gold in porphyry copper deposits its abundance and fate abstract porphyry copper deposits are among the largest reservoirs of gold in the upper crust and are important potential sources for gold in lower temperature epithermal deposits whether gold remains in porphyry copper deposits is important both to their economic attractiveness and to the distribution of gold in the upper crust cu au atomic ratios of porphyry copper ore deposits form a continuous range from about 5000 to 5 000 000 with a median near 40 000 which separates gold rich and gold poor deposits gold is found in porphyry copper deposits in solid solution in cu fe and cu sulfides and as small grains of native gold usually along boundaries of bornite sims ion probe analyses of ore minerals from the gold rich batu hijau kingking and skouries porphyry copper deposits show that bornite contains about 1 ppm au whereas chalcopyrite contains about an order of magnitude less chalcocite and covellite contain 10 20 ppm au but are not abundant enough to account for a significant part of the gold endowment in many porphyry copper deposits the amount of gold presently in solid solution in cu fe sulfides is not adequate to account for all the gold in porphyry copper deposits and the remainder is present as micron scale grains of native gold experiments in the cu fe s au system show that bornite and chalcopyrite can contain about 1000 ppm gold at typical porphyry copper formation temperatures of 600 700 c and indicate that bornite and chalcopyrite in porphyry copper deposits were saturated with respect to gold at temperatures of only 200 300 c in contrast cu au ratios of bulk ore in porphyry copper deposits would require bornite and chalcopyrite to be saturated with respect to gold at temperatures similar to those at which primary potassic ore and alteration are thought to form this indicates that the maximum gold endowment of porphyry copper deposits is probably fixed by the amount of gold that will go into solid solution in cu fe sulfides when the deposit forms at high temperature and that gold is not commonly added later from other sources although it can be redistributed during cooling or later events the experimental data also suggest that high temperature 600 700 c vapors can extract considerably more gold from porphyry copper systems than can low temperature 300 c alteration comparison to cu au ratios of volcanic emissions suggests further that high temperature processes remove copper relative to gold from porphyry copper systems whereas low temperature processes remove gold preferentially and that this can account for deposits with extremely low and high cu au ratios respectively deposits with cu au ratios between about 20 000 and 100 000 however probably reflect different degrees of removal of gold or copper by immiscible sulfides

gold speciation and transport in geological fluids insights from experiments and physical chemical modelling this contribution provides an overview of available experimental thermodynamic and molecular data on au aqueous speciation solubility and partitioning in major types of geological fluids in the earth s crust from low temperature aqueous solution to supercritical hydrothermal magmatic fluids vapours and silicate melts critical revisions of these data allow generation of a set of thermodynamic properties of the auoh aucl 2 auhs and au hs 2 complexes dominant in aqueous hydrothermal solutions however other complexes involving different sulphur forms chloride and alkali metals may operate in high temperature sulphur rich fluids vapours and melts the large affinity of au for reduced sulphur is responsible for au enrichment in s rich vapours and sulphide melts which are important gold sources for hydrothermal deposits thermo dynamic speciation and partitioning data and their comparison with au and s contents in natural fluid inclusions from magmatic hydrothermal gold deposits provide new constraints on the major physical chemical parameters temperature pressure salinity acidity redox and ubiquitous fluid components sulphur carbon dioxide arsenic affecting au concentration transport precipitation and fractionation from other metals in the crust the availability and speciation of sulphur and their changes with the fluid and melt evolution are the key factors controlling gold behaviour in most geological situations

fluid inclusions in quartz from oceanic hydrothermal specimens and the bingham utah porphyry cu deposit a study with pixe and sxrf abstract individual natural fluid inclusions in quartz were selected for non destructive microprobe analysis by synchrotron x ray fluorescence sxrf and proton induced x ray emission pixe in order to compare and contrast the compositions of porphyry type ore forming brines and two types of ocean crustal brines the inclusions contained brines with high salt concentrations typically 20 40 wt total and one or more daughter crystals the x ray and proton beams produced detectable characteristic x rays for many elements and allowed the quantification of concentrations for many elements with atomic number z 14 fluid inclusions associated with the core of the bingham ut porphyry cu mo deposit contain nacl brines that also contain element typical range in ppm k 12 000 100 000 ca 17 000 mn 8000 fe 120 000 cu 8000 zn 5000 br 2000 these values are in good agreement with published estimates and results from sxrf and pixe experiments are generally consistent the bingham fluid compositions closely resemble brines from the porphyry mo cu deposit at questa nm inclusions from two suites of oceanic plutonic rock samples gave pixe results consistent with published sxrf analyses from other inclusions in the same samples new inclusion analyses from the mathematician ridge locality indicate the nacl brines also contain on average element ppm k 3500 ca 35 000 mn 4900 cu 400 zn 200 br 1000 new inclusion analyses from the oceanographer transform locality indicate nacl brines that also contain on average k 37 000 ca 35 000 mn 10 000 cu 400 zn 2200 br 1000 these values are calculated on the assumption that fe in the inclusions is 50 000 ppm compared to continental ore forming brines the oceanic brines have higher ca and lower k and cu concentrations

halogen and ar ar age determinations of inclusions within quartz veins from porphyry copper deposits using complementary noble gas extraction techniques abstract extension of ar ar methodology has been used to determine mineralisation ages from mica inclusions and to simultaneously evaluate the noble gas and halogen composition of inclusion fluids within irradiated quartz vein samples from five porphyry copper deposits samples have been collected from the potassic and propylitic zones of bingham canyon utah and four arizonan deposits silverbell globe miami pinto valley and ray data obtained using three noble gas extraction techniques laser ablation in vacuo crushing and stepped heating are compared with each other laser ablation provides a means for the analysis of individual fluid inclusions but is limited by blank levels and detection limits stepped heating and in vacuo crushing are bulk extraction techniques that preferentially release gases from solid and fluid inclusion phases respectively and can be used in combination to obtain accurate and meaningful ages of mineralisation ages obtained for porphyry copper deposits are as follows bingham canyon 37 1 0 5 ray 65 3 1 5 globe miami 61 7 3 4 pinto valley 63 2 8 0 and silverbell 55 8 1 8 the age of mineralisation at ray is of particular interest as it enables a reported discrepancy in k ar ages to be understood halogen data for the bingham canyon samples gives insight into the partitioning of the heavy halogens br and i between solid and liquid phases

formation of a paleothermal anomaly and disseminated gold deposits associated with the bingham canyon porphyry cu au mo system utah the thermal history of the oquirrh mountains utah indicates that hydrothermal fluids associated with emplacement of the 37 ma bingham canyon porphyry cu au mo deposit extended at least 10 km north of the bingham pit an associated paleothermal anomaly enclosed the barneys canyon and melco disseminated gold deposits and several smaller gold deposits between them previous studies have shown the barneys canyon deposit is near the outer limit of an irregular distal au as geochemical halo about 3 km beyond an intermediate pb zn halo and 7 km beyond a proximal pyrite halo centered on the bingham porphyry copper deposit the melco deposit also lies near the outer limit of the au as halo analysis of several geothermometers from samples collected up to 22 km north of the bingham canyon porphyry cu au mo deposit indicate that most sedimentary rocks of the oquirrh mountains including those at the gold deposits have not been regionally heated beyond the oil window less than about 150 c for geologically reasonable heating durations the maximum sustained temperature at melco 6 km north of the bingham pit and at barneys canyon 7 5 km north of the pit was between 100 c and 140 c as indicated by combinations of conodont color alteration indices of 1 5 to 2 mean random solid bitumen reflectance of about 1 0 percent lack of annealing of zircon fission tracks and partial to complete annealing of apatite fission tracks the pattern of reset apatite fission track ages indicates that the gold deposits are located approximately on the 120 c isotherm of the 37 ma paleothermal anomaly assuming a heating duration of about 106 years the conodont data further constrain the duration of heating to between 5 104 and 106 years at approximately 120 c the 18o of quartzite host rocks generally increases from about 12 6 per mil at the porphyry to about 15 8 per mil approximately 11 km from the bingham deposit this change reflects interaction of interstitial clays in the quartzite with circulating meteoric water related to the bingham canyon porphyry system the 18o and 13c values of limestone vary with respect to degree of recrystallization and proximity to open fractures recrystallized limestone at the melco and barneys canyon gold deposits has the highest 18o values about 30 whereas limestone adjacent to the porphyry copper deposit has the lowest values about 10 the high 18o values for the recrystallized limestone at barneys canyon and melco strongly suggest that mineralization was related to low temperature fluids with exceptionally high 18oh2o values such as could be derived from water in a crater lake of an active volcano the age of formation of the gold deposits has been interpreted to range from jurassic to eocene the mineralized rocks at the barneys canyon and melco deposits are likely the same age as the geochemically similar deposits that are present in north striking late faults that cut the bingham canyon porphyry the patterns of apatite and zircon fission track data conodont color alteration indices solid bitumen reflectivity stable isotope data and mineral zoning are consistent with the gold deposits being genetically related to formation of the 37 ma bingham porphyry deposit we interpret the disseminated gold mineralization to be related to collapse of the bingham canyon hydrothermal system in which isotopically heavy oxidizing acidic waters possibly from an internally draining acidic crater lake mixed with and were entrained into reduced gold bearing meteoric water fluids in the collapsing main stage hydrothermal system most of this fluid mixing and cooling was probably located close to the hydrologic interface between the sedimentary basement rocks and overlying volcanic rocks

a fluid inclusion and stable isotope study of the pebble porphyry copper gold molybdenum deposit alaska abstract the hydrothermal fluid evolution in the supergiant pebble porphyry cu au mo deposit in southwest alaska has been constrained using fluid inclusion and light stable isotope data the deposit is related to 90 ma granodiorite porphyry intrusions and mineralization occurs primarily in sodic potassic potassic and advanced argillic alteration zones throughout the deposit vein quartz hosts intermediate density fluid inclusion assemblages with an average salinity of 9 5 wt nacl equivalent and homogenization temperatures of 377 to 506 c pressure corrections result in trapping temperatures with a maximum of 610 c this early fluid exsolved from a crystallizing magma at depth and underwent phase separation under varying conditions during cooling and depressurization forming two distinct fluid compositions the two fluids formed two hydrothermal alteration assemblages which have different metal signatures in the hydrothermal core in the eastern part of the system high density quartz veins potassic alteration and the most economically significant mineralization are related to 52 wt nacl equivalent brines that coexist with very low density vapor in the western part of the system peripheral to the hydrothermal core lower quartz vein densities accompanied by sodic potassic alteration and lower grade mineralization are associated with 38 wt nacl equivalent brines and low density vapor sulfide mineralization precipitated late in this early alteration event at temperatures between 375 and 330 c fluids related to sodic potassic alteration minerals have 18 o signatures from 6 0 to 10 5 vsmow and d values from 70 to 41 vsmow which are consistent with a magmatic fluid source fluids related to potassic alteration assemblages have 18 o of 1 7 to 2 3 vsmow and d of 68 to 59 vsmow which suggests that the magmatic fluids evolved to lighter oxygen isotope signatures due to quartz precipitation during alteration lower temperature 280 c sericite and illite alteration followed the high temperature magmatic stage and formed from the rising vapor plume as it mixed with varying amounts of meteoric fluid sericite in quartz sericite pyrite alteration on the periphery of the deposit and illite from areas of illite kaolinite alteration which overprints sodic potassic alteration and forms quartz illite pyrite alteration within the deposit are related to low salinity aqueous fluids that have a significant magmatic component 2 1 to 4 1 18 o and 76 to 67 d illite alteration which overprints both potassic alteration and quartz sericite pyrite alteration formed from fluids with a large meteoric component 9 1 to 4 8 18 o and 101 to 90 d the higher vein density and therefore higher permeability in the core of the deposit facilitated ingress of larger amounts of meteoric fluid compared with the more peripheral region advanced argillic alteration and associated high grade mineralization are related to a second pulse of magmatic fluid which did not intersect the two phase field during cooling and depressurization the fluid contracted to form a 3 wt nacl equivalent aqueous fluid that resulted in a sericite pyrite bornite digenite bearing assemblage with a magmatic signature 4 6 to 6 5 18 o and 108 to 102 d at 340 c cooling and mixing of this fluid with meteoric water resulted in a fluid that formed a pyrophyllite quartz sericite chalcopyrite bearing assemblage 8 9 to 0 6 18 o and 110 to 96 d at 300 c compared to older potassic and sodic potassic alteration the advanced argillic alteration has a highly depleted d signature which is attributed to degassing of a crystallizing intrusive fluid source

evolution from magmatic to hydrothermal activity beneath the cerro escorial volcano nw argentina as sampled by erupted quartz and brines abstract large quartz pebbles erupted with the escorial ignimbrite provide insight into the late magmatic evolution of the shallow cooling magmatic hydrothermal system below the cerro escorial volcano of the southern central volcanic zone in the argentine andes the ignimbrite is of relatively small volume crystal rich dacitic in composition and not particularly water rich as amphibole is absent eruption temperature was estimated to be close to 850 c the quartz pebbles provide insight into the magmatic hydrothermal transition beneath the volcano based on textures trace element composition analyzed by laser ablation inductively coupled plasma mass spectrometry and inclusion content the pebbles can be separated into pegmatite like megacrysts and lower temperature epithermal microcrystalline quartz both types are distinct from magmatic phenocrysts present in porphyritic clasts ejected by the ignimbrite the megacrysts show a wide range of trace element concentrations with elevated al concentrations and al ti and ge ti ratios compared to quartz phenocrysts although some contamination by submicroscopic inclusions and cooling to near solidus temperatures may perturb the signal in some cases the range of trace element concentrations in quartz crystals from this system may reflect a change in crystallization conditions from initial precipitation from typical evolved silicate melt to fast growth from residual melt and or fluid in pegmatitic pockets or coarse grained hydrothermal veins at locally variable precipitation conditions abundant primary and secondary silicate melt inclusions and a variety of secondary fluid inclusions are present within the megacrysts in particular brine inclusions are densely packed with salt crystals sometimes anhydrite and or a silicate crystal but no visible liquid at room temperature and co existing vapor inclusions are of very low density heating experiments of brine inclusions reveal last salt and vapor bubble dissolution temperatures around 600 700 c but an immiscible silicate melt surrounding the homogenized salt globule remains even at unreasonably high temperature the co existence of silicate melt and fluid inclusions reinforces the magmatic nature of the fluids while boiling trails of brine with cu concentrations of several percent and vapor point to relatively low pressures

evolution of magmatic vapor to gold rich epithermal liquid the porphyry to epithermal transition at nevados de famatina northwest argentina fluid inclusions in the subeconomic porphyry cu mo au system at nevados de famatina and closely associated high sulfidation epithermal cu au ag as sb te veins at la mejicana northwest argentina were studied to reconstruct the evolution of hydrothermal fluids from their deep magmatic source to the shallow epithermal environment field geology vein petrography fluid inclusion microthermometry and single inclusion microanalysis by laser ablation inductively coupled plasma mass spectrometry la icp ms were combined to determine the evolution of pressure temperature and ore metal concentrations in the fluids cathodoluminescence imaging complements transmitted light petrography to constrain the successive stages of quartz formation and the entrapment sequence of the fluid inclusion populations aqueous liquid inclusions of 5 wt percent nacl equiv salinity trapped in quartz sericite pyrite qsp veins between 360 and 325 c contain unusually high concentrations of cu 400 5 000 ppm as 200 ppm sb and te both up to 100 ppm and au several ppm along with other ore forming elements these veins are paragenetically transitional between subeconomic porphyry copper mineralization exposed in the valley floor and high sulfidation epithermal veins with high au grades which are preserved along a high ridge adjacent to the porphyry stock low density vapor and hypersaline liquid i e brine inclusions were trapped in early formed quartz of the porphyry stockwork veins between 450 and 600 c the brine contains lower cu and au concentrations than coexisting vapor inclusions and texturally even earlier inclusions of intermediate density that are trapped in phenocrysts and some stockwork veins the latter may be equivalent to a parental fluid the low and intermediate density fluids compositionally overlap in salinity with the aqueous liquids recorded by the later transitional quartz sericite pyrite veins fluid inclusions and geologic time relations indicate that the transitional quartz sericite pyrite veins were the channelways for metal rich aqueous liquids that generated the high sulfidation epithermal cu au deposit these mineralizing liquids are interpreted to have evolved by continuous density increase contraction from a low salinity s rich magmatic fluid of low to intermediate density this vaporlike fluid was produced by exsolution from a magma that existed at greater depth during the late stages of cooling of the magmatic hydrothermal complex and probably underwent minor brine separation prior to reaching the present level of exposure epithermal mineral precipitation occurred upon dilution of the low salinity magmatic fluid with meteoric water which entered the hydrothermal system as it was cooled and successively eroded during continued magmatic fluid ascent

gold transporting hydrothermal fluids in the earth s crust an introduction hydrothermal ore deposits that are exploited for gold include both gold only deposits such as orogenic deposits and gold bearing examples of the common hydrothermal deposit types that are formed around upper crustal magmatic centres in particular porphyry and epithermal deposits fluid inclusion data have shown that ore fluids of gold only deposits are compositionally distinct compared to fluids of other deposit types fluids of the latter deposit types are in contrast not distinctive and recent research has been focussed on relating gold content to geochemical and petrological aspects of related magmatic systems and to fluid evolution on migration through the crust this special publication includes an up to date summary of thermodynamic parameters of aqueous au species at high temperatures and pressures a dataset of fluid inclusion properties and compositions from orogenic deposits of different parts of the world several comprehensive case studies of different types of gold deposits and their fluids from the usa brazil egypt slovakia and bulgaria and numerical modelling aimed to define key parameters that affect fluid flow and gold deposition at a range of scales historical and disciplinary context the majority of gold deposits of the earth s crust are generated by fluxes of hot aqueous hydrothermal fluids that are efficiently focussed within relatively small volumes of rock a proportion of this gold is extracted from hydrothermal deposit types such as iron oxide copper gold iocg deposits porphyry deposits and lowand high sulphidation epithermal deposits as a co product with other metals most commonly with copper or silver the other group 12 elements a similar proportion is however a product of gold only hydrothermal deposits including orogenic gold intrusion related gold irgd and carlin type gold deposits in these gold only deposit types au is in most cases not only the only commodity of economic interest in the ore but we can infer from the available multi element compositional data on fluid inclusions that it is the only commodity of interest transported in the hydrothermal fluids of these deposits e g yardley et al 1993 su et al 2009 gold only hydrothermal deposits are thus environments in which gold is very effectively fractionated from other metals presumably as a consequence of gold s unique chemical properties such as high electronegativity and the tendency to form bonds with strong covalent character e g crerar et al 1985 and the strength of relativistic effects on bonding behaviour e g pyykko 2012 the affinity of gold with reduced sulphur in hydrothermal fluids was first experimentally demonstrated by seward 1973 and has been confirmed in all subsequent experimental studies see pokrovski et al 2014 gold only deposits including orogenic gold deposits do appear to be products of hydrothermal fluids that are chemically distinct compared to fluids of other higher temperature hydrothermal ore deposit types including porphyry deposits epithermal deposits and greisens hypersaline fluids are absent at almost all deposits the dominant fluid contains sufficient co2 to form a carbonic phase in fluid inclusions and has relatively low salinity in contrast the fluids of gold rich epithermal and porphyry deposits are not distinct from those of typical deposits of these types at least with respect to compositional fluid parameters that can be constrained through routine microthermometry it is difficult to pinpoint who first recognized that co2 bearing and relatively low salinity ore fluids are characteristic and almost ubiquitous in orogenic gold deposits roedder 1973 in his early comprehensive summary of knowledge of fluid inclusion compositions reported that kravtsov fridman 1965 recorded high co2 in fluid inclusions in gold quartz veins and suggested that its abundance might be an effective exploration tool for gold boyer et al 1967 recognized co2bearing fluid inclusions in quartz veins and summarized the results of other similar studies to suggest a clear relation direct or indirect between gold and co2 in another early work coveney kelly from garofalo p s ridley j r eds gold transporting hydrothermal fluids in the earth s crust geological society london special publications 402 http dx doi org 10 1144 sp402 9 the geological society of london 2014 publishing disclaimer www geolsoc org uk pub ethics at universita di bologna on june 30 2014 http sp lyellcollection org downloaded from

fluid density control on vapor liquid partitioning of metals in hydrothermal systems hot aqueous fluids both vapor and saline liquid are primary transporting media for metals in hydrothermal magmatic systems despite the growing geological evidence that the vapor phase formed through boiling of magmatic ore bearing fluids can selectively concentrate and transport metals the physical chemical mechanisms that control the metal vapor liquid fractionation remain poorly understood we performed systematic experiments to investigate the metal vapor liquid partitioning in model water salt gas systems h2o nacl kcl hcl at hydrothermal conditions measurements show that equilibrium vapor liquid fractionation patterns of many metals are directly related to the densities of the coexisting vapor and liquid phases despite differences in the vapor phase chemistry of various metals that form hydroxide chloride or sulfide gaseous molecules of contrasting volatile properties water solute interaction is a key factor that controls the metal transfer by vapor like fluids in earth s crust these findings allow quantitative prediction of the vapor liquid distribution patterns and vapor phase metal transport in a wide range of conditions our density model accounts well for the vapor brine distribution patterns of na si fe zn as sb and ag observed in fluid inclusions from magmatic hydrothermal deposits for au and cu the partitioning in favor of the liquid phase predicted in a sulfur free system contrasts with the copper and gold enrichment observed in natural vapor like inclusions the formation of stable complexes of cu and au with reduced sulfur may allow for their enhanced transport by sulfur enriched magmatic hydrothermal vapors

copper deposition during quartz dissolution by cooling magmatic hydrothermal fluids the bingham porphyry abstract scanning electron microscope cathodoluminescence imaging is used to map successive generations of fluid inclusions in texturally complex quartz veinlets representing the main stage of ore metal introduction into the porphyry cu au mo deposit at bingham utah following conventional fluid inclusion microthermometry laser ablation inductively coupled plasma mass spectrometry la icpms is applied to quantify copper and other major and trace element concentrations in the evolving fluid with the aim of identifying the ore forming processes textures visible in cathodoluminescence consistently show that the bulk of vein quartz q1 characterized by bright luminescence crystallized early in the vein history cu fe sulfides are precipitated later in these veins in a microfracture network finally filled with a second generation of dull luminescing q2 quartz mapping of brine and vapor inclusion assemblages in these successive quartz generations in combination with la icpms microanalysis shows that the fluids trapped before and after cu fe sulfide precipitation are very similar with respect to their major and minor element composition except for copper copper concentrations in inclusions associated with ore formation drop by two orders of magnitude in a tight pressure temperature interval between 21 and 14 mpa and 425 350 c several hundred degrees below the temperature of fluid exsolution from the magma copper deposition occurs within a limited p t region in which sulfide solubility shows strong normal temperature dependence while quartz solubility is retrograde this permits copper sulfide deposition while secondary vein permeability is generated by quartz dissolution the brittle to ductile transition of the quartz feldspar rich host rocks occurs in the same temperature range which further enhances vein reactivation and promotes cooling and expansion of fluids ascending across the transition from lithostatic to hydrostatic conditions

subepithermal au pd mineralization associated with an alkalic porphyry cu au deposit mount milligan quesnel terrane british columbia canada at the mount milligan cu au porphyry deposit quesnel terrane british columbia canada barren and weakly mineralized late stage hydrothermal veins occur in volcanic rocks adjacent to zones of cu au porphyry mineralization and have overprinted the porphyry stage veins the earliest of the late stage hydrothermal veins are barren and consist of quartz pyrite carbonate chlorite tourmaline these veins are similar to transitional to late stage hydrothermal veins in other alkaline porphyry cu au deposits and we consider these to be the equivalent of transitional post porphyry pre epithermal quartz sericite pyrite veins in calc alkaline porphyry environments a later generation of volumetrically minor mineralized veins are composed of pyrite hg and as bearing quartz carbonate chlorite and contain early electrum arsenopyrite tetra hedrite tennantite platinum group element pge tellurides galena sphalerite barite and chalcopyrite as inclusions in pyrite and a later assemblage of electrum pge tellurides arsenides and antimonides galena sphalerite chalcopyrite and various au ag te bi minerals in annealed fractures and open space infillings in quartz and pyrite metal precipitation in these veins was temporally and spatially associated with the deposition and later recrystallization of pyrite primary fluid inclusions in quartz in the barren and weakly mineralized veins are two phase l v homogenize to liquid over a narrow range in t 170 270 c n 96 12 veins and show a wide range in salinity 4 2 wt nacl equiv to 28 7 wt cacl2 equiv when all samples are considered however individual veins show narrow ranges in salinity and homogenization temperature la icp ms analyses indicate that the fluids were highly enriched in as to 2 260 ppm sb to 230 ppm b to 5 400 ppm au 1 2 ppm and pd 0 5 1 ppm but depleted in cu 80 ppm compared to typical porphyry stage fluids metal ratios in the fluids overlap with bulk rock metal ratios in the mineralized veins the inclusions are interpreted to contain a contracted magmatic vapor produced by boiling that lost cu during the formation of porphyry stage veins at depth fluids show decreasing b as sb and increasing sr ca and salinity with time stable c o and h isotope analyses of vein minerals indicate that mixing of this magmatic fluid with meteoric water was not responsible for metal deposition rather metal precipitation was possibly the result of mixing of the magmatic derived fluid with a heated saline groundwater the precious and accessory metal mineralogy of the hydrothermal veins is similar to that found in low to intermediate sulfidation epithermal systems fluid inclusion microthermometry and chlorite thermometry constrain the approximate formation conditions of the veins between 200 and 1 500 bars and 240 and 280 c after the formation of the mineralized veins circulation of low salinity metal depleted fluids occurred these latest stage fluids may have formed by mixing of the saline magmatic fluid groundwater hybrid with meteoric water the results of this study suggest a genetic link between porphyry stage events and the deposition of au and pge in late stage veins in an alkalic igneous environment recognition of hydrothermal processes involving the transport of au pge as sb bi te b rich fluids in the subepithermal regimes implies that low sulfidation epithermal au deposits may have been present in the shallower parts of the magmatic hydrothermal complex and that there is potential for the discovery of pge rich epithermal veins in less deeply exhumed terranes on the other hand the formation of high grade low sulfidation epithermal au pge deposits may be prohibited if porphyry epithermal transitional fluids precipitate ore metals through mixing with groundwater prior to reaching the level where meteoric water mixing and epithermal boiling normally occur

the bingham canyon porphyry cu mo au deposit iii zoned copper gold ore deposition by magmatic vapor expansion fluid inclusion microthermometry and laser ablation icpms microanalysis are combined with geological and textural observations to reconstruct the spatial and temporal evolution of magmatic fluids that formed the subvolcanic porphyry cu au mo ore deposit at bingham canyon utah the bingham canyon orebody is exposed over 1 6 km vertically and has the shape of an inverted cup with distinct metal zoning fluid inclusions in the barren but highly veined and potassically altered deep center of the system have intermediate density 0 6 g cm 3 and a salinity of 7 wt percent nacl equiv they have subequal concentrations of na k fe and cu and contain minor co2 the intermediate density fluids were trapped as a single phase mostly at 500 c and 800 bars the au cu rich center near the top of the orebody contains low density vapor inclusions 0 2 g cm 3 coexisting with brine inclusions containing 45 wt percent nacl equiv the vertical transition of different inclusion types indicates phase separation of the single phase input fluid upon volume expansion associated with a pressure drop to 200 100 bars mass balance calculation based on all analyzed inclusion components indicates that the mass of the vapor phase exceeded that of the brine by 9 1 the vapor contained cu as its dominant cation 1 5 wt and contributed about 95 percent of the total amount of copper transported to the base of the orebody bornite chalcopyrite and native gold were precipitated in a narrow temperature interval from 430 to 350 c into secondary pore space created by local redissolution of vein quartz as a result of retrograde quartz solubility in the vapor dominated fluid system intermediate density fluid inclusions in the deepest parts of the peripheral copper ore zone have identical density and composition including similar gold contents as those in the deep center microthermometry and statistical estimation of phase proportions in the inclusions show that the vapor in the peripheral cu rich but au poor ore zone remained denser and the separating brine was less saline 36 wt nacl equiv compared to vapor and brine in the central au cu ore zone this indicates that the peripheral fluids experienced a lower degree of phase separation due to slightly higher fluid pressure at equivalent temperature compared to more strongly expanding fluids in the center of the system the systematic zoning of au cu within the ore shell despite compositionally similar input fluids is interpreted to have resulted from slightly different pressure temperature density evolution paths of magmatic fluids copper was selectively precipitated in the peripheral ore zone in contrast to complete coprecipitation of au and cu in the central upflow zone of the vapor plume the formation of particularly rich cu au ore in the center of the upward expanding fluid plume is consistent with published experimental data showing that the solubility of metals in hydrous vapor decreases sharply with falling pressure due to destabilization of the hydration shell around metal complexes in expanding vapor this interpretation supports the classic vapor plume model for porphyry copper ore formation but additionally emphasizes the role of sulfur bearing complexes as a key chemical control on magmatic hydrothermal metal transport and the deposition of cu and au in porphyry ores our interpretation of selective cu au precipitation as a function of vapor density can explain the more general observation that most gold rich porphyry copper deposits are formed in shallow sub volcanic environments whereas deeper seated porphyry cu mo deposits are generally gold poor

the origin of ch4 rich fluids in reduced porphyry skarn cu mo au systems abstract although most of the methane on earth is of biogenic origin significant abiogenic methane has been identified in a variety of geological environments moreover the presence of methane has been reported recently in fluid inclusions from a number of reduced porphyry deposits the genesis of this methane however remains poorly understood here we present results of a study of magma exsolved ch4 rich aqueous fluid inclusions in the seleteguole reduced porphyry skarn cu mo au deposit nw china four types of fluid inclusions namely intermediate density two phase aqueous inclusions low density vapor inclusions brine inclusions and aqueous liquid inclusions have been distinguished on the basis of the phases present at room temperature the intermediate density inclusions were trapped as a single phase and contain 3 8 10 4 mol kg ch4 corresponding to an oxygen fugacity between fmq 1 and fmq 0 5 this attests to the remarkably reduced nature of the fluid the 13c value of the ch4 hosted fluid inclusions ranges from 29 4 to 19 1 pdb which distinguishes this methane from biogenic methane indeed the high homogenization temperature of the ch4 rich inclusions 400 c implies that the ch4 was exsolved directly from the magma given the environment in which the magma was likely generated i e at or immediately above a subducting plate we propose that the methane was produced by reactions involving organic matter bearing carbonate rocks in the subduction zone although cu mo and au in most porphyry systems are interpreted to have been transported under oxidizing conditions our results indicate that reduced aqueous liquids and vapors are also capable of transporting appreciable concentrations of these metals

mobility and h2o loss from fluid inclusions in natural quartz crystals petrographic observations on quartz crystals from the mole granite australia and other localities shed new light on the mechanisms of post entrapment modification of fluid inclusions these modifications include migration away from pseudosecondary trails changes in fluid salinity and density shape distortion and the formation of sweat haloes around strongly deformed inclusions increases in fluid salinity which usually are associated with inclusion migration indicate water losses of up to 50 however la icp ms analysis of unmobilized and mobilized inclusions of the same trail reveals basically unchanged ratios of major and trace element cations with the exception of li which seems to be incorporated into the crystal lattice during migration despite the fact that all these modifications are closely related to deformation processes they occur not only in mechanically deformed quartz but also in free standing crystals in the latter samples stress has been generated internally as a result of brazil twinned growth and compositional zonation these observations and their interpretation leads to a list of practical criteria that should help in differentiating between reliable and suspect fluid inclusions in other samples

the bingham canyon porphyry cu mo au deposit i sequence of intrusions vein formation and sulfide deposition the bingham canyon porphyry copper gold molybdenum deposit is one of the largest and highest grade porphyry orebodies in the world this study focused on the northwest side of the deposit where quartz mon zonite porphyry qmp the first and largest porphyry intrusion hosts the bulk of the high grade copper gold ore 1 0 cu 1 0 ppm au the north northeast trending high grade zone had pre mining dimensions of 1 500 m strike 300 m vertical and 500 m width and contained more than 500 million tonnes mt of ore associated with potassic alteration and abundant quartz veins the lack of superimposed sericitic alteration yielded ideal exposures in which to study the early high temperature stages of ore formation a style of mineralization that in many porphyry deposits represents the major period of copper introduction we mapped multiple porphyry dikes in the sequence 1 qmp 2 latite porphyry lp 3 biotite porphyry bp 4 quartz latite porphyry breccia qlpbx and 5 quartz latite porphyry qlp porphyry dikes faults and quartz veins are steeply dipping and have two dominant orientations north northeast and northwest striking dikes have a north northeast strike but they thicken and develop northwest trending apophyses and host high grade copper gold zones at intersections with northwest faults indicating that magmatic hydrothermal fluids were focused by these structural intersections each porphyry intrusion was accompanied by a similar sequence of veins potassic alteration and sulfides biotite veinlets were followed by fractures with early dark micaceous edm halos of sericite k feldspar biotite andalusite and local corundum containing disseminated bornite chalcopyrite gold edm halos are cut by multiple generations of a quartz veins representing the main cu au ore forming event postdating all intrusions are quartz molybdenite veins followed by quartz sericite pyrite veins cathodoluminescence cl petrography identified distinct a quartz veinlets consisting of dark luminescing quartz filling fractures and dissolution vugs in earlier a quartz veins and adjacent porphyry wall rock these veinlets contain abundant bornite and chalcopyrite and minor k feldspar and are closely linked in time to the introduction of the bulk of the copper and gold although a similar sequence of veins was repeated on emplacement of all porphyry intrusions the vein density and intensity of potassic alteration declined with time the youngest porphyry qlp is mostly weakly mineralized and locally unaltered these observations indicate that magmatic hydrothermal fluids underwent a similar physiochemical evolution during and immediately following emplacement of each of several porphyry dikes the relationship between edm veins and a quartz veins requires that the flux of magmatic fluid from the magma chamber occurred in an episodic manner as opposed to a continuous discharge vein truncation relationships coupled with abrupt changes in copper gold grades sulfide ratios and potassic alteration intensity at porphyry intrusive contacts indicate that the mass of introduced copper and gold decreased significantly during successive porphyry intrusive hydrothermal cycles presumably due to depletion of metals and volatiles in the underlying magma chamber

scanning electron microscope cathodoluminescence analysis of quartz reveals complex growth histories in veins from the butte porphyry copper deposit montana scanning electron microscope cathodoluminescence sem cl analysis of quartz reveals textures that cannot be observed using optical microscopy or backscattered electrons these cryptic textures yield insight into timing and physical conditions of quartz growth especially in environments with multiple quartz precipitation events hydrothermal quartz from quartz sulfide veins in the porphyry copper deposit in butte montana was analyzed by sem cl revealing the following textures euhedral growth zones wide nonluminescing bands that cut across multiple quartz grains rounded luminescent quartz grain cores with euhedral overgrowths nonluminescing splatters of quartz connected by networks of cobweb like nonluminescing quartz in otherwise luminescent quartz concentric growth zones and wide nonluminescent grain boundaries these textures indicate that many veins have undergone fracturing dilation growth of quartz into fluid filled space quartz dissolution and recrystallization of quartz precipitation and dissolution textures indicate that early quartz molybdenite veins formed as a result of pressure fluctuations between lithostatic and hydrostatic at high temperatures and later pyrite quartz veins formed near hydrostatic pressure in response to temperature decrease through and beyond the field of retrograde quartz solubility

composition and evolution of ore fluids in a magmatic hydrothermal skarn deposit the chemistry of brine vapor and low salinity fluid inclusions measured by proton induced x ray emission from the bismark skarn deposit mexico is consistent with an evolving magmatic hydrothermal system with no evidence for external fluid inputs the results support a model that invokes early phase separation of magmatic fluids into brine and vapor two phase field at high temperature and lithostatic pressure followed by the entrapment of a low salinity magmatic fluid one phase field at lower temperature and hydrostatic pressure the early brine and vapor inclusions contain high pb and zn concentrations and low cu however the vapor contains significantly more cu than the brine and was likely transported as a sulfur complex the fluid phase changes observed and behavior of cu are comparable to those of porphyry cu systems the later low salinity fluid at bismark represents a distinct pulse of magmatic fluid with a high k ca ratio in which base metals including cu were transported by chloride complexes paragenetic relationships and variations in the relative concentrations of cu pb and zn suggest that this fluid was primarily responsible for ore deposition the relative cu pb and zn concentrations in fluid inclusions at bismark are consistent with those measured from base metal ores in high temperature carbonate replacement deposits throughout mexico and suggest that the bulk metal budget of these deposits is primarily controlled by magmatic hydrothermal fluids deficient in cu

nondestructive spectroscopic and petrochemical investigations of paleoarchean spherule layers from the icdp drill core barb5 barberton mountain land south africa a paleoarchean impact spherule bearing interval of the 763 m long international continental scientific drilling program icdp drill core barb5 from the lower mapepe formation of the fig tree group barberton mountain land south africa was investigated using nondestructive analytical techniques the results of visual observation infrared ir spectroscopic imaging and micro x ray fluorescence xrf of drill cores are presented petrographic and sedimentary features as well as major and trace element compositions of lithologies from the micrometer to kilometer scale assisted in the localization and characterization of eight spherule bearing intervals between 512 6 and 510 5 m depth the spherule layers occur in a strongly deformed section between 517 and 503 m and the rocks in the core above and below are clearly less disturbed the xrf element maps show that spherule layers have similar petrographic and geochemical characteristics but differences in 1 sorting of two types of spherules and 2 occurrence of primary minerals ni cr spinel and zircon we favor a single impact scenario followed by postimpact reworking and subsequent alteration the spherule layers are al2o3 rich and can be distinguished from the al2o3 poor marine sediments by distinct al oh absorption features in the short wave infrared swir region of the electromagnetic spectrum infrared images can cover tens to hundreds of square meters of lithologies and thus may be used to search for al oh rich spherule layers in al2o3 poor sediments such as eoarchean metasediments where the textural characteristics of the spherule layers are obscured by metamorphism

modeling ore generation in a magmatic context abstract magmatic ore deposit models are constructed from a set of measurables e g ore grade fluid composition structure from which important parameters temperature pressure chemistry can be estimated and possible genetic processes can be constrained such models include direct inverse or iterative problems direct problems separately consider an eulerian and a lagrangian formulation in the first case an analytical approach describes the bulk system from an external frame whereas the lagrangian approach provides a description from a discrete element attached to the system conversely inverse problems mostly rely on a system of equations or differential equations their solution requires a matrix inversion using statistical criteria to bracket errors subsequently an iterative approach is adopted commencing with an initial bulk model that is successively refined to fit the observations the direct problem always results in a unique solution though the formulation is highly overdetermined such unique solution highly depends on the input parameters and multiple solutions vary with the initial imposed conditions conversely the inverse problem is underdetermined by construction atlan 2001 accordingly it provides a set of solutions generally identified and separated by statistical tests as exemplified bythe least squares approximation both methods intrinsically ignore feedback loops iterative methods are weak in quantifying the results based on the insights gained from this review we developed a new integrative model for porphyry deposits that relies on the magmatic segregation of metals through a fluid sparging process a formulation under the direct problem basically considers the enrichment factor for groups of metals e g cu mo au a lagrangian approach using a lattice boltzmann model examines metal diffusion from the melt toward an immiscible phase commonly a salty aqueous fluid metals first diffuse in the melt the motion of which slows down when the mush development reduces the porosity thus tapping the mobile fluid phase gas bubbles turn to tubes they offer more mobility and allow the progression of the fluid phase leading to metal advection followed by metal precipitation the quantitative results are poorly constrained owing to the large uncertainties on the input parameters but the metal enrichment factor fits observations from crustal abundance to ore grade levels nevertheless the results aid in designing an inverse approach linking metal enrichment to metal partitioning diffusion and viscous melt motion from this approach a simple diagram can be deduced using a logarithmic scale to smooth the parametric uncertainties the diagram serves to illustrate the link between the above parameters and metal enrichment also explaining differences in ore grade for different metals magma pairs

high copper content of fluid inclusions in quartz from northern sonora implications for ore genesis theory fluid inclusions in quartz associated with copper and molybdenum bearing breccia pipes in northern sonora mexico contain from 4 000 to 16 000 ppm copper and similar amounts of iron these values suggest that the base metal transporting capability of some postmagmatic fluids is considerable metal bearing hydrous fluids of magmatic origin may undergo sufficient dilution by nonmagmatic waters to lose their magmatic identity and still represent major metal transporting agents thus stable isotope data that indicate the predominance of nonmagmatic water during the formation of an ore deposit may be misleading in terms of the true origin of the metals involved

metal fractionation between magmatic brine and vapor determined by microanalysis of fluid inclusions the major and trace element compositions of individual fluid inclusions from a range of magmatic hydrothermal ore deposits were analyzed by laser ablation inductively coupled plasma mass spectrometry to explore the behavior of ore forming components during fluid phase separation boiling in high temperature saline fluid systems data from 13 samples showing unambiguous evidence for coeval trapping of a liquid brine and a coexisting vapor phase identify two groups of elements with drastically different geochemical behavior na k fe mn zn rb cs ag sn pb and tl preferentially partition into the brine probably as cl complexes whereas cu as au probably as hs complexes and b selectively partition into the vapor fluid phase separation is probably a major previously underestimated process in the chemical differentiation that contributes to the extreme range of selective element enrichments in magmatic hydrothermal systems from deep plutons through porphyry style and greisen deposits to epithermal mineralization and volcanic fumaroles

fluid fluid interactions in the earth s lithosphere fluids rich in water carbon and sulfur species and a variety of dissolved salts are a ubiquitous transport medium for heat and matter in the earth s interior fluid transport through the upper mantle and crust controls the origin of magmatism above subduction zones and results in natural risks of explosive volcanism fluids passing through rocks affect the chemical and heat budget of the global oceans and can be utilized as a source of geothermal energy on land fluid transport is a key to the formation and the practical utilization of natural resources from the origin of hydrothermal mineral deposits through the exploitation of gaseous and liquid hydrocarbons as sources of energy and essential raw materials to the subsurface storage of waste materials such as co2 different sources of fluids and variable paths of recycling volatile components from the hydrosphere and atmosphere through the solid interior of the earth lead to a broad range of fluid compositions from aqueous liquids and gases through water rich silicate or salt melts to carbon rich endmember compositions different rock regimes in the crust and mantle generate characteristic ranges of fluid composition which depending on pressure temperature and composition are miscible to greatly variable degrees for example aqueous liquids and vapors are increasingly miscible at elevated pressure and temperature the degree of this miscibility is however greatly influenced by the presence of additional carbonic or salt components a wide range of fluid fluid interactions results from this partial miscibility of crustal fluids vastly different chemical and physical properties of variably miscible fluids combined with fluid flow from one pressure temperature regime to another therefore have major consequences for the chemical and physical evolution of the crust and mantle several recent textbooks e g walther and wood 1986 carrol and holloway 1994 shmulovich et al 1995

fluid inclusion noble gas and halogen evidence on the origin of cu porphyry mineralising fluids the naturally occurring noble gas isotopes 40ar 36ar 84kr and 129xe and halogens cl br i have been determined simultaneously in irradiated quartz vein samples by noble gas mass spectrometry quartz vein samples were collected from the potassic and propylitic alteration zones of six porphyry copper deposits pcd bingham canyon utah and silverbell ray mission pinto valley and globe miami in arizona in addition analyses of 3he 4he have been obtained from sulphide minerals hosted by the quartz veins at silverbell ray pinto valley and globe miami the majority of pcd fluids studied have br cl and i cl ratios that overlap those of fluids included in mantle diamond suggesting that the salinity had a juvenile origin the high i cl 121 10 6 mole m in samples from the propylitic zone of silverbell is attributed to the presence of sedimentary formation water 3he 4he ratios have r ra values in the range 0 3 to 1 72 and provide evidence for the involvement of a crustal component in addition to mantle volatiles 40ar 36ar ratios vary from meteoric values of 317 in the propylitic zone of bingham canyon and 323 in the skarn alteration of mission up to 3225 in the potassic zone of pinto valley fluids in both the potassic and propylitic alteration zones of every deposit are a mixture of a low salinity end member comprising meteoric water and air and a high salinity end member consisting of a mixed mantle and crustal fluid the 40ar cl ratio of fluid inclusions at pinto valley 10 4 m is similar to values obtained previously for mantle fluids the 40ar cl value is two orders of magnitude lower at bingham canyon where a depleted 36ar concentration 0 2 10 6 cm3 g below that of air saturated water asw and a range of highly fractionated noble gas compositions f84kr 13 and f129xe 160 indicate that boiling and pulsed fluid flow have occurred

experimental studies in model fluid systems numerous observations provide strong evidence that fluid fluid coexistence is a widespread phenomenon in many geological processes i oceanic hydrothermal fluids display a wide range in salinity which clearly indicates fluid phase separation of the circulating seawater see foustoukos and seyfried 2007a ii selective enrichment of certain elements and coeval entrapped inclusions of different co existing fluids highlight the role immiscible fluids play in ore formation see heinrich 2007a iii trace element and stable isotope characteristic as well as equilibrium mineral assemblages in contact aureoles prove immiscible fluids to be a ubiquitous feature in most contact metamorphism see heinrich 2007b iv small scale fluid heterogeneity in eclogitic rocks indicate fluid immiscibility to occur in metamorphic rocks up to high or even ultra high pressure see heinrich 2007b unfortunately fluids are principally non quenchable phases and direct quantitative information on fluid properties at p and t is in most cases not available experimental studies are thus central in studying geologic fluids in general and co existing fluids in particular they are still the primary source of quantitative information on physicochemical properties of co existing crustal fluids they allow e g determine i fluid phase relations as function of p t and x ii physical fluid properties like density and viscosity and iii trace element and isotope fractionation between co existing fluids but also between co existing fluids and solids the experimental data can then be used as input in forward modeling approaches the results and or predictions of which may then be tested in natural systems see driesner and geiger 2007 experimental data on co existing fluids in systems of geological relevance already date back to the flrst half of last century e g keevil 1942 since the 1960ies numerous systematic experimental studies on fluid fluid phase relations at crustal p and t conditions were performed e g sourirajan and kennedy

fluid evolution in a volcanic hosted epithermal carbonate base metal gold vein system alto de la blenda farallon negro argentina alto de la blenda is a 6 6 ma intermediate sulphidation epithermal vein system in the farallon negro volcanic complex which also hosts the 7 1 ma porphyry cu au deposit of bajo de la alumbrera the epithermal vein system is characterised by a large extent and continuity 2 km 400 m open to depth 6 m maximum width and an average gold grade of 8 g t the vein is best developed within an intrusion of a fine grained equigranular monzonite interpreted as the central conduit of a stratovolcano whose extrusive activity ended prior to porphyry cu au emplacement at bajo de la alumbrera which is in turn cut by minor epithermal veins the alto de la blenda vein consists predominantly of variably mn rich carbonates and quartz with a few percent of pyrite sphalerite galena and other sulphide and sulphosalt minerals four phases of vein opening hydrothermal mineralisation and repeated brecciation can be correlated between different vein segments stages 2 and 3 contain the greatest fraction of sulphide and gold they are separated by the emplacement of a polymictic breccia containing clasts of quartz feldspar porphyry as well as basement rocks fluid inclusions in quartz related to stages 2 to 4 are liquid rich with 2 4 wt nacl eq they homogenise between 160 and 300 c with very consistent values within each assemblage vapour inclusions are practically absent in the epithermal vein quartz fragments in the polymictic breccia contain inclusions of intermediate to vapour like density and similar low salinity 3 wt nacl eq besides rare brine inclusions containing halite laser ablation inductively coupled plasma mass spectrometry la icp ms analyses of epithermal inclusions indicate high concentrations of k fe as sb cs and pb that significantly vary within and through subsequent vein stages careful consideration of detection limits for individual inclusions shows high gold concentrations of 0 5 to 3 ppm dissolved in the ore fluid which contains variably high sulphur concentrations in excess over fe and other chalcophile metals compositional variations are interpreted to reflect cooling and contraction of lower density magmatic fluids at depth like those preserved in porphyry clasts that were mechanically transported up by the polymictic breccia ore mineral precipitation from the magmatic fluid occurred by further cooling and possibly minor mixing with surface derived water leading to sulphide saturation de sulphidation of the magmatic fluid and consequent gold precipitation the absence of flash boiling and or reduction by carbonaceous host rocks has led to relatively modest but constant gold grades in the carbonate base metal gold veins of alto de la blenda

hydrothermal evolution of the el teniente deposit chile porphyry cu mo ore deposition from low salinity magmatic fluids the magmatic hydrothermal evolution of the el teniente porphyry cu mo deposit in the central andes in chile is reconstructed based on field relationships scanning electron microscopy cathodoluminescence petrography and fluid inclusion analysis by microthermometry and laser ablation inductively coupled plasma mass spectrometry la icpms three major stages of cu mo mineralization are observed following the barren hydrothermal stage 1 the stage 2 mineralization is characterized by quartz anhydrite stockwork veins and breccias with chalcopyrite bornite and molybdenite both stages 1 and 2 are associated with pervasive potassic alteration quartz anhydrite veins with chalcopyrite bornite and molybdenite associated with phyllic alteration represent stage 3 mineralization stage 4 mineralization linked to the formation of the large braden diatreme is characterized by breccias and rare veins containing a lower temperature assemblage with tourmaline sericite and lesser tennantite bornite and chalcopyrite with late gypsum in local vugs ten fluid types are distinguished in this study based on petrographic and microthermometric criteria such as phase proportions daughter minerals homogenization behavior and salinity the hydrothermal evolution across the stages of cu deposition is characterized by the contraction of a vapor phase originating by phase separation during stage 2 overall cooling of the system at pressures fluctuating around the two phase fluid surface led to a transition from a two phase fluid state dominated by vapor at 410 c and 300 bars in stage 2 to a single phase low salinity fluid derived from cooling and contraction of magmatic vapor to a liquid which dominates during stage 3 mineralization at 350 c and 200 bars copper mineralization mainly formed from the vapor phase and its low salinity liquid derivatives representing a large volume of fluid with an initially high cu content 1 2 0 4 wt cu copper sulfides precipitated upon cooling between 410 and 320 c indicated by a drop of cu na k mn fe ratios of over four orders of magnitude through the evolution of the deposit from stage 2 to stage 4 the highest mo concentrations occur in residual brines resulting from extreme boiling as indicated by concurrent halite saturation recent geochronology cannell 2005 maksaev et al 2004 suggests a relatively long lived magmatic hydrothermal system at el teniente our fluid chemical data show no evidence for major crystal fractionation in a large fluid generating upper crustal magma chamber because cs na k mn fe is constant from pre ore to all syn ore fluids however the initiation of copper mineralization was associated with a 4 to 10 fold increase in the concentration of cu mo li and fe in the inferred main ore forming input fluid compared with pre ore fluids of intermediate salinity and otherwise very similar major and trace element ratios these data indicate that injection from depth of an exceptionally cu mo li and probably also s rich volatile phase into an already actively evolving upper crustal magmatic hydrothermal system triggered the formation of this unusually large and rich copper deposit

porphyry to epithermal transition at the rongna cu au deposit tibet insights from h o isotopes and fluid inclusion analysis abstract the giant rongna cu au deposit is a recently discovered low grade composite porphyry high sulfidation epithermal system in the duolong ore district of central tibet we present fluid inclusion petrography microthermometry stable isotope h o and fluid compositional data la icp ms to constrain the fluid evolution of the rongna deposit hydrothermal quartz and muscovite formed in the porphyry stage yielded fluid values of 8 2 1 0 18oh2o and 75 19 dh2o n 13 pyrophyllite kaolinite and dickite define the isotopic composition of the epithermal fluid 18oh2o 2 2 8 3 dh2o 87 45 this epithermal fluid of lighter oxygen isotope and heavier hydrogen isotope composition still has a magmatic hydrothermal signature and rules out any significant involvement of meteoric water the very high concentration of cu in fluid inclusions from epithermal veins and the common sulfide replacement features suggest that the epithermal mineralization may be partially related with the dissolution and re precipitation of the porphyry stage sulfides combined with fluid inclusion petrography and microthermometric data it is indicated that a single phase fluid exsolved from magma at depth and underwent boiling and cooling forming the porphyry alteration and mineralization with decrease of temperature and pressure the ascending vapor contracted into acid aqueous fluid leaching downward to develop the telescoped high sulfidation epithermal alteration and mineralization

incursion of meteoric water triggers molybdenite precipitation in porphyry mo deposits a case study of the chalukou giant mo deposit there has been a long term debate about the timing of the incursion of meteoric water into porphyry systems and whether it plays an important role in ore precipitation to evaluate the role of meteoric water in the mineralization in porphyry mo deposits typical hydrothermal veins of different stages from the chalukou giant porphyry mo deposit are selected for combined scanning electron microscope cathodoluminescence sem cl fluid inclusion microthermometry and high resolution secondary ion mass spectroscopy sims oxygen isotope analyses multiple generations of quartz are identified in almost all of the veins the barren quartz veins and quartz magnetite veins of the early mo mineralization stage are dominated by granular cl bright quartz emq1 which usually shows dissolution and re deposition textures and are overprinted by cl dark quartz emq2 filled healed fractures the molybdenite precipitation in the quartz molybdenite veins of the main mo mineralization stage is synchronous with small volumes 85 of cl bright quartz mmq1 similar to the quartz molybdenite veins the precipitation of pyrite in the quartz pyrite veins during the transitional stage and sphalerite in the quartz sphalerite pyrite veins during the zn pb mineralization stage are also directly associated with cl dark quartz tsq2 zpq2 the sims oxygen isotopic values of emq1 and mmq1 fall into the range of 5 42 9 79 o with calculated equilibrium fluid compositions of 2 07 6 45 0 indicating a magma dominated fluid composition whereas mmq2 tsq2 and zpq2 have very low oxygen isotopic values from 4 68 to 4 29 parts per thousand with corresponding fluid compositions of 13 64 to 5 94 parts per thousand implying that the fluid formed by the mixing of magmatic water and a large proportion of meteoric water the contrasting sem cl features and oxygen isotopic compositions of the two generations of quartz in the quartz molybdenite veins demonstrate that the incursion of meteoric water into the hydrothermal system occurred earlier than the molybdenite precipitation based on these results and the crosscutting relationships and spatial distribution of the veins we reconstructed the quartz evolutionary sequence during the vein development process after the early precipitation of barren quartz the reduction in fluid pressure from lithostatic to hydrostatic conditions allowed the incursion of convecting cool meteoric water into the relatively hot hydrothermal system and the temperature of the evolved mo rich fluid decreased rapidly from 500 degrees c to 400 degrees c leading to concentrated molybdenite precipitation with small volumes of quartz fluid cooling resulting from the incursion of meteoric water may have played a greater role in the metal precipitation in the chalukou mo deposit than wallrock interactions and fluid boiling moreover this process may have also occurred in other porphyry mo deposits

experimental study of the behavior of copper and zinc in a boiling hydrothermal system vapor liquid partitioning coefficients for cu and zn in aqueous fluid were determined under boiling conditions at 500 650 c and 35 100 mpa in sulfur bearing and sulfur free systems a synthetic fluid inclusion technique was used to sample the experimental system of coexisting vapor rich and liquid rich fluid inclusions the cu and zn concentrations in individual fluid inclusions were then analyzed by synchrotron radiation x ray fluorescence the vapor liquid distribution constant of cu k d m cu vapor m cu liquid where m denotes the molality of metal is found to be strongly dependent on the sulfur content in the experimental solutions in sulfur bearing systems cu preferentially partitions into the vapor phase whereas zn preferentially fractionates into the hypersaline liquid the k d values for cu and zn obtained in this study correspond well with those obtained from natural fluid inclusions in hydrothermal ore deposits the results suggest that differential volatility of metals is an important factor affecting the enrichment of certain metals in different hydrothermal ore deposits

gold in porphyry copper deposits experimental determination of the distribution of gold in the cu fe s system at 400 to 700 c experiments in the system au cu fe s were carried out at temperatures of 400 to 700 c to determine how much gold could be accommodated by bornite and chalcopyrite the two most common ore minerals in porphyry copper gold deposits our results show that for all temperatures bornite contains one order of magnitude more gold than chalcopyrite or intermediate solid solution iss its high temperature equivalent the range of gold concentrations in bornite and chalcopyrite or iss decreases with decreasing temperature from 1 280 to 8 200 ppm au in bornite and 100 to 125 ppm au in iss at 600 c to 235 to 364 ppm au in bornite and 5 to 16 ppm au in chalcopyrite or iss at 500 c and to 13 to 80 ppm au in bornite and 2 to 4 ppm au in chalcopyrite or iss at 400 c the amount of gold in bornite is also strongly dependent on the composition of bornite being highest in stoichiometric bornite compositions cu5fes4 and decreasing toward cu rich and cu poor compositions phase equilibrium constraints for solutions with geologically reasonable reduced sulfur contents indicate that high temperature porphyry copper gold deposits will contain bornite and magnetite whereas lower temperature deposits whether primary or overprinted by phyllic alteration will contain chalcopyrite and pyrite if gold is present in the ore forming solutions more of it will be deposited in high temperature porphyry copper gold deposits where it will be closely associated with bornite coexisting magnetite in these deposits should generate magnetic anomalies lower temperature deposits will contain less gold which is hosted by pyrite as well as chalcopyrite and will lack magnetic anomalies comparison of the amount of gold hosted by natural porphyry copper gold ores to that hosted by bornite and chalcopyrite in our experiments suggests that significant amounts of gold can be lost from these deposits into surrounding hydrothermal systems

the relation between cu au ratio and formation depth of porphyry style cu au mo deposits constraints on gold and copper ore grades in porphyry style cu au mo deposits are re examined with particular emphasis on published fluid pressure and formation depth as indicated by fluid inclusion data and geological reconstruction defining an arbitrary subdivision at a molar cu au ratio of 4 0 104 copper gold deposits have a shallower average depth of formation 2 1 km compared with the average depth of copper molybdenum deposits 3 7 km based on assumed lithostatic fluid pressure from microthermometry the correlation of cu au ratio with depth is primarily influenced by the variations of total au grade despite local mineralogical controls within some ore deposits the overall cu au ratio of the deposits does not show a significant correlation with the predominant type of cu fe sulfide i e chalcopyrite or bornite primary magma source probably contributes to metal endowment on the province scale and in some individual deposits but does not explain the broad correlation of metal ratios with the pressure of ore formation by comparison with published experimental and fluid analytical data the observed correlation of the cu au ratio with fluid pressure can be explained by dominant transport of cu and au in a buoyant s rich vapor coexisting with minor brine in two phase magmatic hydrothermal systems at relatively shallow depth approximately 3 km and greater confining pressure is likely to precipitate copper molybdenum only while sulfur complexed gold remains dissolved in the relatively dense vapor upon cooling this vapor may ultimately contract to a low salinity epithermal liquid which can contribute to the formation of epithermal gold deposits several kilometers above the au poor porphyry cu mo deposit these findings and interpretations imply that petrographic inspection of fluid inclusion density may be used as an exploration indicator low pressure brine vapor systems are favorable for coprecipitation of both metals leading to au rich porphyry copper gold deposits epithermal gold deposits may be associated with such shallow systems but are likely to derive their ore forming components from a deeper source which may include a deeply hidden porphyry copper molybdenum deposit exposed high pressure brine vapor systems or stockwork veins containing a single type of intermediate density inclusions are more likely to be prospective for porphyry copper molybdenum deposits

the role of sulfur in the formation of magmatic hydrothermal copper gold deposits abstract essential resources of many rare metals including copper zinc molybdenum silver and gold occur in natural sulfide mineral deposits understanding the origin of these metal resources has been limited by a lack of data about the geochemistry of sulfur the most important and abundant element of ore deposits we report the first directly measured sulfur concentrations in high temperature fluids together with their ore metal contents using a new method for sulfur quantification in fluid inclusions by laser ablation inductively coupled plasma mass spectrometry la icp ms co genetic brine and vapor inclusions from magmatic hydrothermal ore deposits and granitic intrusions show an excess of sulfur over ore metals as required for efficient ore mineral precipitation the results demonstrate that s cu and au are highly enriched in vapor like magmatic fluids implying that such low salinity fluids are the key agent for the formation of porphyry copper and epithermal gold deposits

relationships between sem cathodoluminescence response and trace element composition of hydrothermal vein quartz laser ablation icp ms data of hydrothermal vein quartz with zonation in scanning electron microscope cathodoluminescence reveal two groups of trace elements one that co varies in concentration with luminosity and another that remains uniform throughout bright luminosity correlates with a high total abundance of trace elements in early quartz including al up to 410 g g ti up to 240 g g k up to 330 g g li up to 8 g g na up to 36 g g and fe up to 20 g g up to 20 times lower concentrations of these elements are associated with dark luminosity in late quartz concentrations of p 21 g g ga 0 3 g g ge 1 3 g g sn 1 5 g g cu 0 3 g g and ag 0 1 g g demonstrate no relationship with luminosity charge balance cannot be achieved for bright luminescent quartz unless the presence of up to 6 g g h not analyzed by la icpms or interstitial al3 is invoked interestingly the inferred 6 g g h remains constant for quartz containing more than 10 mol total trace elements and might represent the solubility of h in hydrothermal quartz at temperatures between 450 and 700 c la icpms results indicate that the fluid chemistry determines the quartz trace element pattern which may serve as a monitor for the chemical environment from which quartz crystallized ratios of na al and ti al are uniform whereas k al evolves toward lower values with decreasing luminosity combined evidence including quartz vein textures silica solubility data and estimates of the temperature of quartz growth suggest that early quartz crystallized fast but late quartz grew more slowly at 350 to 425 c it is speculated that the higher the quartz growth rate is the more trace elements are incorporated into quartz besides the temperature dependence known from the literature clearly growth rate temperature and fluid chemistry are important parameters affecting luminosity however their relative importance may vary from case to case

geology geochronology and geochemistry of the dabate cu mo deposit northern chinese tien shan implications for spatial separation of copper and molybdenum mineralization abstract the dabate deposit is a porphyry cu mo deposit located in the sailimu block northern chinese tien shan the deposit shows a clear separation of cu and mo mineralization with cu mineralization occurring along the edge of the rhyolitic porphyry and mo mineralization in the inner part of the rhyolitic porphyry sm nd isotopic analyses of six fluorite samples from the cu sulfides fluorite veins yield an isochron age of 298 1 5 0 ma and re os isotopic analyses of four molybdenite samples from the molybdenite quartz veins yield an isochron age of 299 6 3 2 ma these geochronological data and accompanying geologic evidence indicate that the cu and mo mineralization belongs to the same hydrothermal system and are closely related to the rhyolitic porphyry which has a youngest zircon 206pb 238u age of 297 3 8 0 ma rare earth element ree and fluid inclusion studies were carried out for fluorite in the cu ores the fluorite related to cu mineralization have high ree 63 4 216 9 ppm and show generally similar ree patterns with the rhyolitic porphyry suggesting that the fluid of cu mineralization is closely related to the rhyolitic porphyry the slight lree depletion and ce depletion of fluorite relative to the rhyolitic porphyry may be due to preferential partitioning of hree into the fluid in neutral to weak alkaline conditions and to mixing with meteoric water which is characterized by ce depletion three types of fluid inclusions were recognized in the fluorite from the cu sulfides fluorite veins liquid vapor lv type co2 bearing c type and solid mineral bearing s type the lv type inclusions have homogenization vapor to liquid temperatures from 175 to 328 c and salinities of 0 4 14 9 wt nacl eqv mode at 0 8 wt nacl eqv and is of h2o nacl composition the c type inclusions have homogenization vapor to liquid temperatures from 206 to 279 c and salinities of 1 6 8 5 wt nacl eqv and is of h2o co2 nacl ch4 composition the s type inclusions have partial homogenization vapor to liquid temperatures of 173 233 c and salinities of 1 2 7 9 wt nacl eqv and is of h2o nacl composition the solid particle in s type inclusions did not change during heating up to 550 c indicating that the solid is not daughter mineral and the s type inclusions are actually the same as the lv type inclusions the lv type inclusions have microthermometric attributes similar to those typically found in the late stages of porphyry deposits whereas the c type inclusions have similar compositions as the inclusions in the mo ores as documented in previous studies at dabate the presence of both lv type and c type inclusions suggests that the cu mineralization may be related to mixing between meteoric water and magmatic fluids as is also indicated by the ree of fluorite comparing with data from mo ores reported in previous studies it is suggested that the mo stage fluids were more reduced and acidic and mo mineralization may be mainly related to fluid pressure decrease and immiscibility whereas the cu stage fluids were more oxidized neutral to weakly alkaline and cu mineralization may be mainly controlled by mixing and cooling the vapor phase produced by fluid immiscibility in the deep area may have carried cu as ag hf co2 and migrated to the outer part of the porphyry precipitated cu sulfides arsenopyrite and fluorite by mixing with meteoric water from the country rocks whereas the liquid phase produced by fluid immiscibility at depth may have carried mo nacl and migrated to the middle west part of the rhyolitic porphyry become immiscible and precipitated molybdenite

compositions of subsurface ices at the mars phoenix landing site 1 nasa s phoenix lander uncovered two types of ice at its 2008 landing site on the northern plains of mars a brighter slab like ice that broke during robotic arm operations and a darker icy deposit spectra from the phoenix surface stereo imager ssi are used to demonstrate that the brighter material consists of nearly pure water ice which probably formed by migration and freezing of liquid water the darker icy material consists of 30 20 wt ice with the remainder composed of fine grained soil indicating that it probably formed as pore ice these two types of ice represent two different emplacement mechanisms and periods of deposition

fluid inclusion evidence for immiscibility in magmatic differentiation abstract after a brief review of recent work on melt inclusions in diamond and in normal magmatic environments the nature of the fluid inclusion evidence for various stages of magmatic immiscibility is summarized during magmatic differentiation by crystal fractionation from originally low volatile content silicate melts yielding normal plutonic rocks through hydrous silicate melts yielding pegmatites to late stage water rich fluids yielding quartz veins and ore deposits the composition of the residual liquid changes drastically in some geologic environments this change in composition of the residual liquid may be continuous with no phase change in the fluid part of the system under most natural conditions however it is far more likely to have one or more stages in the evolution during which globules of a separate new immiscible fluid phase exsolve the term immiscibility is used here in its more general sense to refer to the existence at equilibrium of two or more non crystalline polycomponent solutions fluids differing in properties and generally in composition i believe that the great bulk of the magmatic inclusions that are being studied today have come about through the intervention of one or more such stages of immiscible fluid separation i e magmatic differentiation by fluid immiscibility examples include silicate melt dense co2 fluid silicate melt sulfide melt silicate melt silicate melt silicate melt low density vapor i e vesiculation and as presented in more detail in this paper various stages of silicate melt hydrous saline melt aqueous fluid co2 fluid immiscibility generally only parts of these stages are recorded by the trapping of fluid inclusions and the interpretation of the inclusion record is commonly ambiguous and difficult particularly that stage between hydrous silicate melts and the hydrous saline melts and aqueous solutions responsible for many ore deposits the ambiguity results mainly from problems of inclusion origin and nonrepresentative trapping within any given individual inclusion thus the probability of trapping of only one vs various amounts of two immiscible fluids or of trapping solid phases along with the fluid present severe difficulties in addition there is the almost universal superposition of various stages of trapping of fluids within any given sample these problems can only be approached by very careful petrography and analysis of optimum material combined with field data and experimental p v t x studies of pertinent systems completely unequivocal statements of the course of evolution of the fluids in such natural systems may never be possible

petrology of the yerington batholith nevada evidence for evolution of porphyry copper ore fluids the jurassic yerington batholith western nevada is a composite pluton that contains several centers of porphyry copper mineralization and is exposed in structural cross section at paleodepths ranging from 0 to 8 km within these exposures the mcleod hill quartz monzodiorite bear quartz monzonite and luhr hill granite form successive intrusions that are in turn volumetrically smaller approximately 75 19 and 6 vol respectively more deeply emplaced tops at 65 km 3 luhr hill granite the low cu content approximately 10 ppm of the granite would allow extraction of approximately 50 ppm cu from it during crystallization these data suggest an orthomagmatic model in which both high and low density saline aqueous fluids formed during exsolution of water from the crystallizing luhr hill granite and from which salts cu fe and s strongly partitioned into the high density ore fluid low density fluids may have risen from the magma as a vapor plume mineralization occurred when fluid overpressures caused fracturing of wall rock and upward intrusion of granite porphyry dikes and high density saline ore fluids both the f sub o 2 path during subsolidus cooling and the deposition of most s as chalcopyrite pyrite in ore suggest that reduction of magmatic s to sulfide may have been a mechanism for oxidation of magmatic ferromagnesian silicate and fe ti oxide minerals

can economic porphyry copper mineralization be generated by a typical calc alkaline melt numerical simulation of chlorine and copper partitioning between a crystallizing melt and exsolving aqueous fluids indicates that typical calc alkaline magmas contain sufficient copper chlorine and water to produce economic porphyry copper mineralization neither an elevated copper content in the magma nor an additional large volume of magma are required to provide metals or volatiles the most important variables that determine the volume of melt necessary to produce sufficient copper are the degree of compatible behavior displayed by copper the ratio of initial water in the melt to the water saturation level and the initial chlorine water ratio of the melt the absolute values for initial water in the melt and water content at saturation are relatively unimportant in determining the required melt volume the bulk salinity of the exsolved fluid may vary from 2 0 wt nacl to saturation levels 84 wt nacl at 700 c indicating that boiling is not necessary to produce high salinity brines at appropriate p t xnacl conditions the magmatic aqueous fluid separates into a saline liquid which transports most of the copper and a low salinity vapor the salinities of the two immiscible phases are governed by the p t conditions while the bulk fluid salinity determines the mass fractions of liquid and vapor formed pressure quenching causes rapid crystallization of the aplitic groundmass in porphyritic rocks associated with copper mineralization and significantly reduces the amount of chlorine and copper partitioning to the aqueous fluid this results in abrupt and possibly large reductions in fluid salinity and causes copper to become concentrated in the melt as copper is transported from the melt by the earliest exsolving fluids in deep 2 0 kbar systems and by late exsolving fluids in shallow 0 5 kbar systems the relative timing of pressure quenching aplite formation and fluid transport of copper from the melt can vary significantly in systems produced under different confining pressures model results incorporating petrologic constraints determined for yerington nevada are in good agreement with observed mineralization