Fluid Inclusion Microthermometry and Implications for the Mechanisms of Ore-Grade Gold Mineralization in Epithermal System, Lalab Orebody, Sibutad, Zamboanga del Norte, Philippines

The Sibutad gold deposit has gold associated in quartz veins. The most important of these is the Lalab orebody, which contains ore‐grade gold, predominantly, in milky quartz veins and veinlets. Here, alteration quartz and fine‐grained crystalline clear and milky quartz were formed from hydrothermal fluids in three stages, namely stages I, II and III. Fluid inclusion microthermometry was carried out on stage I milky quartz, stage II fine‐grained alteration quartz and stage III milky quartz ± barite veins and veinlets. Homogenization temperatures (T_H) are >248°C in stage I, 214–232°C in stage II and 186–239°C in stage III. These fluid inclusions have salinity between 1 and 2 wt% NaCl equivalent. In terms of gold assay, stage I drill‐core samples have gold grades 0.53–0.76 g/ton Au, stage II samples have 1.12–3.70 g/ton Au and stage III samples have 9.06–23.88 g/ton Au. This correlation suggests that gold was precipitated from the stage II and III fluids.     

Kinetic Study of the Reactions of Ozone with Polycyclic Aromatic Hydrocarbons Adsorbed on Atmospheric Model Particles

In this experimental study, rate constants were measured for the reactions of ozone with 13 polycyclic aromatic hydrocarbons (PAHs) adsorbed on different types of particles. Graphite and silica were chosen to model, respectively, carbonaceous and mineral atmospheric particles. The pseudo-first order rate constants were obtained from the fit of the experimental decay of particulate PAH concentrations versus time. Second order rate constants were calculated considering the ozone gaseous concentration. At room temperature, rate constants varied, in the case of graphite particles, between (1.5 ± 0.5) × 10⁻¹⁷ and (1.3 ± 0.7) × 10⁻¹⁶ cm³ molecule⁻¹ s⁻¹ for chrysene and dibenzo[a,l]pyrene, respectively, and, in the case of silica particles, between (1.5 ± 0.3) × 10⁻¹⁷ and (1.4 ± 0.3) × 10⁻¹⁶ cm³ molecule⁻¹ s⁻¹ for fluoranthene and benzo[a]pyrene, respectively. Different granulometric parameters (particle size, pore size) and different PAH concentrations were tested in the case of silica particles. Heterogeneous reactions of ozone with particulate PAHs are shown to be more rapid than those occurring in the gas-phase, and may be competitive with atmospheric photodegradation.     

Interpreting the hydrological history of a temporary pond from chemical and microscopic characterization of siliceous microfossils

The hydrological history of a temporary pond in South Carolina was inferred from a 5500-year record of siliceous microfossils, including diatoms, freshwater sponge spicules, chrysophyte cysts, plates of testate amoebae and plant phytoliths. Microfossil abundance was estimated by microscopic quantification of siliceous particles and by chemical extractions of silica. Diatom, sponge and mineral particle volumes were correlated with silica concentrations attributable to these fractions. Both techniques suggested a sequence of four distinct community types. Basal sediments (4630–5520 ¹⁴C YBP) containing phytoliths and sponge spicules indicative of a wetland community were covered by sediments dominated by the remains of planktonic protists (3750–4630 ¹⁴C YBP) suggesting a transition from a vegetated marsh to an open-water, permanently flooded pond. Microfossil assemblages above this zone indicate the return of a wetland community ca. 3750 YBP that persisted until recently, when pond water levels stabilized as a result of seepage from a reservoir constructed nearby in 1985. This study suggests that the suite of siliceous microfossils commonly found in pond sediments can be used to infer historical alternations between macrophyte and plankton-dominated states in shallow basins. Regional climate inferences from this record include a mid-Holocene hydrological maximum and the onset of the modern climate ca. 3500 YBP.     

Character of sediments entering the Costa Rica subduction zone: Implications for partitioning of water along the plate interface

Abstract   Sediments deposited off the Nicoya Peninsula advect large volumes of water as they enter the Costa Rica subduction zone. Seismic reflection data, together with results from Ocean Drilling Program Leg 170, show that hemipelagic mud comprises the upper ∼135 m of the sediment column (ranging from 0 to 210 m). The lower ∼215 m of the sediment column (ranging from 0 to 470 m) is pelagic carbonate ooze. We analyzed samples from 60 shallow (<7 m) cores to characterize the spatial variability of sediment composition on the incoming Cocos Plate. The bulk hemipelagic sediment is 10 wt% opal and 60 wt% smectite on average, with no significant variations along strike; the pelagic chalk contains approximately 2 wt% opal and <1 wt% smectite. Initially, most of the water (96%) in the subducting sediment is stored in pore spaces, but the pore water is expelled during the early stages of subduction by compaction and tectonic consolidation. Approximately 3.6% of the sediment's total water volume enters the subduction zone as interlayer water in smectite; only 0.4% of the water is bound in opal. Once subducting strata reach depths greater than 6 km (more than 30 km inboard of the subduction front), porosity drops to less than 15%, and temperature rises to greater than 60°C. Under those conditions, discrete pulses of opal and smectite dehydration should create local compartments of fluid overpressure, which probably influence fluid flow patterns and reduce effective stress along the plate boundary fault.     

Determining Biogenic Silica in Marine Samples by Tracking Silicate and Aluminium Concentrations in Alkaline Leaching Solutions

This study introduces an alkaline leaching technique for the simultaneous analysis of biogenic silica and aluminium in sediments. Measuring aluminium facilitates the discrimination between silica from the biogenic (BSiO₂) and the non-biogenic fraction, because it originates almost solely from the lithogenic phase. The method was tested using fine-grained silicagel, standard clay minerals, artificial sediments, and natural samples ranging from fresh diatoms to aged sediment from different depositional settings. To determine the BSiO₂ content, four different models each describing the dissolution curves, but of increasing complexity, were applied and for each different type of sample the optimum model was selected on the basis of F-test statistics. For mixtures of silicagel and clay minerals, the contribution of Si from the dissolution of clay was negligible compared to Si originating from silicagel. For natural samples with high clay content, complex dissolution curves were observed and single-phase first order dissolution was the exception. This deviation from `ideal' behavior could only be recognized because of high-resolution sampling, especially in the first 20 minutes of the experiment. For most of the samples, the distinction between the biogenic silica fraction and the silica originating from dissolution of clays could be made on the basis of the Si/Al ratios and reactivity constants of the dissolving phases calculated with the models. Clay minerals typically dissolve slowly at a Si/Al ratio close to 1–2, depending on the type of clay mineral. In contrast, biogenic silica displays a wide range of reactivities and Si/Al ratios. Fresh biogenic silica from the water column usually has a high reactivity and a low Al content. Aged biogenic silica from the sediments has a lower reactivity, but Si/Al ratios as low as 5 were found. The method as described here therefore presents an accurate method to analyze biogenic silica in marine sediments with a relatively high clay mineral content.     

High-resolution seismic stratigraphy of the Yamato Basin, Japan Sea and its geological application

Abstract High-resolution seismic stratigraphy of the Yamato Basin, Japan Sea, was successfully established using core-log-seismic data integration. The construction of synthetic seismograms by the combination of physical properties and well-log data from the Ocean Drilling Program (ODP) Site 797 was the key to accomplishing the high-resolution seismic stratigraphy. To achieve resolution comparable with well-log data and core lithology, single channel seismic reflection data taken from ODP underway geophysics were reprocessed, and then carefully compared with synthetic seismogram, core and well log profiles to identify seismic units. Ten seismic stratigraphic units were identified at the site, and seismic stratigraphic interpretation was successfully extended from the site to the nearby area along the Yamato Basin margin. The opal-A/opal-CT (biogenic silica/metastable diagenetic silica) boundary has different appearances at places from strong to weak, and mostly discontinuous. One of the significant results achieved from this study is clear distinction of the opal-A/CT boundary from a very strong reflector, which appears at 22 m below the opal-A/CT boundary. Through well-log and physical properties characterization of the different units, resistivity was found to be the best indicator of diatom content and with gamma-ray it also is an indicator of chert layers in the opal-CT zone. Velocity is not greatly effected by diatom ooze in the opal-A zone, however, it shows strong peaks and has an indirect relationship with gamma-ray in the opal-CT zone. Finally, successful correlation of Gamma-ray Attenuation Porosity Evaluator density and resistivity peaks with strong seismic reflectors from upper and lower stratified layers may provide new information on the late Neogene paleoceanography of the Japan Sea in high-resolution scale.     

Molecular dynamics modeling of stishovite

A Morse-stretch potential charge equilibrium force field for silica system has been employed to simulate the thermodynamics of stishovite with the molecular dynamics (MD) method. The equation of state, thermal expansivity and melting curve of stishovite have been obtained. This simple force field yielded results in accordance with the static and dynamic experiments. The stishovite melting simulation appears to validate the interpretation of superheating of the solid along the Hugoniot in the shock melting experiments. MD simulations show that the thermal expansivity of stishovite at lowermost mantle conditions is a weak function of temperature. The phase diagram of silica up to the mega bar regime is proposed based on the experimental and theoretical studies. The related physical and geophysical implications are addressed.     

Influence of colloidal silica grout on liquefaction potential and cyclic undrained behavior of loose sand

Cyclic triaxial tests were performed to investigate the influence of colloidal silica grout on the deformation properties of saturated loose sand. Distinctly different deformation properties were observed between grouted and ungrouted samples. Untreated samples developed very little axial strain prior to the onset of liquefaction. However, once liquefaction was triggered, large strains occurred rapidly and the samples collapsed within a few additional loading cycles. In contrast, grouted sand samples experienced very little strain during cyclic loading. Additionally, the strain accumulated uniformly throughout loading rather than rapidly prior to collapse and the samples never collapsed. Cyclic triaxial tests were done on samples stabilized with colloidal silica at concentrations of 5, 10, 15, and 20%. In general, samples stabilized with higher concentrations of colloidal silica experienced very little strain during cyclic loading. Sands stabilized with lower concentrations tolerated cyclic loading well, but experienced slightly more strain. Thus, treatment with colloidal silica grout significantly increased the deformation resistance of loose sand to cyclic loading.     

Hydrothermal Alteration and Cu-Au Mineralization at Nena High Sulfidation-type Deposit, Frieda River, Papua New Guinea

Abstract. The Nena Cu‐Au deposit, located in the Frieda River mineral district of northwestern mainland Papua New Guinea, is a composite structurally‐lithologically controlled high sulfidation (HS) system. Its hydrothermal alteration and Cu‐Au mineralization are presented in this paper. Initially propylitized andesitic volcanics veined by epithermal quartz were pervasively superimposed by zoned HS alteration. The zonation grades from vuggy silica core to sulfur‐rich, pyritic silica‐alunite halo followed by pyrophyllite‐dickite‐kaolinite interval and finally to thin illite‐smectite margin, suggesting progressive decrease in temperature and increase in pH. This zonation is enveloped by chlorite‐epidote‐calcite‐gypsum alteration. The acid altered rocks were then invaded by multiple phases of pyrite, subsequently crosscut by quartz, vein alunite and barite. Then sequential deposition of bladed covellite, enargite, luzonite and stibioluzonite occurred from the NW to the SE portions of the deposit, forming a zonation suggestive of progressive decrease in temperature, sulfur fugacity and sulfidation stage. Most ore mineralization occurs in the vuggy silica core. Gold mineralization commenced from the transition of enargite to luzonite and continued throughout the stibioluzonite stage. Associated with gold deposition are Au‐rich pyrite, tennantite‐tetrahedrite, chalcopyrite‐bornite, native tellurium, electrum, calaverite, bismuthinite and galena. Native sulfur occupied the remaining cavities and represents the waning stage of the hydrothermal system. Fluid inclusions studies distinguished magmatic (>300–350d?C, 9–15 wt% NaCl equiv.) and meteoric (<150–200d?C, 1–2 wt% NaCl equiv.) fluids (Holzberger et al., 1996). Temperatures and salinities of fluid inclusions from barite associated with Cu sulfides show a general decrease from NW (330d?C, 9–15 wt% NaCl equiv.) to SE (172d?C, 10 wt% NaCl equiv.) parts of the deposit, indicating gradual entrainment of ground water (Hitchman and Espi, 1997). Interaction of magmatic fluids with meteoric water accompanied by changes in temperature, salinity, acidity and oxidation state of the resultant fluids is interpreted to have been the main cause of metal precipitation. Finally, supergene processes generated Au zone with an underlying chalcocite‐covellite‐digenite blanket over the primary sulfides at depth. Gold occurs as lattice constituent in scorodite, limonite‐goethite and jarosite. Chalcocite is more abundant and widespread than other Cu sulfides. Acidic fluids deposited powdery alunite and kaolinite, vein alunite and amorphous silica. Weakly secondary biotite‐quartz altered porphyry located below the known HS Cu‐Au deposit contains chalcopyrite‐bornite and is overprinted by quartz‐alunite‐pyro‐phyllite‐pyrite assemblage. This feature indicates close temporal, spatial and genetic relation between the two deposit types.     

Mass Transfer, Oxygen Isotopic Variation and Gold Precipitation in Epithermal System: A Case Study of the Hishikari Deposit, Southern Kyushu, Japan

Abstract: Transportation of various kinds of elements occurred in wall rocks (Quaternary andesites) during the hydrothermal alteration accompanied by the Hishikari epithermal gold mineralization. For example, K₂O and MgO contents of wall rocks decrease away from the gold-quartz veins, while (CaO+Na₂O) content increases, and SiO₂ content is variable near the veins. Hydrothermal alteration zoning and bulk compositional variations in wall rocks suggest that the mixing of hydrothermal solution and acidic groundwater took place an important role as the cause for the hydrothermal alteration and bulk compositional variations. The relationship between dissolved silica concentration and temperature of hydrothermal solution mixed with groundwater is obtained based on precipitation kinetics-fluid flow–mixing model, and the computed results are compared with the distribution of SiO₂ minerals (quartz and cristobalite) in the hydrothermal alteration zones. This comparison suggests that the most reasonable flow rate of fluids migrating through hydrothermal alteration zones, and A/M (A: surface area of rocks interacting with fluid, M: mass of fluid) are estimated to be ca. 10^-4.2 m/sec, and ca. 0.10 m²/kg, respectively. The mixing of two fluids (hydrothermal solution and acidic groundwater) can also explain δ¹⁸O zoning in the altered country rocks, hydrothermal alteration zoning from K-feldspar through K-mica to kaolinite from the center (veins) to margin, and deposition of gold.