Principal features of impact-generated hydrothermal circulation systems: mineralogical and geochemical evidence

Any hypervelocity impact generates a hydrothermal circulation system in resulting craters. Common characteristics of hydrothermal fluids mobilized within impact structures are considered, based on mineralogical and geochemical investigations, to date. There is similarity between the hydrothermal mineral associations in the majority of terrestrial craters; an assemblage of clay minerals–zeolites–calcite–pyrite is predominant. Combining mineralogical, geochemical, fluid inclusion, and stable isotope data, the distinctive characteristics of impact‐generated hydrothermal fluids can be distinguished as follows: (i) superficial, meteoric and ground water and, possibly, products of dehydration and degassing of minerals under shock are the sources of hot water solutions; (ii) shocked target rocks are sources of the mineral components of the solutions; (iii) flow of fluids occurs mainly in the liquid state; (iv) high rates of flow are likely (10^?4 to 10^?3 m s^?1); (v) fluids are predominantly aqueous and of low salinity; (vi) fluids are weakly alkaline to near‐neutral (pH 6–8) and are supersaturated in silica during the entire hydrothermal process because of the strong predominance of shock‐disordered aluminosilicates and fusion glasses in the host rocks; and (vii) variations in the properties of the circulating solutions, as well as the spatial distribution of secondary mineral assemblages are controlled by temperature gradients within the circulation cell and by a progressive cooling of the impact crater. Products of impact‐generated hydrothermal processes are similar to the hydrothermal mineralization in volcanic areas, as well as in modern geothermal systems, but impacts are always characterized by a retrograde sequence of alteration minerals.     

Pyrophyllite formation in the thermal aureole of a hydrothermal system in the Lower Saxony Basin,Germany

A combined clay mineralogical, fluid inclusion, and K‐Ar study of Upper Jurassic metasediments at the Gehn (Lower Saxony Basin, Germany) provides evidence for a transient hydrothermal event during Upper Cretaceous basin inversion centered on a prominent gravimetric anomaly. Kaolinite and smectite in Oxfordian pelitic parent rocks that cap a deltaic sandstone unit were locally transformed into pyrophyllite, 2M₁ illite, R3 illite–smectite, chlorite, and berthierine at the Ueffeln quarry. The pyrophyllite‐bearing metapelites lack bedding‐parallel preferred orientation of sheet silicates and experienced peak temperatures of about 260–270°C consistent with microthermometric data on quartz veins in the underlying silicified sandstones. The presence of expandable layers in illite–smectite and high Kübler Index values indicate that the thermal event was rather short‐lived. K‐Ar dating of the <0.2 μm fraction of the pyrophyllite‐bearing Ueffeln metapelite yields a maximum illitization age of 117 ± 2 Ma. Lower trapping temperatures of aqueous fluid inclusions in quartz veins and the absence of pyrophyllite in metapelites of the Frettberg quarry in a distance of about 2.5 km from the Ueffeln quarry infer maximum paleotemperatures of only 220°C. The highly localized thermal anomaly at Ueffeln suggests fault‐controlled fluid migration and heat transfer that provided a thermal aureole for pyrophyllite formation in the metapelites rather than metamorphism due to deep burial. A pH neutral hydrothermal fluid that formed by devolatilization reactions or less likely by mixing of meteoric and marine waters that interacted at depth with shales is indicated by the low salinity (3–5 wt. % NaCl equiv.) of aqueous inclusions, their coexistence with methane–carbon dioxide‐dominated gas inclusions as well as carbon, hydrogen, and oxygen isotope data. The upwelling zone of hydrothermal fluids and the thermal maximum is centered on a gravimetric anomaly interpreted as an igneous intrusion (‘Bramsche Massif’) providing the heat source for the intrabasinal hydrothermal system.     

High‐temperature magmatic fluid exsolved from magma at the Duobuza porphyry copper–gold deposit,Northern Tibet

The Duobuza porphyry copper–gold deposit (proven Cu resources of 2.7 Mt, 0.94% Cu and 13 t gold, 0.21 g t^?1 Au) is located at the northern margin of the Bangong‐Nujiang suture zone separating the Qiangtang and Lhasa Terranes. The major ore‐bearing porphyry consists of granodiorite. The alteration zone extends from silicification and potassic alteration close to the porphyry stock to moderate argillic alteration and propylitization further out. Phyllic alteration is not well developed. Sericite‐quartz veins only occur locally. High‐temperature, high‐salinity fluid inclusions were observed in quartz phenocrysts and various quartz veins. These fluid inclusions are characterized by sylvite dissolution between 180 and 360°C and halite dissolution between 240 and 540°C, followed by homogenization through vapor disappearance between 620 and 960°C. Daughter minerals were identified by SEM as chalcopyrite, halite, sylvite, rutile, K–feldspar, and Fe–Mn‐chloride. They indicate that the fluid is rich in ore‐forming elements and of high oxidation state. The fluid belongs to a complex hydrothermal system containing H₂O – NaCl – KCl ± FeCl₂ ± CaCl₂ ± MnCl₂. With decreasing homogenization temperature, the fluid salinity tends to increase from 34 to 82 wt% NaCl equiv., possibly suggesting a pressure or Cl/H₂O increase in the original magma. No coexisting vapor‐rich fluid inclusions with similar homogenization temperatures were found, so the brines are interpreted to have formed by direct exsolution from magma rather than trough boiling off of a low‐salinity vapor. Estimated minimum pressure of 160 MPa imply approximately 7‐km depth. This indicates that the deposit represents an orthomagmatic end member of the porphyry copper deposit continuum. Two key factors are proposed for the fluid evolution responsible for the large size of the gold‐rich porphyry copper deposit of Duobuza: (i) ore‐forming fluids separated early from the magma, and (ii) the hydrothermal fluid system was of magmatic origin and highly oxidized.     

Evidence for volcanic ash fall in the Maya Lowlands from a reservoir at Tikal,Guatemala

Powder X-ray diffraction and petrographic analyses of reservoir sediments from Tikal, Guatemala have identified significant quantities of decomposed volcanic ash in the form of smectite and euhedral bipyramidal quartz crystals. X-ray fluorescence trace element content analysis was used to eliminate distant Sahara-Sahel and Antilles sources. The Zr/Y and Ni/Cr ratios of reservoir sediment from Tikal are consistent with a source from Central American volcanism (e.g., Guatemalan and Salvadoran). AMS radiocarbon dating of the smectite and crystalline quartz-rich reservoir sediments show that volcanic ash fell during the Preclassic, Classic, and Postclassic Maya cultural periods. It may now be possible to develop an effective chronology of ash fall at Tikal and the greater Peten.     

Mobilization of ore fluids during Alpine metamorphism: evidence from hydrothermal veins in the Variscan basement of Western Carpathians,Slovakia

Hydrothermal polymetallic veins of the Gemeric unit of the Western Carpathians are oriented coherently with the foliation of their low‐grade Variscan basement host. Early siderite precipitated from homogeneous NaCl‐KCl‐CaCl₂‐H₂O brines with minor CO₂, while immiscible gas–brine mixtures are indicative of the superimposed barite, quartz–tourmaline and quartz–sulphide stages. The high‐salinity aqueous fluid (18–35 wt%) found in all mineralization stages corresponds to formation water modified by interaction with crystalline basement rocks at temperatures between 140 and 300°C. High brominity (around 1000 ppm in average) resulted from evaporation and anhydrite precipitation in a Permo‐Triassic marine basin, and from secondary enrichment by dissolution of organic matter in the marine sediments at diagenetic temperatures. Sulphate depletion reflects thermogenic reduction during infiltration of the formation waters into the Variscan crystalline basement. Crystallization temperatures of the siderite fill (140–300°C) and oxygen isotope ratios of the parental fluids (4–10‰) increase towards the centre of the Gemeric cleavage fan, probably as a consequence of decreasing water/rock ratios in rock‐buffered hydrothermal systems operating during the initial stages of vein evolution. In contrast, buoyant gas–water mixtures, variable salinities and strongly fluctuating P–T parameters in the successive mineralization stages reflect transition from a closed to an open hydrothermal system and mixing of fluids from various sources. Depths of burial were 6–14 km (1.7–4.4 kbar, in a predominantly lithostatic fluid regime) during the siderite and barite sub‐stages of the north‐Gemeric veins, and up to 16 km (1.6–4.5 kbar, in a hydrostatic to lithostatic fluid regime) in the quartz–tourmaline stage of the south‐Gemeric veins. The fluid pressure decreased down to approximately 0.6 kbar during crystallization of sulphides. U‐Pb‐Th, ⁴⁰Ar/³⁹Ar and K/Ar geochronology applied to hydrothermal muscovite–phengite and monazite, as well as cleavage phyllosilicates in the adjacent basement rocks and deformed Permian conglomerates corroborated the opening of hydrothermal veins during Lower Cretaceous thrusting and their rejuvenation during Late Cretaceous sinistral transpressive shearing and extension.     

Source of ore fluids at the Kalahari Goldridge deposit, Kraaipan greenstone belt, South Africa: evidence from Sr, C and O isotope signatures in carbonates

The Kalahari Goldridge deposit is located in the Archaean Kraaipan greenstone belt in the north-west province of South Africa. Gold mineralization in this deposit is hosted within banded iron formation which is flanked by a mafic schist in the footwall and clastic metasedimentary units in the hanging wall. Data from carbonate minerals from mineralized veins and bulk rock from the A and D zone ore bodies have helped to define the ultimate origin of the ore-forming fluids and their migration history. Carbon isotope ratios of carbonates from both the A and D zone ore bodies have tight clustering from −7.6 to −5.3‰ that indicates a unique origin for the ore-forming fluids associated with the mineralization at Kalahari Goldridge. The δ¹⁸O values of the carbonates have been influenced by temperature gradients and variable degrees of fluid–rock interaction promoting oxygen isotope exchange between ore fluid and host rocks. Minimum ⁸⁷Sr/⁸⁶Sr ratio values of 0.70354 in mineralized veins are most consistent with ore-forming fluids being relatively pristine with a mantle origin. Strontium and the corresponding ore-forming fluids were most likely derived from mantle-derived magmatic rocks probably represented by the meta-basaltic rocks that underlie the ferruginous package in the Kraaipan greenstone belt. Strontium isotopic composition of vein carbonates show considerable variation in ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.70354 to 0.73914. This is consistent with an ore fluid composition that has been modified by the addition of radiogenic Sr possibly during passage of fluid through siliciclastic country rock concomitant with the observed hydrothermal alteration.     

New insights from reactive transport modelling: the formation of the sericitic vein envelopes during early hydrothermal alteration at Butte, Montana

A reactive transport computer code has been employed to model hydrothermal alteration of a granitoid rock bordering a discrete vein channel. The model suggests that the grey sericitic and sericitic with remnant biotite alteration envelopes at the porphyry copper deposit at Butte, Montana, can be formed by a reducing, low pH, and low salinity fluid under constant temperature and pressure conditions of approximately 400 °C and less than 100 MPa during a time span of approximately 100 years or less. Hydrothermal alteration has little effect on the porosity of the host rock (Butte Quartz Monzonite), and the diffusivity of the aqueous species also changes little. A sequence of mineral reaction fronts characterizes the alteration envelopes. The biotite dissolution front occurs closest to the vein channel and marks the transition from the grey sericitic to sericitic with remnant biotite envelope. The plagioclase dissolution front occurs farthest into the matrix and marks the edge of relatively fresh Butte Quartz Monzonite. From the properties of the quasi‐stationary state approximation ( Lichtner 1988 ; Lichtner 1991 ), it follows that once the sequence of reaction fronts is fully established, their relative locations remain constant and the widths of the reaction zones increase with the square root of time.     

Hydrothermal control on organic matter alteration and illite precipitation, Mt Isa Basin, Australia

Abundant illite precipitation in Proterozoic rocks from Northern Lawn Hill Platform, Mt Isa Basin, Australia, occurred in organic matter‐rich black shales rather than in sandstones, siltstones and organic matter‐poor shales. Sandstones and siltstones acted as impermeable rocks, as early diagenetic quartz and carbonate minerals reduced the porosity–permeability. Scanning and transmission electron microscopy (SEM and TEM) studies indicate a relation between creation of microporosity–permeability and organic matter alteration, suitable for subsequent mineral precipitation. K–Ar data indicate that organic matter alteration and the subsequent illite precipitation within the organic matter occurred during the regional hydrothermal event at 1172 ± 50 (2σ) Ma. Hot circulating fluids are considered to be responsible for organic matter alteration, migration and removal of volatile hydrocarbon, and consequently porosity–permeability creation. Those rocks lacking sufficient porosity–permeability, such as sandstones, siltstones and organic matter poor shales, may not have been affected by fluid movement. In hydrothermal systems, shales and mudstones may not be impermeable as usually assumed because of hydrocarbons being rapidly removed by fluid, even with relatively low total organic carbon.     

Granite‐related overpressure and volatile release in the mid crust: fluidized breccias from the Cloncurry District,Australia

The source and transport regions of fluidized (transported) breccias outcrop in the Cloncurry Fe‐oxide–Cu–Au district. Discordant dykes and pipes with rounded clasts of metasedimentary calc–silicate rocks and minor felsic and mafic intrusions extend several kilometres upwards and outwards from the contact aureole of the 1530 Ma Williams Batholith into overlying schists and amphibolites. We used analytical equations for particle transport to estimate clast velocities (≥20 m sec^?1), approaching volcanic ejecta rates. An abrupt release of overpressured magmatic‐hydrothermal fluid is suggested by the localization of the base of the breccias in intensely veined contact aureoles (at around 10 km, constrained by mineral equilibria), incorporation of juvenile magmatic clasts, the scale and discordancy of the bodies, and the wide range of pressure variation (up to 150 MPa) inferred from CO₂ fluid inclusion densities and related decrepitation textures. The abundance of clasts derived from depth, rather than from the adjacent wallrocks, suggests that the pressure in the pipes was sufficient to restrict the inwards spalling of fragments from breccia walls; that is, the breccias were explosive rather than implosive, and some may have vented to the surface. At these depths, such extreme behaviour may have been achieved by release of dissolved fluids from crystallizing magma, in combination with a strongly fractured and fluid‐laden carapace, sitting under a strong, low permeability barrier. The relationship of these breccias to the Ernest Henry iron‐oxide–Cu–Au deposit suggests they may have been sources of fluids or mechanical energy for ore genesis, or alternately provided permeable pathways for later ore fluids.     

A vector of high‐temperature paleo‐fluid flow deduced from mass transfer across permeability barriers (quartz veins)

Quartz veins acted as impermeable barriers to regional fluid flow and not as fluid‐flow conduits in Mesoproterozoic rocks of the Mt Painter Block, South Australia. Systematically distributed asymmetric alteration selvedges consisting of a muscovite‐rich zone paired with a biotite‐rich zone are centered on quartz veins in quartz–muscovite–biotite schist. Geometric analysis of the orientation and facing of 126 veins at Nooldoonooldoona Waterhole reveals a single direction along which a maximum of all veins have a muscovite‐rich side, irrespective of their specific individual orientation. This direction represents a Mesoproterozoic fluid‐flow vector and the veins represent permeability barriers to the flow. The pale muscovite‐rich zones formed on the downstream side of the vein and the dark biotite‐rich zones mark the upstream side. The alteration couplets formed from mica schist at constant Zr, Ga, Sc, and involved increases in Si, Na, Al and decreases in K, Fe, Mg for pale alteration zones, and inverse alteration within dark zones. The asymmetry of the alteration couplets is best explained by the pressure dependence of mineral–fluid equilibria. These equilibria, in combination with a Darcian flow model for coupled advection and diffusion, and with permeability barriers imposed by the quartz veins, simulate the pattern of both fluid flow and differential, asymmetric metasomatism. The determined vector of fluid flow lies along the regional foliation and is consistent with the known distribution of regional alteration products. The presence of asymmetric alteration zones in rock containing abundant pre‐alteration veins suggests that vein‐rich material may have generally retarded regional fluid flow.     

Fluid chemistry in the Solitaire and Dodo hydrothermal fields of the Central Indian Ridge

Fluid chemistry and microbial community patterns in chimney habitats were investigated in two hydrothermal fields located at the Central Indian Ridge. Endmember hydrothermal fluid of the Solitaire field, located ~3 km away from the spreading center, was characterized by moderately high temperature (307°C), Cl depletion (489 mm ), mildly acidic pH (≥4.40), and low metal concentrations (Fe ≤ 105 μm and Mn = 78 μm ). Chloride depletion indicates that the subseafloor source fluid had undergone phase separation at temperatures higher than ~390°C while the metal depletion was likely attributable to fluid alteration occurring at a venting temperature of around 307°C. These different temperature conditions suggested from fluid chemistry might be associated with an off‐spreading center location of the field that allows subseafloor fluid cooling prior to seafloor discharge. The microbial community in the chimney habitat seemed comparable to previously known patterns in typical basalt‐hosted hydrothermal systems. Endmember hydrothermal fluid of the Dodo field, standing on center of the spreading axis, was characterized by high H₂ concentration of 2.7 mm . The H₂ enrichment was likely attributable to fresh basalt–fluid interaction, as suggested by the nondeformed sheet lava flow expansion around the vents. Thermodynamic calculation of the reducing pyrite–pyrrhotite–magnetite (PPM) redox buffer indeed reproduced the H₂ enrichment. The quantitative cultivation test revealed that the microbial community associated with the hydrothermal fluid hosted abundant populations of (hyper)thermophilic hydrogenotrophic chemolithoautotrophs such as methanogens. The function of subseafloor hydrogenotrophic methanogenic populations dwelling around the H₂‐enriched hydrothermal fluid flows was also inferred from the ¹³C‐ and D‐depleted signature of CH₄ in the collected fluids. It was observed that the hydrothermal activity of the Dodo field had ceased until 2013.     

Hydrothermal activity associated with the Ries impact event, Germany

Combined field studies, optical and scanning electron microscopy, and electron microprobe studies of impactites from the Ries impact structure, Germany, have allowed a clearer picture of the hydrothermal system associated with the Ries impact event to be made. Hydrothermal alteration is concentrated within impact‐generated suevites in the interior of the crater (crater suevites) and around the periphery (surficial suevites), with minor alteration in the overlying sedimentary crater‐fill deposits. The major heat source for the Ries hydrothermal system was the suevite units themselves. Hydrothermal alteration of crater‐fill suevites is pervasive in nature and comprises several distinct alteration phases that vary with depth. An early phase of K‐metasomatism accompanied by minor albitization of crystalline basement clasts and minor chloritization, was followed by pervasive intermediate argillic alteration (predominantly montmorillonite, saponite, and illite) and zeolitization (predominantly analcite, erionite, and clinoptilolite). Hydrothermal fluids were typically weakly alkaline during the main stage of alteration. In contrast to the crater‐fill suevites, alteration within surficial suevites was typically restricted to montmorillonite and phillipsite deposition within cavities and fractures. The pervasive nature of the alteration within the crater‐fill suevites was likely due to the presence of an overlying crater lake; whereas alteration within surficial suevites typically occurred under undersaturated conditions with the main source of water being from precipitation. There are exceptional outcrops of more pervasively altered surficial suevites, which can be explained as locations where water pooled for longer periods of time. Hydrothermal fluids were likely a combination of meteoric waters that percolated down from the overlying crater lake and groundwaters that flowed in from the surrounding country rocks.     

Retrograde P–T evolution and high temperature–low pressure fluid circulation in relation to late Hercynian intrusions: a mineralogical and fluid inclusion study of the Charroux-Civray plutonic complex (north-western Massif Central, France)

The calc‐alkaline plutonic complex from Charroux‐Civray (north‐western part of the French Massif Central) displays multiphase hydrothermal alteration. Plutonic rocks, as well as early retrograde Ca–Al silicate assemblages, which have crystallized during cooling and uplifting of the plutonic series, are affected by multiphase chlorite–phengite–illite–carbonate alteration linked to intense pervasive fluid circulation through microfractures. The petrographic study of alteration sequences and their associated fluid inclusions in microfissures of the plutonic rocks, as well as in mineral fillings of the veins, yields a reconstruction of the P–T–X evolution of the Hercynian basement after the crystallization of the main calc‐alkaline plutonic bodies. This reconstruction covers the uplift of the basement to its exposure and the subsequent burial by Mesozoic sediments. Cooling of the calc‐alkaline plutonic series started at solidus temperatures (～650°C), at a pressure of about 4 kbar (1 bar = 10⁵ N m^?2), as indicated by magmatic epidote stability, hornblende barometry and fluid inclusion data. Cooling continued under slightly decreasing pressure during uplift down to 2–3 kbar at 200–280°C (prehnite–pumpellyite paragenesis). Then, a hot geothermal circulation of CO₂‐bearing fluids was induced within the calc‐alkaline rocks leading to the formation of greisen‐like mineralizations. During this stage, temperatures around 400–450°C were still high for the inferred depths (～2 kbar). They imply abnormal heat flows and thermal gradients of 60–80°C km^?1. The hypothesis of the existence of one large or a succession of smaller peraluminous plutons at depth, supported by geophysical data, suggests that localized heat flows were linked to concealed leucogranite intrusions. As uplift continued, greisen mineralization was subsequently affected by the chlorite–phengite–dolomite assemblage, correlated with aqueous and nitrogen‐bearing fluid circulations in the temperature range of 400–450°C. In a later stage, a continuous temperature decrease at constant pressure (～0.5 kbar) led to the alteration of the dolomite–illite–chlorite type in the 130–250°C temperature range.     

A PRELIMINARY PETROGRAPHIC ANALYSIS OF CYPRIOT WHITE SLIP II WARE*

Samples of Late Bronze Age White Slip II ware from Cyprus were analysed using optical and scanning electron microscopy in conjunction with energy and wavelength dispersive analyse The slip has a novel granular nature and the coarser aggregates are impressed into the outer surface of the body, indicating that it was applied to a moist surface before the vessels were fired. It has a consistent mineral assemblage (Mg‐chlorite + illite‐smectite + sphene + anatase/rutile ± albite) which is very similar to that of hydrothermally altered zones associated with copper orebodies in the Troodos Massif which were mined in antiquity Our analysis suggests that the raw material for the slip was not found at the ground surface, because the alteration assemblage is unaffected by oxidation and copper carbonate or iron staining. It may, therefore, be a by‐product of sub‐surface ore extraction     

Hydrogeology of the Krafla geothermal system,northeast Iceland

The Krafla geothermal system is located in Iceland's northeastern neovolcanic zone, within the Krafla central volcanic complex. Geothermal fluids are superheated steam closest to the magma heat source, two‐phase at higher depths, and sub‐boiling at the shallowest depths. Hydrogen isotope ratios of geothermal fluids range from ?87‰, equivalent to local meteoric water, to ?94‰. These fluids are enriched in ¹⁸O relative to the global meteoric line by +0.5–3.2‰. Calculated vapor fractions of the fluids are 0.0–0.5 wt% (~0–16% by volume) in the northwestern portion of the geothermal system and increase towards the southeast, up to 5.4 wt% (~57% by volume). Hydrothermal epidote sampled from 900 to 2500 m depth has δD values from ?127 to ?108‰, and δ¹⁸O from ?13.0 to ?9.6‰. Fluids in equilibrium with epidote have isotope compositions similar to those calculated for the vapor phase of two‐phase aquifer fluids. We interpret the large range in δD_EPIDOTE and δ¹⁸O_EPIDOTE across the system and within individual wells (up to 7‰ and 3.3‰, respectively) to result from variable mixing of shallow sub‐boiling groundwater with condensates of vapor rising from a deeper two‐phase reservoir. The data suggest that meteoric waters derived from a single source in the northwest are separated into the shallow sub‐boiling reservoir, and deeper two‐phase reservoir. Interaction between these reservoirs occurs by channelized vertical flow of vapor along fractures, and input of magmatic volatiles further alters fluid chemistry in some wells. Isotopic compositions of hydrothermal epidote reflect local equilibrium with fluids formed by mixtures of shallow water, deep vapor condensates, and magmatic volatiles, whose ionic strength is subsequently derived from dissolution of basalt host rock. This study illustrates the benefits of combining phase segregation effects in two‐phase systems during analysis of wellhead fluid data with stable isotope values of hydrous alteration minerals when evaluating the complex hydrogeology of volcano‐hosted geothermal systems.     

Monitoring fluid chemistry in iron oxide–copper–gold‐related metasomatic processes,eastern Mt Isa Block,Australia

Most researchers in the Proterozoic eastern Mt Isa Block, NW Queensland, Australia, favour magmatic fluid and salt sources for sodic‐(calcic) alteration and iron oxide–copper–gold mineralization. Here we compare spatial, mineralogic and stable isotope data from regional alteration assemblages with magmatic and magmatic‐hydrothermal interface rocks in order to track chemical and isotopic variations in fluid composition away from inferred fluid sources. Tightly clustered δ¹⁸O values for magnetite, quartz, feldspar and actinolite for igneous‐hosted samples reflect high temperature equilibration in the magmatic‐hydrothermal environment. In contrast, these minerals record predominantly higher δ¹⁸O values in regional alteration and Cu–Au mineralization. This dichotomy reflects partial equilibration with isotopically heavier wallrocks and slightly lower temperatures. Increases in Si concentrations of metasomatic amphiboles relative to igneous amphiboles in part reflect cooling of metasomatic fluids away from igneous rocks. Variations in X_Mg for metasomatic amphiboles indicate local wallrock controls on amphibole chemistry, while variations in X_Cl/X_OH ratios for amphiboles (at constant X_Mg) indicate variable aH₂O/aHCl ratios for metasomatic fluids. Biotite geochemistry also reflects cooling and both increases and decreases in aH₂O/aHCl for fluids away from plutonic rocks. Decreased aH₂O/aHCl ratios for metasomatic fluids reflect in part scavenging of chlorine out of meta‐evaporite sequences, although this process requires already saline fluids. Local increases in aH₂O/aHCl ratios, as well as local decreases in δ¹⁸O values for some minerals (most notably haematite and epithermal‐textured quartz), may indicate ingress of low salinity, low δ¹⁸O fluids of possible meteoric origin late in the hydrothermal history of the region. Taken together, our observations are most consistent with predominantly magmatic sources for metasomatic fluids in the eastern Mt Isa Block, but record chemical and isotopic variations along fluid flow paths that may be important in explaining some of the diversity in alteration and mineralization styles in the district.     

Breccia verde di Sparta,an elusive decorative stone used in antiquity

Breccia verde di Sparta is the traditional name given by the Roman marmorarii of the 19th century to a brecciated volcanic rock whose unknown precise provenance has been determined here for the first time through exploration of the broader area of Psefí (south of Krokees, province of Sparta, Peloponnese, Greece). This location was well known in antiquity and in modern times for having been exploited by the Romans for an important green porphyry named lapis lacedaemonius, nowadays also known as porfido verde antico. This breccia has been seldom used in Roman times for opera sectilia; in contrast, it appears more frequently reused in medieval floors; it is also frequently present in historical lithotecs formed in the 19th and 20th centuries. To fully characterise it and determine its relationships with green porphyry, breccia verde di Sparta samples from the newly discovered source have been thoroughly studied minero-petrographically and geochemically, and their complex genesis has been reconstructed. It appears that after extrusion the original brecciated basaltic andesite underwent extensive hydrothermal low-grade metamorphism, with a complete alteration of the igneous assemblage and minerals that preserved only part of the clinopyroxene phenocrysts. Alteration was accompanied by crystallisation of abundant epidote and chlorite, which imparted its predominant green colour to the rock. These breccias intruded in the lithoclases of the porphyry.     

Electron backscatter diffraction investigation of length‐fast chalcedony in agate: implications for agate genesis and growth mechanisms

Agates of volcanic origin contain a range of silica minerals, with chalcedony and quartz arranged in concentric bands. Although agates are abundant worldwide, little is known about the genesis of their characteristic banding patterns. Current hypotheses suggest the bands result either from precipitation from convecting siliceous hydrothermal influxes or by in situ crystallization of a silica gel. This study combines the use of a variety of analytical techniques, including electron backscatter diffraction (EBSD), cathodoluminescence (CL), and Fourier transform infrared (FT‐IR) spectroscopy, to characterize the silica minerals present and investigate their spatial and crystallographic relationships in the banding arrangement. Microstructural and spectroscopic observations reveal that chalcedony bands are composed of amorphous silica that also contains nanocrystalline and later‐formed microcrystalline quartz. Nano‐ and microcrystalline quartz grew with a‐axes perpendicular to the growth substrate, typical of length‐fast chalcedony. The bands formed as a result of discrete influxes of silica‐rich fluid. Within these individual bands, there is a sequence of minerals: chalcedony‐A (with amorphous silica and nanocrystalline quartz) → chalcedony‐MQ (with microcrystalline quartz) → quartz. This sequence is reflected in the degree of crystallinity, crystal orientations and water content and is analogous to a diagenetic cycle; the initial chalcedony portion of the band commences with amorphous silica with nanocrystalline quartz followed by fibrous microcrystalline quartz crystals; chalcedony then grades into larger equiaxial mesoquartz crystals. This paragenetic sequence suggests a viable model for the growth of chalcedony in agates.     

Application of boron isotopes to the understanding of fluid–rock interactions in a hydrothermally stimulated oil reservoir in the Alberta Basin, Canada

Boron isotope ratios of reservoir minerals and fluids can be a useful geothermometer and monitor of fluid–rock interactions. In Cold Lake oil sands of northern Alberta, there is a large variation in δ¹¹B of the produced waters generated during steam injection and recovery of oil and water. The higher temperature waters (～ 200 °C) have isotopically light δ¹¹B values (+ 3‰ to + 14‰) and high B contents (～150 p.p.m.). It is inferred that the range of δ¹¹B values of the hydrothermal fluids results from reaction with the reservoir rock, and is a function of the temperature of the fluid–rock interaction. The distinct B geochemistry of the produced waters can be used to show that there is no detectable mixing of the oil recovery waters with the regional formation waters or shallow groundwater aquifers containing potable water. Examination of B isotope ratios of reservoir minerals, before and after steam injection, allows the evaluation of sources of B in the reservoir. The only significant phase containing B is pumice. It shows generally positive δ¹¹B values before steam injection and negative values after steam, with δ¹¹B as low as ? 28‰. Other possibly reactive phases include clay minerals and organic matter, but their abundance is not great enough to impact on the isotopic composition of the produced waters. This information makes it possible to evaluate the boron isotope fractionation equation derived from experimental data ( Williams LB (2000) Boron isotope geochemistry during burial diagenesis. PhD Dissertation. The University of Calgary, Alberta, Canada; Williams LB, Hervig RL, Holloway JR, Hutcheon I (2001a) Boron isotope geochemistry during diagenesis: Part 1. Experimental determination of fractionation during illitization of smectite. Geochimica et Cosmochimica Acta, in press). The results show that the fractionation curve predicts the difference between δ¹¹B of the pumice and hydrothermal fluids in the Cold Lake reservoir. This not only indicates that the reservoir fluids have approached boron isotope equilibrium with the reservoir rock, but also shows that B isotopes provide a useful geothermometer for hydrothermally stimulated oil reservoirs.     

Comparing closed system, flow-through and fluid infiltration geochemical modelling: examples from K-alteration in the Ernest Henry Fe-oxide–Cu–Au system

Potassic alteration of rocks adjacent to, and within the Ernest Henry Fe‐oxide–Cu–Au deposit is used here as a test case to investigate fluid–rock interactions using various equilibrium dynamic geochemical modelling approaches available in the HCh code. Reaction of a simple K–Fe–(Na,Ca) brine (constrained by published fluid inclusion analysis) with an albite‐bearing felsic volcanic rock, resulted in predicted assemblages defined by (i) K‐feldspar–muscovite–magnetite, (ii) biotite–K‐feldspar–magnetite, (iii) biotite–quartz–albite and (iv) albite–biotite–actinolite–pyroxene with increasing rock buffering (decreasing log w/r). Models for isothermal–isobaric conditions (450°C and 2500 bars) were compared with models run over a T–P gradient (450 to 200°C and 2500 to 500 bars). Three principal equilibrium dynamic simulation methods have been used: (i) static closed system, where individual steps are independent of all others, (ii) flow‐through and flush, where a part of the result is passed as input further along the flow line, and (iii) fluid infiltration models that simulate fluid moving through a rock column. Each type is best suited to a specific geological fluid–rock scenario, with increasing complexity, computation requirements and approximation to different parts of the natural system. Static closed system models can be used to quickly ascertain the broad alteration assemblages related to changes in the water/rock ratio, while flow‐through models are better suited to simulating outflow of reacted fluid into fresh rock. The fluid infiltration model can be used to simulate spatially controlled fluid metasomatism of rock, and we show that, given assumptions of porosity relationships and spatial dimensions, this model is a first‐order approximation to full reactive transport, without requiring significant computational time. This work presents an overview of the current state of equilibrium dynamic modelling technology using the HCh code with a view to applying these techniques to predictive modelling in exploration for mineral deposits. Application to the Ernest Henry Fe‐oxide–Cu–Au deposit demonstrates that isothermal fluid–rock reaction can account for some of the alteration zonation around the deposit.