltration of recent surface waters is restricted to the uplifted basin margins, with a lateral extent of less than 5 km from outcrop, and is characterized by ¹²⁹I/I ratios in excess of 1500 × 10⁻¹⁵ and meteoric δD, δ¹⁸O, and ³⁶Cl/Cl signatures. The rest of the basin is characterized by several subsets of formation waters which have undergone variable degrees of iodine enrichment through diagenesis as well as variable degrees of dilution. The first subgroup is found in coals of relatively low vitrinite reflectance and moderate enrichment of iodine. This subgroup predominantly consists of entrapped pore fluids, although it may also contain waters which infiltrated the coals at the time of the Laramide uplift, between 25 and 30 Ma. A second subgroup consists of formation waters associated with coals of high vitrinite reflectance. Despite subsequent uplift, the high iodine concentrations and low ¹²⁹I/I ratios of this subgroup, as well as a moderate depletion of deuterium relative to ¹⁸O, suggest that these waters were not significantly altered since the time when diagenetic reactions occurred in the deepest portion of the basin. A third subgroup, with higher δD and δ¹⁸O values as well as higher ¹²⁹I/I ratios, extends roughly west to east at the New Mexico-Colorado state line and corresponds to a region of extensive fracturing of the coalbeds. In this case, the higher ¹²⁹I/I ratios are probably due to contributions of fissiogenic ¹²⁹I through fracture flow, perhaps from deeper formation waters. Our results do not support models of subsequent basin-wide groundwater migration in the Fruitland Formation. The combined use of ¹²⁹I and ³⁶Cl with stable isotope studies provides valuable information as to the hydrologic history of coalbed methane deposits, as well as their potential for commercial exploitation.     

Systematics in the fission track annealing of minerals

A linear relationship exists between annealing temperatures and activation energies of fission tracks for different minerals. The temperature and activation energy needed to erase 50% of the tracks in minerals depend on the lattice energy per mole. These relationships make possible predictions about the stability of tracks in silicates, provided their chemical composition is known or a few isochronal annealing data are available.     

Eigenschaften und Bildung aufweitbarer (quellbarer) Dreischicht-Tonminerale in Böden aus Sedimenten

Contributions to Mineralogy and Petrology - Mineralogische, chemische und kolloidchemische Untersuchungen an den Tonfraktionen von Böden aus Sedimenten haben gezeigt,     

Regional distribution and temporal trends of some contaminants in the water of the Baltic Sea

During a cruise on board RV Gauss in May/June 1988, joint investigations into organochlorine compounds, dissolved trace metals, petroleum hydrocarbons and basic hydrography were carried out at representative stations of the Baltic Monitoring Programme (BMP). The aim of the cruise was to study distribution patterns and — using previous data — to establish temporal trends if at all discernible.Each group of contaminants investigated showed specific characteristics, with differences even between compounds within the same group. The differences are due to:

Rb-sr dating of epithermal vein mineralization stages in the eastern Harz Mountains (Germany) by paleomixing lines

A method is evaluated that enables the dating of binary isotopic paleomixing in hydrothermal alteration assemblages by iterative reconstruction and regression of corresponding two-component mixing lines from conventional Rb-Sr data. The model has been applied to illite-bearing granulometric fractions of hydrothermally altered sedimentary rocks associated with epithermal vein mineralization in the eastern Harz Mountains, Germany. These veins are characterized by a principal quartz-sulfide stage containing quartz, base metal sulfides, and siderite and a subsequent dominant calcite-fluorite-quartz stage. Rb-Sr analyses were performed on untreated granulometric fractions, HCl-treated residues, corresponding HCl leachates, and cogenetic vein minerals obtained from two silicified rock samples related to the quartz-sulfide and the calcite-fluorite-quartz mineralization, respectively.Neither the untreated nor the HCl-leached fractions of these rock samples yield statistically robust and geochronologically meaningful isochrons. When applying the binary mixing model, however, two well-defined paleomixing lines can be reconstructed for the HCl-treated fractions of the rock samples and associated vein minerals at model ages of 226 ± 1 Ma (quartz-sulfide alteration) and 209 ± 2 Ma (calcite-fluorite-quartz alteration). We examine the significance and reliability of these model ages and the corresponding paleomixing lines by means of statistical and geological criteria and discuss the effects of leaching experiments performed on the granulometric fractions using 1 N HCl as well as the nature and origin of the components dissolved in the acid leachates.Our results suggest that the mixing model provides a successful dating concept for isotopic disequilibrium processes during low-temperature hydrothermal events that produce binary mixtures among newly formed alteration phases.     

Nickeloan pyrite from Prangenhaus quarry, Niederberg area, Germany—A short communication

The mineral chemistry of two nickeloan pyrite samples from the Prangenhaus quarry, Wülfrath, is presented. Sample PRH 5: main zone=4.32-9.7 wt% Ni (0.089-0.202 atoms per formula unit (a.p.f.u.)), 0.21-1.31 wt% Co (0.004-0.027 a.p.f.u.); rim zone=11.76-22.38 wt% Ni (0.244-0.466 a.p.f.u. ), 1.35-8.16 wt% Co (0.028-0.168 a.p.f.u.). Sample PRH 6: 6.75-11.33 wt% Ni (0.139-0.234 a.p.f.u.), 0.86-2.46 wt% Co (0.018-0.051 a.p.f.u.). Estimated Fe/Ni and Fe/Co ratios of the hydrothermal fluids forming the nickeloan pyrite point to very local fluctuations in the chemistry of the ore forming fluids in the Prangenhaus quarry. The presence of nickeloan pyrite indicates formation temperatures below 137 °C, which is in accordance with earlier findings of formation temperatures for sphalerite (60-130 °C) in the Niederberg area.     

An experimental investigation of Na incorporation in cordierite in low P/high T metapelites

Mineralogy and Petrology - The aim of this experimental study was to investigate the incorporation of Na in cordierite in metapelites as a function of temperature and pressure using natural...     

Single-crystal structure and Raman spectroscopy of synthetic titanite analog CaAlSiO<Subscript>4</Subscript>F

Synthetic CaAlSiO₄F, the Al-F analog of titanite, has been investigated using single-crystal synchrotron diffraction experiments at Beamline X06DA (Swiss Light Source, Paul Scherrer Institute, Villigen, Switzerland) and Raman spectroscopy. The presented structural model with 40 parameters was refined against 506 unique reflections to a final R _{o b s} of 0.026 (space group A2/a, a = 6.9120(11), b = 8.5010(10), c = 6.435(2) Å, β = 114.670(11)°, and Z = 4) and exhibits less distorted coordination polyhedra than earlier models from powder data. Vibrational spectra were calculated in harmonic approximation at the Γ point from fully relaxed energy optimisations of the crystal structure, using 3D-periodic density functional theory with Gaussian basis sets and the software CRYSTAL06. The lattice parameters of the fully relaxed structure were in good agreement with the experimental values, with the calculated values 0.8 ± 0.4 % too large; the monoclinic angle was calculated 0.4° too large. The agreement of the calculated Raman frequencies with the observed ones was very good, with standard deviation ±3 cm^?1 and maximum deviations of ±7 cm^?1. Furthermore, a detailed discussion of the atomic displacements associated with each Raman mode is given.     

A proposed new type of arsenian pyrite: Composition, nanostructure and geological significance

This report describes a new form of arsenian pyrite, called As³⁺-pyrite, in which As substitutes for Fe [(Fe,As)S₂], in contrast to the more common form of arsenian pyrite, As¹⁻-pyrite, in which As¹⁻ substitutes for S [Fe(As,S)₂]. As³⁺-pyrite has been observed as colloformic overgrowths on As-free pyrite in a hydrothermal gold deposit at Yanacocha, Peru. XPS analyses of the As³⁺-pyrite confirm that As is present largely as As³⁺. EMPA analyses show that As³⁺-pyrite incorporates up to 3.05 at % of As and 0.53 at. %, 0.1 at. %, 0.27 at. %, 0.22 at. %, 0.08 at. % and 0.04 at. % of Pb, Au, Cu, Zn, Ni, and Co, respectively. Incorporation of As³⁺ in the pyrite could be written like: As³⁺+yAu⁺+1-y(□)⇔2Fe²⁺; where Au⁺ and vacancy (□) help to maintain the excess charge. HRTEM observations reveal a sharp boundary between As-free pyrite and the first overgrowth of As³⁺-pyrite (20-40 nm thick) and co-linear lattice fringes indicating epitaxial growth of As³⁺-pyrite on As-free pyrite. Overgrowths of As³⁺-pyrite onto As-free pyrite can be divided into three groups on the basis of crystal size, 8-20 nm, 100-300 nm and 400-900 nm, and the smaller the crystal size the higher the concentration of toxic arsenic and trace metals. The Yanacocha deposit, in which As³⁺-pyrite was found, formed under relatively oxidizing conditions in which the dominant form of dissolved As in the stability field of pyrite is As³⁺; in contrast, reducing conditions are typical of most environments that host As¹⁻-pyrite. As³⁺-pyrite will likely be found in other oxidizing hydrothermal and diagenetic environments, including high-sulfidation epithermal deposits and shallow groundwater systems, where probably kinetically controlled formation of nanoscale crystals such as observed here would be a major control on incorporation and release of As³⁺ and toxic heavy metals in oxidizing natural systems.