Mineralized and unmineralized calderas in Spain; Part II, evolution of the Rodalquilar caldera complex and associated gold-alunite deposits

The Rodalquilar caldera complex is located in the western part of the Cabo de Gata volcanic field in southeastern Spain and is the first documented example of epithermal gold-alunite mineralization within a caldera in Europe. The Rodalquilar caldera is an oval collapse structure having a maximum diameter of 8 km and formed at 11 Ma from eruption of the Cinto ash-flow tuff. The oval Lomilla caldera, with a diameter of 2 km, is nested within the central resurgent dome of the older Rodalquilar caldera. The Lomilla caldera resulted from the eruption of the Lazaras ash-flow tuff which was ponded within the moat of the Rodalquilar caldera. The last phase of volcanic activity in the caldera complex was the emplacement of hornblende andesite flows and intrusions. This magmatic event resulted in structural doming of the caldera, opening of fractures and faults, and provided the heat source for the large hydrothermal systems which deposited quartz-alunite type gold deposits and base metal vein systems. The gold-alunite deposits are enclosed in areas of intense acid sulfate alteration and localized in ring and radial faults and fractures present in the east wall of the Lomilla caldera. Like other acid-sulfate type deposits, the Rodalquilar gold-alunite deposits are closely related in time and space to porphyritic, intermediate composition magma emplaced along caldera structures but unrelated to the caldera forming magmatic system.     

Polarized X-ray absorption spectroscopy of metal ions in minerals

We have made use of the nearly complete linear polarization of synchrotron radiation to study the polarization dependence of X-ray absorption near-edge structure (XANES) and extended fine structure (EXAFS) in oriented single crystals of gillespite (BaFe²⁺ Si₄O₁₀; Fe^{2 +} in square-planar coordination, point symmetry C ₄), anatase (TiO₂; Ti⁴⁺ in octahedral coordination, point symmetry D _2d), and epidote (Ca₂(Al, Fe³⁺)₃SiO₄)₃(OH); Fe³⁺ in distorted octahedral coordination, point symmetry (C _s). For gillespite, the Fe K-XANES spectrum varies strongly with E-vector orientation of the incident X-ray beam. When the E-vector lies in the plane of the FeO₄ group (i.e., perpendicular to the c-axis), multiple-scattering features at 7127 and 7131 eV intensify, whereas when the E-vector is perpendicular to the plane of the FeO₄ group (i.e., parallel to the c-axis), a strongly-polarized 1s to 4p bound state transition occurs at 7116 eV and a localized continuum resonance occurs at 7122 eV. The Fe-K-EXAFS spectrum of gillespite is also highly polarization dependent. When the E-vector is perpendicular to c, all four nearest-neighbor oxygens around Fe²⁺ contribute to the EXAFS signal; when E is parallel to c, the EXAFS signal from nearest-neighbors is reduced by at least 86%. The unpolarized Ti K-XANES spectrum of anatase has three relatively strong pre-edge features at 4967.1, 4969.9, and 4972.7 eV which have resisted definitive interpretation in past studies. The lowest energy feature has a strong xy polarization dependence, suggesting a large amount of 4p _x,y character, and it is also very sharp, indicating a well-defined transition energy. Both of these observations are consistent with an excitonic state with a binding energy of 2.8 eV. The two higher energy features, which are characteristic of octahedrally-coordinated Ti⁴⁺, show little polarization dependence and are probably due to 1s to 3d bound-state transitions, with a small degree of np character in the final state wavefunction. Interpretation of the polarization dependence of Fe K-XANES spectra for epidote is not as straightforward due to the lower space group symmetry (P2₁/m) relative to gillespite (P4/ncc) and anatase (I4₁/amd) and the lower point group symmetry (C _s) of the M(3) site which contains most of the Fe³⁺ in the epidote structure. However, the presence of a shoulder at 7121 eV in the E parallel to b spectrum and its absence in the E normal to bc spectrum are consistent with it being a 1s to 4p _z bound-state transition. Strong, weakly x, y polarized features near 7126 eV in both spectra are most likely due to localized continuum transitions. Also, the 1s to 3d pre-edge intensity varies in intensity with E-vector orientation which is consistent with displacement of Fe³⁺ from the center of the M(3) octahedral site. Analysis of EXAFS spectra of epidote in these two polarizations yields bond distances which are within 0.04 Å of previous single-crystal X-ray diffraction analysis. This study demonstrates the utility of polarized X-ray absorption spectroscopy in quantifying the energies and orbital compositions of final state wavefunctions associated with various X-ray induced transitions in transition-metal containing minerals. It also shows that reasonably accurate M-O distances can be obtained for individual bonds oriented in crystallographically non-equivalent directions.     

Oxygen diffusion rates in quartz exchanged with CO2

Oxygen self diffusion rates were determined in quartz samples exchanged with¹⁸O-enriched CO₂ between 745 and 900°C and various pressures, and the diffusion profiles were measured using an ion microprobe. The activation energy (Q) and preexponential factor (D₀) at P(CO₂) = P(tot) = 100 bar, for diffusion parallel to the c-axis are 159 ( ± 13) kJ/g atom and 2.10 (+0.75/ −0.55) × 10⁻⁸ cm²/s. This rate is approximately 100 times slower than that obtained from hydrothermal experiments and 100 times faster than a previous 1-bar quartz-O₂ exchange experiment. The oxygen diffusion rate measured at 0.6 bar, 888°C, and at 900°C in vacuum is in agreement with the previous 1-bar exchange experiments with¹⁸O₂. The effect of higher CO₂ pressures is small. At 900°C, the diffusion rate exchanged with CO₂ is = 2.35 × 10⁻¹⁵ cm²/s at 100 bar, 2.24 × 10⁻¹⁵ cm²/s at 3.45 kbar and 8.13 × 10⁻¹⁵ cm²/s at 7.2 kbar.There is probably a diffusing species, other than oxygen, that enhances the oxygen diffusion rate in these quartz-CO₂ systems, relative to that occurring at very low pressures or in a vacuum. The effect of this diffusing species, however, is not as strong as that associated with H₂O. Preserved oxygen isotope fractionations between coexisting minerals in a slowly cooled, high-grade metamorphic terrane will vary depending upon whether a water-rich phase was present or not. Closure temperatures will be approximately 100°C higher in rocks where no water-rich phase was present during cooling. The measured fractionations between coexisting minerals in metamorphic rocks may potentially be used as a sensor of water presence during retrogression.     

High-frequency sequences and their stacking patterns: sequence-stratigraphic evidence of high-frequency eustatic cycles

A hierarchy of interpreted eustatic cyclicity in siliciclastic sedimentary rocks has a pattern of superposed cycles with frequencies in the ranges of 9–10 m.y., 1–2 m.y., 0.1–0.2 m.y., and 0.01–0.02 m.y. (second- through fifth-order cyclicity, respectively). Stratigraphic units displaying this cyclicity include composite sequences, sequences, and parasequences. On the Exxon global cycle chart, fundamental third-order cycles (1–2 m.y. average duration) stack into related groups (second-order cycles: 9–10 m.y. duration). A much larger pattern (about 200 m.y.) is interpreted as tectonically controlled eustasy probably related to sea-floor spreading rates.

One and probably two higher orders of cyclicity (fourth-order: 0.1–0.2 m.y.; and fifth-order: 0.01–0.02 m.y.) are now observed in work with well logs, cores, and outcrops in areas of very rapid deposition. These frequencies are in the range of Milankovitch cycles, and may represent part of the Milankovitch hierarchy which has been widely interpreted for cyclical units in carbonate rocks.

High-frequency (fourth-order) sequences, which form at a 0.1–0.2 m.y. cyclicity, have all the stratal attributes of conventional sequences, including constituent parasequences and systems tracts, and play a dominant role controling reservoir, source, and sealing rock distribution. A consistent hierarchy of stratigraphy is observed. Parasequences (probable fifth-order cyclicity) stack into sets to form systems tracts in fourth-order sequences. Groups (sets) of fourth-order sequences are deposited between major third-order boundaries within third-order composite sequences. Sequences in these sets stack in prograding and backstepping patterns to form third-order lowstand, transgressive, and highstand sequence sets.

Third-order sequence boundaries are marked by greater basinward shifts in facies, by larger more widespread incised valleys, and by more extensive onlap than are fourth-order sequence boundaries. Third-order condensed sections commonly are widespread, faunally rich, and widely correlated biozone and mapping markers. Fourth-order sequence analysis helps to understand reservoir, source, and seal distribution at the play and prospect scale. An example from the Gulf of Mexico is discussed.     

Corporate strategy, business strategy and activity location

Analysis of locational patterns and change within an industry may be assisted by division of industry participants into groups based on corporate and business strategies. These strategies reflect the assets of the companies and the characteristics of the industry. They affect the locational needs, behavior and impact of the companies. Hypothesized effects of strategy are explored in a brief study of U.S. semiconductor manufacturers. Of the possible strategic considerations, corporate diversification and integration, and business scale and cost/price position seem to be the most relevant for this industry.     

Volatiles H2O,CO2, and Cl in a subduction related basalt

The products of the 1974 eruption of Fuego, a subduction zone volcano in Guatemala, have been investigated through study of silicate melt inclusions in olivine. The melt inclusions sampled liquids in regions where olivine, plagioclase, magnetite, and augite were precipitating. Comparisons of the erupted ash, groundmass, and melt inclusion compositions suggest that the inclusions represent samples of liquids present in a thermal boundary layer of the magma body. The concentrations of H₂O and CO₂ in glass inclusions were determined by a vacuum fusion manometric technique using individual olivine crystals (Fo77 to Fo71) with glass inclusion compositions that ranged from high-alumina basalt to basaltic andesite. Water, Cl, and K₂O concentrations increased by a factor of two as the olivine crystals became more iron-rich (Fo77 to Fo71) and as the glass inclusions increased in SiO₂ from 51 to 54 wt.% SiO₂. The concentration of H₂O in the melt increased from 1.6 wt.% in the least differentiated liquid to about 3.5% in a more differentiated liquid. Carbon dioxide is about an order of magnitude less abundant than H₂O in these inclusions. The gas saturation pressures for pure H₂O in equilibrium with the melt inclusions, which were calculated from the glass inclusion compositions using the solubility model of Burnham (1979), are given approximately by P(H₂O)(Pa)=(SiO₂−48.5 wt.%) × 1.45 × 10⁷. The concentrations of water in the melt and the gas saturation pressures increased from about 1.5% to 3.5% and from 300 to 850 bars, respectively, during pre-eruption crystallization.     

On modelling the seasonal thermodynamic cycle of sea ice in studies of climatic change

Recent work in modelling climatic changes due to increased atmospheric CO₂ has shown the maximum change to occur in the polar regions as a result of seasonal reductions in sea ice coverage. Typically, sea ice thermodynamics is modelled in a very simple way, whereby the storage of both sensible and latent heat within the ice is ignored, and the effects of snow cover on conductivity and on surface albedo and of oceanic heat flux on bottom ablation may also be neglected. This paper considers whether omission of these processes is justified within the context of quantitatively determining regional climatic changes. A related question, whether omission of ice dynamics can be justified, is not considered.Relatively complete one-dimensional models of sea-ice thermodynamics have previously been developed and tested for a variety of environmental conditions by Maykut and Untersteiner (1969, 1971) and by Semtner (1976). A simpler model which neglects the storage of sensible and latent heat is described in the Appendix to Semtner (1976). In that model, the errors in annual-mean ice thickness which would arise from neglect of heat storage can be compensated by increases in albedo and in conductivity. Here we examine the seasonal cycle of ice thickness predicted by such a model and find significant errors in phase (one month lead) and in amplitude (50% overestimate). The amplitude errors are enhanced as snowfall and oceanic heat flux diminish (or are neglected). This suggests that substantial errors may occur in climate simulations which use very simple formulations of sea ice thermodynamics, whereby early and excessive melting exaggerates the seasonal disappearance of sea ice.To illustrate the above point, two models are configured to examine the local response of Arctic sea ice to a quadrupling of atmospheric CO₂. The first model neglects a number of physical processes and mimics the behavior of sea ice found in Manabe and Stouffer (1980), both for present and enhanced levels of CO₂. The more complete second model gives a better simulation of Arctic ice for the present level of CO₂ and shows a reduced response to CO₂ quadrupling relative to that in Manabe and Stouffer (1980). In particular, the change in surface temperature is cut by a factor of two. In view of this result, a more complete treatment of sea ice thermodynamics would seem warranted in further studies of climate change. Only a minor computational increase is required.A portion of this study is supported by the U.S. Department of Energy as a part of its Carbon Dioxide Research Program.The National Center for Atmospheric Research is sponsored by the National Science Foundation.     

Late glacial and late Holocene moraines in the Cerros Cuchpanga, central Peru

Small ice fields on the western cordillera northeast of Lima were expanded to three times their present size in the recent past, and the regional snow line was probably about 100 m lower than it is today. Outwash from the expanded glaciers formed deltas of silt in valley-bottom lakes. When the ice lobes retreated, the reduced outwash was trapped behind recessional moraines, and the clear meltwater infiltrated into the limestone bedrock and emerged at the heads of the deltas in spring pools. The delta surfaces then became covered with peat, and radiocarbon dates for the base of the peat (1100 ± 70 and 430 ± 70 yr B.P. for two different deltas) indicate that the maximum ice advance was older than those dates and, thus, older than the Little Ice Age of many north-temperate regions. Much older moraines date from expansion of the same local summit glaciers to even lower levels in the main valleys, which had previously been inundated by the cordilleran ice field. The cordilleran deglaciation and this expansion of local glaciers probably occurred between 12,000 and 10,000 yr ago, on the basis of slightly contradictory radiocarbon dates.