Thermochronological evolution of calcite formation at the potential Yucca Mountain repository site, Nevada: Part 2 fluid inclusion analyses and UPb dating

The presence of two-phase fluid inclusions in thin secondary mineral crusts at the potential Yucca Mountain nuclear waste repository has raised questions regarding the origin, timing, and temperature of past fluid flow through the repository horizon. The geologically recent passage of fluids with high temperatures would call into question the suitability of the site for the storage of high level nuclear waste. This study determined the thermal history of fluid flow through the site using fluid inclusion analyses and constrained the timing of thermal fluids by dating silica minerals spatially associated with the fluid inclusions using U-Pb techniques. Results provide a detailed time-temperature history of fluid migration through primary and secondary pore spaces during the past 8 to 9 million years. One hundred and fifty-five samples were collected in the unsaturated zone from the C-shaped Exploratory Studies Facility (ESF), the ECRB cross drift which crosses the potential repository horizon, and exploratory alcoves. Detailed petrographic and paragenetic studies indicated that the oldest secondary minerals consisted of heterogeneously distributed calcite with lesser chalcedony, quartz, opal, and fluorite. The oldest secondary minerals were overgrown by intermediate bladed calcite. The youngest secondary minerals include chemically distinct Mgenriched, growth-zoned sparry calcite (MGSC) and intergrown U-enriched opal. Fluid inclusion petrography indicated that 50 % of the samples (n = 78) contained fluid inclusion assemblages with two-phase fluid inclusions, and that assemblages of liquid-only fluid inclusions represent \u3e 96% of all fluid inclusions within the secondary minerals. Assemblages of two-phase inclusions also contain liquid-only inclusions that did not nucleate a vapor-bubble owing to formation at relatively low temperatures. Virtually all two-phase fluid inclusions occur in paragenetically old calcite; rare two-phase inclusion assemblages were observed in old fluorite (n = 3) and quartz (n = 2). Rare two-phase fluid inclusions were observed in early-intermediate calcite; sparse, irregularly shaped liquid-only inclusions form the only fluid inclusion assemblages observed in late-intermediate minerals and young MGSC. Homogenization temperatures for calcite across the site are generally 45 - 60 °C, but higher temperatures reaching 83 °C were recorded in the north portal and ramp of the ESF and cooler temperatures of ~ 35 - 45 °C were recorded in the intensely fracture zone. Samples from lithophysal cavities in the ESF and ECRB contain multiple populations of two-phase inclusions. Inclusion temperatures are highest in early calcite (\u3e 45 °C) and cooler in paragenetically younger early calcite, indicating cooling with time. The cooler temperatures coincide with temperatures recorded in the intensely fractured zone and indicate that secondary minerals in the intensely fractured zone began to precipitate later than secondary minerals in other locations. Freezing point depressions determined for inclusions range from -0.2 to -1.6 °C indicating trapping of a low salinity fluid. A small number of fluid inclusions in fluorite and quartz were identified and evaluated. Four inclusions in these minerals homogenized at temperatures higher than those recorded for calcite (91 ° - 95 °C) . Two approaches were used to constrain the timing of thermal fluids at Yucca Mountain. First, the age of MGSC was determined, and it provides a minimum age for fluids with elevated temperatures owing to the presence of only liquid-only inclusions in MGSC. Results indicate that MGSC began to precipitate across the site between 2.90 ± 0.06 Ma and about 1.95 ± 0.06 Ma, and MGSC has continued to precipitate to within the last half million years. These ages constrain fluids with elevated temperatures to have accessed the site more than about 2.90 Ma. Second, more precise temporal constraints were determined for samples in which datable opal or chalcedony occur in the intermediate or older parts of the mineral crusts, or are spatially related to 2-phase fluid inclusions. Such ages indicate that two-phase fluid inclusions are older than 5.32 ± 0.02 Ma, and that fluids with elevated temperatures were present at Yucca Mountain before this time. Results from this study are consistent with a model of descending meteoric water that infiltrated the cooling tuff sequence, became heated, and precipitated secondary minerals within the vadose zone. Fluid inclusions indicate that fluids with elevated temperatures were present during the early history of Yucca Mountain. Sparse, liquid-only fluid inclusions in late intermediate to young calcite indicate that secondary minerals were precipitated from low temperature fluids during the past 5 million years. This study demonstrates that the hypothesis of geologically recent upwelling hydrothermal fluids is untenable and should not disqualify Yucca Mountain as a potential nuclear waste storage site

Bulk rock composition and geochemistry of olivine-hosted melt inclusions in the Grey Porri Tuff and selected lavas of the Monte dei Porri volcano, Salina, Aeolian Islands, southern Italy.

The Aeolian Islands are an arcuate chain of submarine seamounts and volcanic islands, lying just north of Sicily in southern Italy. The second largest of the islands, Salina, exhibits a wide range of compositional variation in its erupted products, from basaltic lavas to rhyolitic pumice. The Monte dei Porri eruptions occurred between 60 ka and 30 ka, following a period of approximately 60,000 years of repose. The bulk rock composition of the Monte dei Porri products range from basaltic-andesite scoria to andesitic pumice in the Grey Porri Tuff (GPT), with the Monte dei Porri lavas having basaltic-andesite compositions. The typical mineral assemblage of the GPT is calcic plagioclase, clinopyroxene (augite), olivine (Fo72−84) and orthopyroxene (enstatite) ± amphibole and Ti-Fe oxides. The lava units show a similar mineral assemblage, but contain lower Fo olivines (Fo57−78). The lava units also contain numerous glomerocrysts, including an unusual variety that contains quartz, K-feldspar and mica. Melt inclusions (MI) are ubiquitous in all mineral phases from all units of the Monte dei Porri eruptions; however, only data from olivine-hosted MI in the GPT are reported here. Compositions of MI in the GPT are typically basaltic (average SiO2 of 49.8 wt %) in the pumices and basaltic-andesite (average SiO2 of 55.6 wt %) in the scoriae and show a bimodal distribution in most compositional discrimination plots. The compositions of most of the MI in the scoriae overlap with bulk rock compositions of the lavas. Petrological and geochemical evidence suggest that mixing of one or more magmas and/or crustal assimilation played a role in the evolution of the Monte dei Porri magmatic system, especially the GPT. Analyses of the more evolved mineral phases are required to better constrain the evolution of the magma

Mineral chemistry of the Tissint meteorite: Indications of two-stage crystallization in a closed system

The Tissint meteorite is a geochemically depleted, olivine-phyric shergottite. Olivine megacrysts contain 300–600 μm cores with uniform Mg# (~80 ± 1) followed by concentric zones of Fe-enrichment toward the rims. We applied a number of tests to distinguish the relationship of these megacrysts to the host rock. Major and trace element compositions of the Mg-rich core in olivine are in equilibrium with the bulk rock, within uncertainty, and rare earth element abundances of melt inclusions in Mg-rich olivines reported in the literature are similar to those of the bulk rock. Moreover, the P Kα intensity maps of two large olivine grains show no resorption between the uniform core and the rim. Taken together, these lines of evidence suggest the olivine megacrysts are phenocrysts. Among depleted olivine-phyric shergottites, Tissint is the first one that acts mostly as a closed system with olivine megacrysts being the phenocrysts. The texture and mineral chemistry of Tissint indicate a crystallization sequence of: olivine (Mg# 80 ± 1) → olivine (Mg# 76) + chromite → olivine (Mg# 74) + Ti-chromite → olivine (Mg# 74–63) + pyroxene (Mg# 76–65) + Cr-ulvöspinel → olivine (Mg# 63–35) + pyroxene (Mg# 65–60) + plagioclase, followed by late-stage ilmenite and phosphate. The crystallization of the Tissint meteorite likely occurred in two stages: uniform olivine cores likely crystallized under equilibrium conditions; and a fractional crystallization sequence that formed the rest of the rock. The two-stage crystallization without crystal settling is simulated using MELTS and the Tissint bulk composition, and can broadly reproduce the crystallization sequence and mineral chemistry measured in the Tissint samples. The transition between equilibrium and fractional crystallization is associated with a dramatic increase in cooling rate and might have been driven by an acceleration in the ascent rate or by encounter with a steep thermal gradient in the Martian crust

Effect of water activity on rates of serpentinization of olivine

The hydrothermal alteration of mantle rocks (referred to as serpentinization) occurs in submarine environments extending from mid-ocean ridges to subduction zones. Serpentinization affects the physical and chemical properties of oceanic lithosphere, represents one of the major mechanisms driving mass exchange between the mantle and the Earth’s surface, and is central to current origin of life hypotheses as well as the search for microbial life on the icy moons of Jupiter and Saturn. In spite of increasing interest in the serpentinization process by researchers in diverse fields, the rates of serpentinization and the controlling factors are poorly understood. Here we use a novel in situ experimental method involving olivine micro-reactors and show that the rate of serpentinization is strongly controlled by the salinity (water activity) of the reacting fluid and demonstrate that the rate of serpentinization of olivine slows down as salinity increases and H2O activity decreases

Fluid Inclusions in Astromaterials: Direct Samples of Early Solar System Aqueous Fluids

We have become increasingly aware of the fundamental importance of water, and aqueous alteration, on primitive solar-system bodies. All classes of astromaterials studied show some degree of interaction with aqueous fluids. We have direct observations of cryovolcanism of several small solar system bodies (e.g. Saturnian and Jovian moons), and indirect evidence for this process on the moons Europa, Titan, Ganymede, and Miranda, and the Kuiper Belt object Charon, and so are certain of the continuing and widespread importance of aqueous processes across the solar system. Nevertheless, we are still lacking fundamental information such as the location and timing of the aqueous alteration and the detailed nature of the aqueous fluid itself

Thermochronological evolution of calcite formation at the proposed Yucca Mountain repository site, Nevada: Part 1, secondary mineral paragenesis and geochemistry

In the near future a decision will be made as to whether or not Yucca Mountain, 90 miles northwest of Las Vegas, Nevada is a suitable site for a permanent, underground, high level nuclear waste repository. A major factor in determining the suitability of Yucca Mountain as a repository is the potential for the site to be flooded by water during the regulatory lifetime. The current study was undertaken to examine the past fluid history at the site, to gain a better understanding of the possibility of flooding in the near geologic future. To estimate the past fluid flux into the repository horizon, research has focused on secondary minerals that precipitated in open space in lithophysal cavities, fractures, and breccias in the host Miocene tuffs. U.S. Geological Survey researchers concluded that secondary minerals formed from descending surficial meteoric fluids in a vadose environment. State of Nevada scientists observed 2-phase fluid inclusions with homogenization temperatures of 35 to 85 °C in secondary minerals and concluded that these minerals formed in the phreatic environment from upwelling hydrothermal fluids. They further concluded that upwelling hydrothermal fluids repeatedly invaded the site, have invaded the site in the recent geologic past, and could do so again making Yucca Mountain an unsafe site for high level nuclear waste storage. These studies did not constrain the timing of incursion of the fluids with elevated temperatures or the extent of this fluid flux across the site. This report provides the geologic context for subsequent fluid inclusion and geochronological studies (Wilson et al., 2002) that identified the temperature and extent of the fluid incursion and placed absolute temporal constraints on the fluid history at Yucca Mountain. Here we describe a detailed paragenetic study that determined the depositional history of secondary minerals at Yucca Mountain. One hundred and fifty-five samples of secondary minerals were collected from lithophysal cavities, fractures, and breccias at Yucca Mountain. Extensive petrography, paragenetic studies, and microprobe mapping indicate that early secondary minerals were heterogeneously distributed across the site and consist of variable amounts of calcite, opal, chalcedony, fluorite, and quartz. Early calcite contained variable trace amounts of Mg (up to 1.3 wt. %). Intermediate minerals consist of mainly calcite, often in bladed habits, with minor opal, and chalcedony and quartz. These minerals contain no diagnostic trace element variations. The latest secondary minerals deposited across the site consist of sparry calcite and minor intergrown opal. This sparry calcite exhibits fine (~ 50 u.m) Mg-enriched and depleted growth zones and is chemically distinct from all other calcite. Mg-enriched growth-zoned sparry calcite (MGSC) contains up to ~ 1.0 wt. % Mg and has been identified in \u3e 65 % of the samples collected from across the site. MGSC and associated opal are always the paragenetically youngest minerals; where MGSC is not present, young secondary minerals did not precipitate. Calcite exhibits ranges for 513C from -8.5 %o to 9.5 %o, and for 818O from 5.2 %o to 22.1 %o. Samples exhibit generally consistent trends of decreasing C and increasing O isotopic compositions from paragenetically older to younger calcite. C and O isotope signatures for MGSC are between 16 %o and 20 %o for 618O and -3 %o and -8.5 %o for 513C. However, signatures for the various stages are not unique and are not diagnostic in correlating secondary mineral stages across the site. Early calcite is generally more luminescent than later calcite, but luminescence was not sufficiently consistent to aid in constraining the paragenetic sequence. LA-ICP-MS analyses indicate that higher levels of U, Th, and Sr are locally present in MGSC compared to paragenetically early calcite, however, this variation is not present in all samples. An important observation is that 90% of primary and secondary open space in the tuffs at Yucca Mountain contains no secondary mineral record. Where secondary minerals are present, the older secondary mineral record is heterogeneous across the site. However, MGSC, which forms the youngest part of the secondary mineral record, is present in a majority of samples and exhibits a more homogeneous distribution across the site. Secondary mineral abundances and textures indicate that secondary minerals precipitated in a vadose environment. The observed features are not consistent with secondary mineral precipitation in a phreatic environment saturated with aqueous fluids. Growth zoning in the outermost MGSC is consistent with formation from discontinuous influx of small fluid volumes with variable Mg content from surficial fluids that percolated downwards. Fluctuations in the Mg content in MGSC may be related to climate changes that occurred in the last few million years

Synthetic fluid inclusions in natural quartz. IV. Chemical analyses of fluid inclusions by SEM/EDA: Evaluation of method

The compositions of individual synthetic fluid inclusions in the systems NaCl-KCl, NaCl-CaCl2 and NaCl-KCl-CaCl2 have been semi-quantitatively determined by energy dispersive analysis of precipitates produced during thermal decrepitation. Inclusions containing known mixtures of 20 wt.% total salinity were synthesized by healing fractures in natural quartz at 600-700[deg]C and 5-7 kbars for 7-10 days. The two-phase, daughter-free inclusions homogenized at 170-250[deg]C, began to decrepitate after about 100[deg] of overheating and by 360-420[deg]C a significant number of decrepitates had formed on the polished surface. Peak heights generated by EDA (raster mode) of these decrepitates were standardized using both single and mixed salt standards evaporated to dryness in a vacuum. Although the mixed salt standards better approximated the decrepitate compositions, difficulties were encountered in producing micronscale homogeneity and the single salts yielded more reliable results.Eight different solutions of 20-23 wt.% total salinity were run and in all the samples the average compositions of 10-20 discrete, single inclusion decrepitates fell with 6 wt.% (0.2 to 5.2) of the actual composition, suggesting that the decrepitates were chemically representative of their precursor inclusions. However, not all decrepitates analyzed provided similarly accurate results. Electron mapping revealed that fracture-aligned decrepitates were often chemically inhomogeneous and thus had to be avoided. A sample decrepitated at 500[deg]C yielded spurious results suggesting that chloride volatility may become a significant problem when temperatures in excess of 450[deg]C are required for decrepitation. Decrepitates with diameters between 10 and 30 [mu]m yielded more consistent and accurate results than smaller or larger decrepitates on the same samples.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/27326/1/0000349.pd

The Patricia Zn–Pb–Ag epithermal ore deposit: An uncommon type of mineralization in northeastern Chile

The Patricia ore deposit represents an unusual example of economic Zn–Pb–Ag mineralization at the northernmost end of the Late Eocene–Oligocene metallogenic belt in Chile. It is hosted by volcano-sedimentary units, which are typically tuffaceous and andesitic breccias. The ore body consists of a set of subvertical E-W vein systems developed under a sinistral strike-slip regime that included transtensive domains with generalized extensional structures where the ores were deposited. The deposit is divided into two blocks by a set of NNW-ESE-trending reverse faults, which uplifted the eastern block and exhumed thicker and deeper parts of the deposit. At least 200 m of volcano-sedimentary pile hosting the mineralization has been eroded in this block. By contrast, the western block exposes a shallower part of the system where cherts, amorphous silica and jasperoids occur. Three main stages of mineralization have been defined: (1) pre-ore stage is characterized by early quartz, pyrite and arsenopyrite, (2) base-metal and silver stage; characterized by sphalerite (6 to 15 mol% FeS), galena, chalcopyrite, pyrrhotite and Ag-bearing minerals (freibergite, polybasite, stephanite, pyrargyrite, freieslebenite and acanthite) and (3) post-ore stage; characterized by late quartz, kutnohorite and minor sulfides (arsenopyrite, sphalerite, pyrite, galena, Ag-bearing minerals and Pb-sulfosalts). Whole-ore geochemistry shows two groups of elements that are positively correlated; 1) Ag–Cd–Cu–Pb–Zn related to the base metal sulfides and 2) Au–As–Ge–Sb–W related to arsenopyrite and pyrite. Hydrothermal alteration is pervasive in the outcropping mineralized areas, including silicification and locally, vuggy silica textures. At depth, chloritic and sericitic alteration is developed along vein selvages and is superimposed to the regional propylitic alteration. Fluid inclusions indicate that the base-metal ores were deposited from 250 to 150 °C moderate salinity fluids (1–9 wt.% NaCl). The pre-ore stage is characterized by a saline fluid (6–22 wt.% NaCl) and between 210 and 250 °C whereas the post-ore stage has salinity of 4–8 wt.% and temperature from 175 to 215 °C. Cooling was the mechanism of ore mineral precipitation in the Patricia deposit, although mixing of fluids could have occurred in the pre-ore stage. Mineralogical, geochemical and fluid inclusion evidence is consistent with an intermediate sulfidation (IS) epithermal deposit type. This study highlights the high potential for hidden economic mineralization at depth in the western block and for extension of the ore body both to the south and to deeper levels in the eastern block of the Patricia ore deposit. To a larger extent, the implications of finding such polymetallic epithermal style of mineralization in the northern Chile Precordillera is relevant both to the regional metallogenic perspective and to the exploration potential of the region, where the late Eocene–early Oligocene metallogenic belt apparently disappears.This research was financially supported by the project CGL2010 – 17668 (Ministerio de Economía y Competitividad of Spain) and the company Herencia Resources Plc.Peer reviewe

Mineral chemistry of the Tissint meteorite: Indications of two-stage crystallization in a closed system

The Tissint meteorite is a geochemically depleted, olivine-phyric shergottite. Olivine megacrysts contain 300–600 μm cores with uniform Mg# (~80 ± 1) followed by concentric zones of Fe-enrichment toward the rims. We applied a number of tests to distinguish the relationship of these megacrysts to the host rock. Major and trace element compositions of the Mg-rich core in olivine are in equilibrium with the bulk rock, within uncertainty, and rare earth element abundances of melt inclusions in Mg-rich olivines reported in the literature are similar to those of the bulk rock. Moreover, the P Kα intensity maps of two large olivine grains show no resorption between the uniform core and the rim. Taken together, these lines of evidence suggest the olivine megacrysts are phenocrysts. Among depleted olivine-phyric shergottites, Tissint is the first one that acts mostly as a closed system with olivine megacrysts being the phenocrysts. The texture and mineral chemistry of Tissint indicate a crystallization sequence of: olivine (Mg# 80 ± 1) → olivine (Mg# 76) + chromite → olivine (Mg# 74) + Ti-chromite → olivine (Mg# 74–63) + pyroxene (Mg# 76–65) + Cr-ulvöspinel → olivine (Mg# 63–35) + pyroxene (Mg# 65–60) + plagioclase, followed by late-stage ilmenite and phosphate. The crystallization of the Tissint meteorite likely occurred in two stages: uniform olivine cores likely crystallized under equilibrium conditions; and a fractional crystallization sequence that formed the rest of the rock. The two-stage crystallization without crystal settling is simulated using MELTS and the Tissint bulk composition, and can broadly reproduce the crystallization sequence and mineral chemistry measured in the Tissint samples. The transition between equilibrium and fractional crystallization is associated with a dramatic increase in cooling rate and might have been driven by an acceleration in the ascent rate or by encounter with a steep thermal gradient in the Martian crust