Abstract A shock-induced polymorph (TiO2 II) of anatase and rutile has been identified in breccias from the late Eocene Chesapeake Bay impact structure. The breccia samples are from a recent, partially cored test hole in the central uplift at Cape Charles, Virginia. The drill cores from 744 to 823 m depth consist of suevitic crystalline-clast breccia and brecciated cataclastic gneiss in which the TiO2 phases anatase and rutile are common accessory minerals. Electron-microprobe imaging and laser Raman spectroscopy of TiO2 crystals, and powder X-ray diffraction (XRD) of mineral concentrates, confirm that a high-pressure, α-PbO2 structured polymorph of TiO2 (TiO2 II) coexists with anatase and rutile in matrix-hosted crystals and in inclusions within chlorite. Raman spectra of this polymorph include strong bands at wavenumbers (cm.1) 175, 281, 315, 342, 356, 425, 531, 571, and 604; they appear with anatase bands at 397, 515, and 634 cm-1, and rutile bands at 441 and 608 cm-1. XRD patterns reveal 12 lines from the polymorph that do not significantly interfere with those of anatase or rutile, and are consistent with the TiO2 II that was first reported to occur naturally as a shock-induced phase in rutile from the Ries crater in Germany. The recognition here of a second natural shock-induced occurrence of TiO2 II suggests that its presence in rocks that have not been subjected to ultrahigh-pressure regional metamorphism can be a diagnostic indicator for confirmation of suspected impact structures.

A rhyolitic hyaloclastite from Ponza Island, Italy, was hydrothermally altered, producing four distinct alteration zones based on X-ray diffraction mineralogy and field textures: (1) nonpervasive argillic zone; (2) propylitic zone; (3) silicic zone; and (4) sericitic zone. The unaltered hyaloclastite is volcanic breccia with clasts of vesiculated obsidian in a matrix of predominantly pumice lapilli. Incomplete alteration of the hyaloclastite resulted in the nonpervasive argillic zone, characterized by smectite and disordered opal-CT. The other three zones exhibit more complete alteration of the hyaloclastite. The propylitic zone is characterized by mixed-layer illite-smectite (I-S) with 10 to 85% I, mordenite, opal-C, and authigenic K-feldspar (akspar). The silicic zone is characterized by I-S with greater than or equal to90% I, pure illite, quartz, akspar, and occasional albite. The sericitic zone consists primarily of I-S with greater than or equal to66% I, pure illite, quartz, and minor akspar and pyrite. K/Ar dates of I-S indicate hydrothermal alteration occurred at 3.38 +/- 0.08 Ma.Oxygen isotope compositions of I-S systematically decrease from zones 1 to 4. In the argillic zone, smectite has delta(18)O values of 21.7 to 22.0parts per thousand and I-S from the propylitic, silicic, and sericitic zones ranges from 14.5 to 16.3parts per thousand, 12.5 to 14.0parts per thousand, and 8.6 to 11.9parts per thousand, respectively. delta(18)O values for quartz from the silicic and sericitic zones range from 12.6 to 15.9parts per thousand. By use of isotope fractionation equations and data from authigenic quartz-hosted primary fluid inclusions, alteration temperatures ranged from 50 to 65degreesC for the argillic zone, 85 to 125degreesC for the propylific zone, 110 to 210degreesC for the silicic zone, and 145 to 225degreesC for the sericitic zone. Fluid inclusion data and calculated delta(18)O(water) values indicate that hydrothermal fluids were seawater dominated.Mass-transfer calculations indicate that hydrothermal alteration proceeded in a relatively open chemical system and alteration in the sericitic zone involved the most extensive loss of chemical species, especially Si. Systematic gains in Mg occur in all alteration zones as a result of I-S clay mineral formation, and systematic losses of Na, Ca, and K occur in most zones. With the exception of Ca, calculations of mass transfer associated with hydrothermal alteration on Ponza agree with chemical fluxes observed in laboratory experiments involving hydrothermal reactions of rhyolite and seawater. The anomalous Ca loss at Ponza may be due to hydrothermal formation of anhydrite and later low-temperature dissolution. On the basis of Mg enrichments derived from circulating seawater, we estimate the following minimum water/rock ratios: 9, 3, 6, and 9 for the argillic, propylitic, silicic, and sericitic zones, respectively. Hydrothermal fluid pH for the propylitic and silicic zones was neutral to slightly basic and relatively acidic for the sericitic zone as a result of condensation of carbonic and perhaps other acids. Copyright (C) 2003 Elsevier Science Ltd.

Armoring of limestone is a common cause of failure in limestone-based acid-mine drainage (AMD) treatment systems. Limestone is the least expensive material available for acid neutralization, but is not typically recommended for highly acidic, Fe-rich waters due to armoring with Fe(III) oxyhydroxide coatings. A new AMD treatment technology that uses CO2 in a pulsed limestone bed reactor minimizes armor formation and enhances limestone reaction with AMD. Limestone was characterized before and after treatment with constant flow and with the new pulsed limestone bed process using AMD from an inactive coal mine in Pennsylvania (pH=2.9, Fe =150 mg/l, acidity =1000 mg/l CaCO3). In constant flow experiments, limestone is completely armored with reddish-colored ochre within 48 h of contact in a fluidized bed reactor. Effluent pH initially increased from the inflow pH of 2.9 to over 7, but then decreased to <4 during the 48 h of contact. Limestone grains developed a rind of gypsum encapsulated by a 10- to 30-μm thick, Fe-Al hydroxysulfate coating. Armoring slowed the reaction and prevented the limestone from generating any additional alkalinity in the system. With the pulsed flow limestone bed process, armor formation is largely suppressed and most limestone grains completely dissolve resulting in an effluent pH of >6 during operation. Limestone removed from a pulsed bed pilot plant is a mixture of unarmored, rounded and etched limestone grains and partially armored limestone and refractory mineral grains (dolomite, pyrite). The ∼30% of the residual grains in the pulsed flow reactor that are armored have thicker (50- to 100-μm), more aluminous coatings and lack the gypsum rind that develops in the constant flow experiment. Aluminium-rich zones developed in the interior parts of armor rims in both the constant flow and pulsed limestone bed experiments in response to pH changes at the solid/solution interface.

Abstract This report describes the first occurrence of the rare mineral mandarinoite (Fe3+2Se3O9 · 6H2O) in China. It occurs in the Lower Permian Maokou Formation carbonaceous shale in Yutangba Village east of Enshi City in southwestern Hubei Province. The shale is selenium‐rich and contains native selenium, V‐Mo‐Cr‐bearing iron oxide, clay and quartz. Weathering of the selenium in the bedrock under moderate to high redox conditions in the presence of ferric iron has formed mandarinoite.

Coal will be a dominant energy source in both developed and developing countries for at least the first half of the 21st century. Environmental problems associated with coal, before mining, during mining, in storage, during combustion, and postcombustion waste products are well known and are being addressed by ongoing research. The connection between potential environmental problems with human health is a fairly new field and requires the cooperation of both the geoscience and medical disciplines. Three research programs that illustrate this collaboration are described and used to present a range of human health problems that are potentially caused by coal. Domestic combustion of coal in China has, in some cases, severely affected human health. Both on a local and regional scale, human health has been adversely affected by coals containing arsenic, fluorine, selenium, and possibly, mercury. Balkan endemic nephropathy (BEN), an irreversible kidney disease of unknown origin, has been related to the proximity of Pliocene lignite deposits. The working hypothesis is that groundwater is leaching toxic organic compounds as it passes through the lignites and that these organics are then ingested by the local population contributing to this health problem. Human disease associated with coal mining mainly results from inhalation of particulate matter during the mining process. The disease is Coal Worker's Pneumoconiosis characterized by coal dust-induced lesions in the gas exchange regions of the lung; the coal worker's “black lung disease”.

Southwest Guizhou Province is one of the most important areas of disseminated, sediment-hosted-type Au deposits in China and is an important area of coal production. The chemistry of most of the coals in SW Guizhou is similar to those in other parts of China. Their As content is near the Chinese coal average, but some local, small coal mines contain high As coals. The highest As content is up to 3.5 wt.% in the coal. The use of high As coals has caused in excess of 3000 cases of As poisoning in several villages. The high As coals are in the Longtan formation, which is an alternating marine facies and terrestrial facies. The coals are distributed on both sides of faults that parallel the regional anticlinal axis. The As content of coal is higher closer to the fault plane. The As content of coal changes greatly in different coal beds and different locations of the same bed. Geological structures such as anticlines, faults and sedimentary strata control the distribution of high As coals. Small Au deposits as well as Sb, Hg, and Th mineralization, are found near the high As coals. Although some As-bearing minerals such as pyrite, arsenopyrite, realgar (?), As-bearing sulfate, As-bearing clays, and phosphate are found in the high As coals, their contents cannot account for the abundance of As in some coals. Analysis of the coal indicates that As mainly exists in the form of As5+ and As3+, perhaps, combined with organic compounds. The occurrence of such exceptionally high As contents in coal and the fact that the As is dominantly organically associated are unique observations.

Domestic coal combustion has had profound adverse effects on the health of millions of people worldwide. In China alone several hundred million people commonly burn raw coal in unvented stoves that permeate their homes with high levels of toxic metals and organic compounds. At least 3,000 people in Guizhou Province in southwest China are suffering from severe arsenic poisoning. The primary source of the arsenic appears to be consumption of chili peppers dried over fires fueled with high-arsenic coal. Coal samples in the region were found to contain up to 35,000 ppm arsenic. Chili peppers dried over high-arsenic coal fires adsorb 500 ppm arsenic on average. More than 10 million people in Guizhou Province and surrounding areas suffer from dental and skeletal fluorosis. The excess fluorine is caused by eating corn dried over burning briquettes made from high-fluorine coals and high-fluorine clay binders. Polycyclic aromatic hydrocarbons formed during coal combustion are believed to cause or contribute to the high incidence of esophageal and lung cancers in parts of China. Domestic coal combustion also has caused selenium poisoning and possibly mercury poisoning. Better knowledge of coal quality parameters may help to reduce some of these health problems. For example, information on concentrations and distributions of potentially toxic elements in coal may help delineate areas of a coal deposit to be avoided. Information on the modes of occurrence of these elements and the textural relations of the minerals and macerals in coal may help predict the behavior of the potentially toxic components during coal combustion.

Silicate-melt inclusions from lavas and pyroclastics from a selected suite of pre-A.D. 1631 interplinian Mt. Somma–Vesuvius lavas and scoria have been experimentally homogenized and studied by microthermometry, electron microprobe (EMPA) and secondary-ion mass spectrometry (SIMS) to examine pre-eruptive volatile content and magma evolution. The melt inclusions have a bubble about 0.06% their volume, uncommonly contain non-condensable gas but do not contain any dense fluid phases. Clinopyroxene-hosted inclusions yield homogenization temperatures (Th) from 1170 to 1260°C, most between 1220 and 1240°C; plagioclase-hosted inclusions have Th from 1210 to 1230°C; these values are typical for the Vesuvius environment. The dominant factor controlling major element variability in the inclusions is clinopyroxene fractionation; MgO varies from 5 to 3 wt%, SiO2 varies from 60 to 48 wt%, total alkalis vary from 15 to 4 wt%, and CaO varies from 13 to 5 wt%. H2O varies from 2.7 to 0.6 wt% and is decoupled from incompatible element evolution suggesting vapor saturation during trapping. Chlorine and F vary from 1.0 wt% to 0 and 0.63 to 0 wt%, respectively. Bulk rock and limited matrix glass analyses show that the lavas lost about half of their F and Cl content except for the A.D. 472–1631 lava which contains similar Cl abundances as the bulk rock. SO3 varies from 0.5 to 0 wt% and compared with matrix glass and bulk rock demonstrate that the lavas have lost essentially all sulfur. The samples can be classified into three age groups, >25,000 yr B.P., 25,000–17,000 yr B.P., and A.D. 472–1631. There is a systematic increase in some components, e.g., total alkalis, SO3, Cl, Li, B, and Sr with the youth of the sample and a decrease in others, e.g., Zr and Y. However, on average these samples seem less evolved than later A.D. 1631–1944 lavas.

Fluid inclusions were measured from a feldspathoid-bearing syenite xenolith entrained in trachyte from Ponza, one of the islands of the Pontine Archipelago, located in the Gulf of Gaeta, Italy. The feldspathoid-bearing syenite consists mainly of potassium feldspar, clinopyroxene, amphibole, biotite, titanite, manganoan magnetite, apatite with minor nosean, Na-rich feldspar, pyrrhotite, and rare cheralite. Baddeleyite and zirkelite occur associated with manganoan magnetite. Detailed electron-microprobe analysis reveals enrichments in REE, Y, Nb, U, Tn as well as Cl and F in appropriate phases. Fluid inclusions observed in potassium feldspar are either silicate-melt or aqueous inclusions. The aqueous inclusions can be further classified as. (1) one-phase vapor, (2) two-phase (V + L) inclusions, vapor-rich inclusions with a small amount of CO2 in most cases; homogenization of the inclusions always occurred in the vapor phase between 359 and 424 degrees C, salinities vary from 2.9 to 8.5 wt. % NaCl equivalent; and. (3) three-phase and multiphase inclusions (hypersaline/sulfur-rich aqueous inclusions sometimes with up to 8 or more solid phases). Daughter minerals dissolve on heating before vapor/liquid homogenization. Standardless quantitative scanning electron microscope X-ray fluorescence analysis has tentatively identified the following chloride and sulfate daughter crystals; halite, sylvite, glauberite, arcanite, anhydrite, and thenardite. Melting of the daughter crystals occurs between 459 and 536 degrees C (54 to 65 wt. % NaCl equivalent) whereas total homogenization is between 640 and 755 degrees C. The occurrence of silicate-melt inclusions and high temperature, solute-rich aqueous inclusions suggests that the druse or miarolitic texture of the xenolith is late-stage magmatic.The xenolith from Ponza represents a portion of the peripheral magma chamber wall that has recorded the magmatic/hydrothermal transition and the passage of high solute fluids enriched in chlorides, sulfur, and incompatible elements.

High-TiO2, quartz-normative (HTQ) tholeiite sheets of Early Jurassic age have intruded mainly Late Triassic sedimentary rocks in several early Mesozoic basins in the eastern United States. Field observations, petrographic study, geochemical analyses and stable isotope data from three HTQ sheet systems in the Culpeper basin of Virginia and Maryland and the Gettysburg basin of Pennsylvania were used to develop a general model of magmatic differentiation and magmatic-hydrothermal interaction for HTQ sheets. The three sheet systems have remarkably similar major-oxide and trace-element compositions. Cumulus and evolved diabase in comagmatic sheets separated by tens of kilometers are related by igneous differentiation. Differentiated diabase in all three sheets have petrographic and geochemical signatures and fluid inclusions indicating hydrothermal alteration beginning near magmatic temperatures and continuing to relatively low temperatures. Sulfur and oxygen isotope data are consistent with a magmatic origin for the hydrothermal fluid.The three sheet systems examined apparently all had a similar style of crystal-liquid fractionation that requires significant lateral migration of residual magmatic liquid. The proposed magmatic model for HTQ sheets suggests that bronzite-laden Magma was intruded in an upper crustal magma chamber, with bronzite phenocrysts collecting in the lower part of the magma chamber near the feeder dike. Early crystallization of augite and Ca-poor pyroxene before significant plagioclase crystallization resulted in density-driven migration of lighter residual magmatic liquids along lateral and vertical pressure gradients towards the upper part of the sheet. The influence of water on the physical properties of the residual liquid, including density, viscosity and liquidus temperature, may have facilitated the lateral movement more than 15 km up dip in the sheets. Exsolution of a Cl- and S-rich metal-bearing aqueous fluid from residual magma resulted in concentration and redistribution of incompatible and aqueous-soluble elements in late-stage differentiated rocks. This proposed hydrothermal mechanism has important economic implications as it exerts a strong control on the final distribution of noble metals in these types of diabase sheets.

Detailed sampling of the Vesuvius lavas erupted in the period A.D. 1631–1944 provides a suite of samples for comprehensive chemical analyses and related studies. Major elements (Si, Ti, Al, Fetotal, Mn, Mg, Ca, Na, K and P), volatile species (Cl, F, S, H2O+, H2O− and CO2), and ferrous iron (Fe2+) were determined for one hundred and forty-nine lavas and five tephra from the A.D. 1631–1944 Vesuvius activity. The lavas represent a relatively homogeneous suite with respect to SiO2, TiO2, FeOtotal, MnO and P2O5, but show systematic variations among MgO, K2O, Na2O, Al2O3 and CaO. The average SiO2 content is 48.0 wt.% and the rocks are classified as tephriphonolites according to their content of alkalis. All of the lavas are silica-undersaturated and are nepheline, leucite, and olivine normative. There is no systematic variation in major-element composition with time, over the period A.D. 1631–1944. The inter-eruption and intra-eruption compositional differences are the same magnitude. The lavas are highly porphyritic with clinopyroxene and leucite as the major phases. Fractionation effects are not reflected in the silica content of the lavas. The variability of MgO, K2O, Na2O, and CaO can be modelled as a relative depletion or accumulation of clinopyroxene.

Mt. Somma-Vesuvius (Naples, Italy) has erupted potassium-rich and silica-undersaturated products during a complicated history of plinian and non-plinian events. Coarse-grained cognate nodules are commonly found in the pyroclastics and are upper crustal in origin. We examined cumulate and subeffusive nodules from the 3800 y.B.P. Avellino. A.D. 79 Pompei, and A.D. 472 Pollena eruptions. Silicate-melt and liquid-vapor fluid inclusion studies in clinopyroxene from both types of nodules have been used to assess the fluids attending crystallization and to place constraints on the pressure and temperature of nodule formation. Thermometric and volumetric data from primary and pseudosecondary CO2-H2O and CO2 and coeval silicate-melt fluid inclusions indicate that they were trapped at a pressure of ∼1 to ∼2.5 kbar at ∼1200°C. This suggests a crystallization depth of ∼4 to ∼10 km. The H2O-bearing fluid inclusions are abundant from plinian eruptions in contrast to non-plinian eruptions where H2O-bearing fluid inclusions were rare. The presence of primary H2O-CO2 fluid inclusions indicates that an immiscible, supercritical H2O-CO2 fluid was in the nodule-forming environment. The H2O-bearing fluid inclusions in plinian nodules may record a higher pre-eruptive H2O content in the bulk magma that is dramatically reflected in the eruption dynamics.

Silicate-melt inclusions hosted by clinopyroxene, leucite, olivine, and plagioclase phenocrysts have been studied by petrography and microthermometry. Fourteen lavas erupted during the Mt. Vesuvius (southern Italy) recent activity (A.D. 1631-1944) have been examined. Bubble and inclusion volumes have been measured and the bubble represents from 2 to 7 vol.% (average values) of the inclusion; the minimum and maximum values range from 0.2 to 84 vol.%. Raman spectroscopic analyses indicate that some bubbles may contain low density CO2. Microthermometric experiments with a LEITZ 1350 heating stage were used to homogenize 64 silicate-melt inclusions in clinopyroxene, leucite, and plagioclase. The homogenization temperatures for clinopyroxene and leucite are similar and range from 1150 to 1265-degrees-C (+/- 20-degrees); whereas, the homogenization temperature measured in plagioclase is lower (1110 and 1210-degrees-C [+/- 20-degrees]). These data arc compatible with a relatively volatile-poor environment during most phenocryst crystallization at depth; however, the presence of uncommon, large, gas-rich inclusions indicates volatile-rich conditions during some episodes of phenocryst crystallization.

Field and geochemical studies of granitic plutons belonging to the Serre batholith, in southern Calabria, show that some of these plutons are associated with minor molybdenite, base-metal occurrences, and granitophile geochemical anomalies. The results of a geochemical survey of granitic bedrock and treatment of the data by statistical techniques indicate a grouping of geochemically anomalous samples, with clusters of high R-mode factor scores that identify potential hosts of significant granite-related mineralization, especially Mo, Sn, and W. Especially favourable hosts are siliceous and generally potassic differentiated granitic rocks, especially near the village of San Todaro, and near Bagni di Guida, Monte Cola, Monte Crocco and Mongiana. These areas are candidates for more detailed exploration, as they contain clustering of significant geochemical anomalies for Mo, Rb, W, Cu, Nb, etc., and more importantly, these granites are known to host base-metal sulphide veins. Granite specialization indices for (Rb/Sr>5, K/Rb<200 and Rb3/Ba.Sr.K>0.1) are also typical of granitic rocks hosting base-metal and granitophile mineralization; high-factor scores for the associations K-Rb-Ba-Al-Pb, Nb-Sn, Sn-As and Cu-Sn are also found.Intrusive rocks from the Serre batholith, and from the nearby Sila batholith, in northern Calabria, have similar fluid inclusion features; both contain fluid inclusions that resemble those from granites known to show mineralization elsewhere. A common characteristic of inclusions in Sn-bearing granitic rocks and those in the Serre batholith is the correlation between homogenization temperature and salinity, suggesting mixing of magmatic saline fluids with cooler, lower salinity meteoric waters. There is no evidence, however, that vigorous, voluminous, and intense alteration by boiling and high salinity hydrothermal systems were developed in the Serre batholith, Sulphide-bearing veins near Bagni di Guida and San Todaro, two of the most important areas identified in this study as potential hosts, probably reflect episodic tectonic adjustments that momentarily dropped the pressure from lithostatic to hydrostatic, producing boiling and minor hydrothermal alteration. Known sulphide occurrences in the Serre batholith are thus unlikely to be expressions of a major hydrothermal alteration and mineralization system, unless the occurrences represent the distal effects of such a system.

The Sila batholith is the focus of an extensive petrogenetic research program, which includes an assessment of its potential to host granite-related ore deposits. Univariate and multivariate statistical techniques were applied to major- and minor-element rock geochemical data. The analysis indicates that the highest potential for mineralization occurs in corundum-normative, peraluminous, unfoliated, relatively late-stage plutons. The plutons are enriched in Rb, Nb, Ta and U, but depleted in Fe, Mg and Sr. The K/Rb, Ba/Rb, Rb/Sr and Rb3/Ba.Sr.K indices and high R-factor scores of Si-K-Rb are typical of mineralized granitic rocks.A reconnaissance fluid inclusion study indicates that the sub-solidus rock was infiltrated by solutions of widely different temperatures (50-416-degrees-C) and variable salinites (0 to approximately 26 wt.% NaCl equivalent). The higher-temperature solutions probably represent granite or magmatic-related Hercynian fluids, whereas the lower-temperature fluids may be either Hercynian or Alpine in age. Fluids with characteristics typical of mineralized "porphyry" systems have not been recognized.

A fluid inclusion study of core from the Mofete 1, Mofete 2, Mofete 5, San Vito 1, and San Vito 3 geothermal wells (Campi Flegrei, Campania, Italy) indicates that the hydrothermal minerals were precipitated from aqueous fluids (±CO2) that were moderately saline (3–4 wt.% NaCl equiv.) to hypersaline (> 26 wt.% NaCl equiv.) and at least in part, boiling. Three types of primary fluid inclusions were found in authigenic K-feldspar, quartz, calcite, and epidote: (A) two-phase [liquid (L) + vapor (V)], liquid-rich inclusions with a range of salinity; (B) two-phase (L + V), vaporrich inclusions with low salinity; and (C) three-phase [L + V + crystals (NaCL)], liquid-rich inclusions with hypersalinity. Results of microthermometric and crushing studies are reported for twenty drill core samples taken from the lower portions of the five vertical wells.