Geology Reports⌕ Search

Geology topics

Richard J. Moscati

Publications and source records attributed to Richard J. Moscati.

18 recordsLinked to original sources

The petrogenesis of Þingmúli volcano, East Fjords, Iceland

In this work we revisit Þingmúli volcano (Þ = Th), a classic locality known as an example of a complete tholeiitic differentiation. Þingmúli is a ~ 9.5 Ma extinct central volcano located in the East Fjords of Iceland, in which the whole compositional spectrum from basalt to rhyolites have erupted. These volcanic products have been previously considered as petrogenetically related by an ideal fractionation trend, regardless any temporal relationship or volumetric considerations. Here we report new whole-rock geochemistry, mineral chemistry, isotope analyses, estimation of residence times of the different eruptive deposits, and an update of the original petrogenetic model. Our results highlight that an enriched source, likely spinel lherzolites, generated transitional-alkaline basaltic melts after 15–20% of partial melting at depths of 40–45 km. Many of these basaltic melts erupted at various stages of the volcano's history, while others remained longer in the volcanic plumbing system. These evolved by fractional crystallisation into basaltic andesite magmas with a residence time of ~5 years based on the crystal size distribution of the plagioclase population. Isotopic differences between the basalts/basaltic andesites ( 87 Sr/ 86 Sr ~ 0.7034; 143 Nd/ 144 Nd ~ 0.51315) and the erupted rhyolites ( 87 Sr/ 86 Sr ~ 0.7037; 143 Nd/ 144 Nd ~ 0.51304) indicate that the latter are not petrogenetically related to the former. Therefore, instead of a fractional crystallisation mechanism to generate the rhyolites, we propose the partial melting of ignimbrite layers located beneath the volcano. The broad range of trace element concentrations in andesites and dacites and their different isotopic values compared to the basalts strongly suggest that these magmas have been generated by magma mixing between basaltic and rhyolitic melts, similar to modern day Icelandic volcanoes such as Hekla. These results highlight the need to revisit previously studied Icelandic classic localities and reassess their traditionally proposed petrogenetic models.

Þingmúli volcano, East Fjords↗

Pb-Pb and U-Pb dating of cassiterite by in situ LA-ICPMS: Examples spanning ~1.85 Ga to ~100 Ma in Russia and implications for dating Proterozoic to Phanerozoic tin deposits.

This paper investigates applicability of cassiterite to dating ore deposits in a wide age range. We report in situ LA-ICPMS U-Pb and Pb-Pb dating results ( n = 15) of cassiterite from six ore deposits in Russia ranging in age from ~1.85 Ga to 93 Ma. The two oldest deposits dated at ~1.83–1.86 Ga are rare metal Vishnyakovskoe located in the East Sayan pegmatite belt and tin deposits within the Tuyukan ore region in the Baikal folded region. Rare metal skarn deposits of Pitkäranta ore field in the Ladoga region, Fennoscandian Shield are dated at ~1.54 Ga. Cassiterite from the Mokhovoe porphyry tin deposit located in western Transbaikalia is 810 ± 20 Ma. The youngest cassiterite was dated from the deposits Valkumei (Russian North East, 108 ± 2 Ma) and Merek (Russian Far East, 93 ± 2 Ma). Three methods of age calculations, including 208 Pb/ 206 Pb- 207 Pb/ 206 Pb inverse isochron age, Tera-Wasserburg Concordia lower intercept age, and 207 Pb-corrected 206 Pb*/ 238 U age were used and the comparison of the results is discussed. In all cases, the dated cassiterite from the ore deposits agreed, within error, with the established period of magmatism of the associated granitic rock

Chuya-Kodar complex, East Sayan belt, Merek Greise↗

LA-ICPMS U-Pb dating reveals cassiterite inheritance in the Yazov granite, Eastern Siberia: Implications for tin mineralization

U-Pb dating of cassiterite and zircon from the Yazov granite (Transbaikalia region, Eastern Siberia, Russia) and cassiterite from spatially associated tin mineralization in the Tuyukan ore district in the Tonod uplift was conducted using in situ laser ablation inductively coupled plasma mass spectrometry. These analyses allow comparison of isotopic systematics for both minerals, especially related to transport in granitic magma. These data are also useful for understanding possible genetic links between the granite and the tin mineralization. Most of the U-Pb zircon analyses define a 206 Pb/ 238 U age of 719 ± 15 Ma for the granite; in addition, several zircon cores define an inheritance age of 1839 ± 21 Ma. U-Pb data for 10 nearly concordant analyses of disseminated cassiterite from the same samples yield a 206 Pb/ 238 U age of 1838 ± 34 Ma. This is the first documented evidence of cassiterite inheritance in granitic magma. These data indicate the robust character of U-Pb isotope systematics in cassiterite, comparable to that in zircon. The presence of numerous inclusions of cassiterite in zircon from the Yazov granite (revealed by nanotomography) supports the interpretation of inherited cassiterite included during Neoproterozoic zircon crystallization. The data indicate that high tin concentrations in the Yazov granite are due to the incorporation of older cassiterite crystals from country rock, not coeval cassiterite crystallization. Cassiterite samples from two ore occurrences spatially associated with the Yazov granite yield Pb-Pb isochron ages of 1.86–1.82 Ga, indicating that tin mineralization occurred in the Paleoproterozoic, nearly 1 Ga before emplacement of the Yazov granite. Tin mineralization of the ore region is probably related to ~ 1.85 Ga Chuya-Kodar tin-bearing granitic rocks that host tin deposits. These results have broad implications for understanding how critical elements, such as tin, may become enriched in rare-metal granites and how they are related to regional to global geodynamic processes.

Siberia↗

Monazite and cassiterite Usingle bondPb dating of the Abu Dabbab rare-metal granite, Egypt: Late Cryogenian metalliferous granite magmatism in the Arabian-Nubian Shield

The Abu Dabbab rare-metal granite in the Eastern Desert of Egypt is a highly-evolved alkali-feldspar granite with transitional magmatic-hydrothermal features. Extreme geochemical fractionation and the associated significant Ta Sn resource make the Abu Dabbab intrusion an important feature in the metallogenic evolution of the Arabian-Nubian Shield. U Pb dating by laser ablation sector field (SF)-ICPMS analysis of igneous monazite yields a Concordia age of 644.7 ± 2.3 Ma, identical within uncertainty to a lower intercept Tera-Wasserburg isochron age of 644.2 ± 2.3 Ma obtained from hydrothermal cassiterite. Both ages place tight constraints on the timing of magmatic-hydrothermal processes in the Abu Dabbab granite which represents the oldest highly-evolved granite recognized so far in the Pan-African Arabian-Nubian Shield. Thus, the new ages also date the start of a period of late-orogenic metalliferous granite magmatism, when the basement of the Eastern Desert underwent a geodynamic transition from a compressive subduction-collision regime towards orogenic collapse in the late Cryogenian.

Gondwana Research↗

U-Pb geochronology of tin deposits associated with the Cornubian Batholith of southwest England: Direct dating of cassiterite by in situ LA-ICPMS

The Cornwall and Devon vein- and greisen-type copper and tin deposits of southwest England are spatially and genetically related to shallow-seated granitic intrusions. These late Variscan intrusions, collectively known as the Cornubian Batholith, extend over 200 km and form a continuous granitic spine from the Isles of Scilly Granite in the west to the Dartmoor Granite in the east. The granitic plutons of the Cornubian Batholith were intruded from ~ 295 to 270 Ma without a major hiatus. Twelve samples of cassiterite (SnO 2 ) were obtained from tin deposits associated with seven different plutons within the Cornubian Batholith for in situ LA-ICPMS U–Pb dating. This study of cassiterite was undertaken to obtain the first results of direct dating of ore mineral to refine the geochronology of tin mineralization in this region. Of the cassiterite samples analyzed, the oldest ages were determined within the Kit Hill and Hingston–Gunnislake Granites in the central part of the Cornubian Batholith. The Hingston–Gunnislake cassiterite, from Drakewalls Mine, was the oldest sample dated at 291.8 ± 3.4 Ma. The next oldest dates, 290.5 ± 2.8 and 288.5 ± 2.9 Ma, were from two cassiterite samples extracted from the adjacent Kit Hill Consolidated Mines within the Kit Hill Granite. At the eastern end of the study area, two cassiterite samples within the Dartmoor Granite produced ages of 286.0 ± 1.8 and 284.1 ± 1.3 Ma. The youngest sample from this study, 275.4 ± 1.6 Ma, is from the Balleswidden Mine within the westernmost Land’s End Granite. The cassiterite dates do not reveal any readily observable relationship between ore ages and geographic relationship from west to east throughout the Cornubian Batholith. Incorporating the associated errors, the geochronology does indicate continuous mineralization within the granites for ~ 21 million years, from ca. 295 to 274 Ma. This span falls within the established period of granitic magmatism of ca. 295 to 270 Ma for the Cornubian Batholith and further confirms the reliability of in situ LA-ICPMS U–Pb dating of cassiterite.

Mineralium Deposita↗

Major element and oxygen isotope geochemistry of vapour-phase garnet from the Topopah Spring Tuff at Yucca Mountain, Nevada, USA

Twenty vapour-phase garnets were studied in two samples of the Topopah Spring Tuff of the Paintbrush Group from Yucca Mountain, in southern Nevada. The Miocene-age Topopah Spring Tuff is a 350 m thick, devitrified, moderately to densely welded ash-flow tuff that is zoned compositionally from high-silica rhyolite to latite. During cooling of the tuff, escaping vapour produced lithophysae (former gas cavities) lined with an assemblage of tridymite (commonly inverted to cristobalite or quartz), sanidine and locally, hematite and/or garnet. Vapour-phase topaz and economic deposits associated commonly with topaz-bearing rhyolites (characteristically enriched in F) were not found in the Topopah Spring Tuff at Yucca Mountain. Based on their occurrence only in lithophysae, the garnets are not primary igneous phenocrysts, but rather crystals that grew from a F-poor magma-derived vapour trapped during and after emplacement of the tuff. The garnets are euhedral, vitreous, reddish brown, trapezohedral, as large as 2 mm in diameter and fractured. The garnets also contain inclusions of tridymite. Electron microprobe analyses of the garnets reveal that they are almandine-spessartine (48.0 and 47.9 mol.%, respectively), have an average composition of (Fe 1.46 Mn 1.45 Mg 0.03 Ca 0.10 )(Al 1.93 Ti 0.02 )Si 3.01 O 12 and are comparatively homogeneous in Fe and Mn concentrations from core to rim. Composited garnets from each sample site have δ18O values of 7.2 and 7.4‰. The associated quartz (after tridymite) has δ 18 O values of 17.4 and 17.6‰, values indicative of reaction with later, low-temperature water. Unaltered tridymite from higher in the stratigraphic section has a δ 18 O of 11.1‰ which, when coupled with the garnet δ 18 O values in a quartz-garnet fractionation equation, indicates isotopic equilibration (vapour-phase crystallization) at temperatures of ~600°C. This high-temperature mineralization, formed during cooling of the tuffs, is distinct from the later and commonly recognized low-temperature stage (generally 50–70°C) of calcite, quartz and opal secondary mineralization, formed from downward-percolating meteoric water, that locally coats fracture footwalls and lithophysal floors.

Nevada↗

In situ LA-ICPMS U–Pb dating of cassiterite without a known-age matrix-matched reference material: Examples from worldwide tin deposits spanning the Proterozoic to the Tertiary

Cassiterite (SnO 2 ), a main ore mineral in tin deposits, is suitable for U–Pb isotopic dating because of its relatively high U/Pb ratios and typically low common Pb. We report a LA-ICPMS analytical procedure for U–Pb dating of this mineral with no need for an independently dated matrix-matched cassiterite standard. LA-ICPMS U-Th-Pb data were acquired while using NIST 612 glass as a primary non-matrix-matched standard. Raw data are reduced using a combination of Iolite™ and other off-line data reduction methods. Cassiterite is extremely difficult to digest, so traditional approaches in LA-ICPMS U-Pb geochronology that utilize well-characterized matrix-matched reference materials (e.g., age values determined by ID-TIMS) cannot be easily implemented. We propose a new approach for in situ LA-ICPMS dating of cassiterite, which benefits from the unique chemistry of cassiterite with extremely low Th concentrations (Th/U ratio of 10 −4 or lower) in some cassiterite samples. Accordingly, it is assumed that 208 Pb measured in cassiterite is mostly of non-radiogenic origin—it was initially incorporated in cassiterite during mineral formation, and can be used as a proxy for common Pb. Using 208 Pb as a common Pb proxy instead of 204 Pb is preferred as 204 Pb is much less abundant and is also compromised by 204 Hg interference during the LA-ICPMS analyses. Our procedure relies on 208 Pb/ 206 Pb vs 207 Pb/ 206 Pb (Pb-Pb) and Tera-Wasserburg 207 Pb/ 206 Pb vs 238 U/ 206 Pb (U-Pb) isochron dates that are calculated for a ~1.54 Ga low-Th cassiterite reference material with varying amounts of common Pb that we assume remained a closed U-Pb system. The difference between the NIST 612 glass normalized biased U-Pb date and the Pb-Pb age of the reference material is used to calculate a correction factor (F) for instrumental U-Pb fractionation. The correction factor (F) is then applied to measured U/Pb ratios and Tera-Wasserburg isochron dates are obtained for the unknown cassiterite analyzed in the same analytical session. This allows for U-Pb dating of cassiterite of any age with no need for an independently dated matrix-matched reference material, nor assumptions about the isotopic composition o f common Pb. Results for cassiterite from tin deposits in Bolivia, Brazil, China, Russia, Saudi Arabia, South Africa, Spain, and the United Kingdom, with ages ranging from ~20 Ma to ~2060 Ma, demonstrate the applicability of this approach across a broad range of geologic time. These ages are in good agreement with published geochronology of the host rocks assoc iated with the tin deposits and with previously published U-Pb ages of some cassiterites from the same deposits. Thus, our in situ LA-ICPMS methodology verifies the use of cassiterite as a reliable U-Pb mineral-geochronometer with the advantages of fast and relatively low cost in situ analyses with moderate spatial resolution.

Chemical Geology↗

Igneous and detrital zircon U-Pb and Lu-Hf geochronology of the late Meso- to Neoproterozoic northwest Botswana rift: Maximum depositional age and provenance of the Ghanzi Group, Kalahari Copperbelt, Botswana and Namibia

New igneous and detrital zircon laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) U-Pb geochronology and Lu-Hf isotopic data are presented for the Mesoproterozoic Kgwebe Formation and the unconformably overlying Ghanzi Group in northwestern Botswana. The Makgabana Hills porphyritic rhyolite flow from the Ghanzi area yielded a U-Pb concordia age of 1085.5 ± 4.5 Ma and provides a new maximum depositional age for the unconformably overlying Ghanzi Group. Detrital zircon (n = 448) from the Ghanzi Group yielded a 207 Pb/ 206 Pb age distribution with a dominant (70 to 90%) Mesoproterozoic population (∼1450 to ∼1050 Ma), a smaller (5 to 20%) Paleoproterozoic (∼2200 to ∼1700 Ma) population, and a few (n = 4) older (∼3000 Ma to ∼2450 Ma) grains. A maximum depositional age constraint of ∼1060 to ∼1050 Ma was obtained for middle and upper Ghanzi Group based on the weighted-mean 207 Pb/ 206 Pb age of the youngest clusters of overlapping zircon ages for each sample. Initial hafnium ratios (εHf i ) and corresponding crustal residence model ages (T C DM ) for the Paleoproterozoic zircon populations indicate either fractionation from a chondritic uniform reservoir (CHUR) or mixing between juvenile mantle and older crustal components. Mesoproterozoic zircon with εHf i values between −20 and +15 and T C DM model ages between 3000 and 1200 Ma suggest that the source terrane(s) contained magmatic rocks including both juvenile material and substantially reworked Paleoproterozoic and possibly Archean crust. Comparison with a compilation of published U-Pb, Lu-Hf, and Sm-Nd data from the Kalahari Craton suggests that the predominant Mesoproterozoic zircon population was derived from the Namaqua Sector, Rehoboth Basement Inlier, Kwando Complex, and Choma-Kalomo Block; some zircon may have had distal sources in adjacent Rodinia landmasses. Both Archean cratonic components and juvenile ∼1200 to ∼1000 Ma magmatic rocks of the Natal Sector and the Maud and Mozambique belts on the eastern margin of the craton are unlikely sources for the detrital zircon based on isotopic composition. Sediment transported from the western margin of the Kalahari Craton entered the northwest Botswana rift and mixed with sediments from the Rehoboth Basement Inlier and Paleo- to Mesoproterozoic terranes that bound the northwest Botswana rift.

Precambrian Research↗

Geologic map of the upper Arkansas River valley region, north-central Colorado

This 1:50,000-scale U.S. Geological Survey geologic map represents a compilation of the most recent geologic studies of the upper Arkansas River valley between Leadville and Salida, Colorado. The valley is structurally controlled by an extensional fault system that forms part of the prominent northern Rio Grande rift, an intra-continental region of crustal extension. This report also incorporates new detailed geologic mapping of previously poorly understood areas within the map area and reinterprets previously studied areas. The mapped region extends into the Proterozoic metamorphic and intrusive rocks in the Sawatch Range west of the valley and the Mosquito Range to the east. Paleozoic rocks are preserved along the crest of the Mosquito Range, but most of them have been eroded from the Sawatch Range. Numerous new isotopic ages better constrain the timing of both Proterozoic intrusive events, Late Cretaceous to early Tertiary intrusive events, and Eocene and Miocene volcanic episodes, including widespread ignimbrite eruptions. The uranium-lead ages document extensive about 1,440-million years (Ma) granitic plutonism mostly north of Buena Vista that produced batholiths that intruded an older suite of about 1,760-Ma metamorphic rocks and about 1,700-Ma plutonic rocks. As a result of extension during the Neogene and possibly latest Paleogene, the graben underlying the valley is filled with thick basin-fill deposits (Dry Union Formation and older sediments), which occupy two sub-basins separated by a bedrock high near the town of Granite. The Dry Union Formation has undergone deep erosion since the late Miocene or early Pliocene. During the Pleistocene, ongoing stream incision by the Arkansas River and its major tributaries has been interrupted by periodic aggradation. From Leadville south to Salida as many as seven mapped alluvial depositional units, that range in age from early to late Pleistocene, record periodic aggradational events along these streams that are commonly associated with deposition of glacial outwash or bouldery glacial-flood deposits. Many previously unrecognized Neogene and Quaternary faults, some of the latter with possible Holocene displacement, have been identified on lidar (light detection and ranging) imagery which covers 59 percent of the map area. This imagery has also permitted more accurate remapping of glacial, fluvial, and mass-movement deposits and aided in the determination of their relative ages. Recently published 10 beryllium cosmogenic surface-exposure ages, coupled with our new geologic mapping, have revealed the timing and rates of late Pleistocene deglaciation. Glacial dams that impounded the Arkansas River at Clear Creek and possibly at Pine Creek failed at least three times during the middle and late Pleistocene, resulting in catastrophic floods and deposition of enormous boulders and bouldery alluvium downstream; at least two failures occurred during the late Pleistocene during the Pinedale glaciation.

Colorado↗

U-Pb ages and geochemistry of zircon from Proterozoic plutons of the Sawatch and Mosquito ranges, Colorado, U.S.A.: Implications for crustal growth of the central Colorado province

A broad study of zircons from plutonic rocks of the Sawatch and Mosquito ranges of west-central Colorado (U.S.A.) was undertaken to significantly refine the magmatic chronology and chemistry of this under-studied region of the Colorado province. This region was chosen because it lies just to the north of the suspected arc-related Gunnison-Salida volcano-plutonic terrane, which has been the subject of many recent investigations—and whose origin is still debated. Our new results provide important insights into the processes active during Proterozoic crustal evolution in this region, and they have important ramifications for broader-scope crustal evolution models for southwestern North America. Twenty-four new U-Pb ages and sequentially acquired rare-earth element (REE), U, Th, and Hf contents of zircon have been determined using the sensitive high-resolution ion microprobe-reverse geometry (SHRIMP-RG). These zircon geochemistry data, in conjunction with whole-rock major- and trace-element data, provide important insights into zircon crystallization and melt fractionation, and they help to further constrain the tectonic environment of magma generation. Our detailed zircon and whole-rock data support the following three interpretations: (1) The Roosevelt Granite in the southern Sawatch Range was the oldest rock dated at 1,766 ± 7 Ma, and it intruded various metavolcanic and metasedimentary rocks. Geochemistry of both whole-rock and zircon supports the contention that this granite was produced in a magmatic arc environment and, therefore, is likely an extension of the older Dubois Greenstone Belt of the Gunnison Igneous Complex (GIC) and the Needle Mountains (1,770–1,755 Ma). Rocks of the younger Cochetopa succession of the GIC, the Salida Greenstone Belt, and the Sangre de Cristo Mountains (1,740–1,725 Ma) were not found in the Sawatch and Mosquito ranges. This observation strongly suggests that the northern edge of the Gunnison-Salida arc terrane underlies the southern portion of the Sawatch and Mosquito ranges. (2) Calc-alkalic to alkali-calcic magmas intruded this region approximately 55 m.y. after the Roosevelt Granite with emplacement of pre-deformational plutons at ca. 1,710 Ma (e.g., Henry Mountain Granite and diorite of Denny Creek), and this continued for at least 30 m.y., ending with emplacement of post-deformational plutons at ca. 1,680 Ma (e.g., Kroenke Granodiorite, granite of Fairview Peak, and syenite of Mount Yale). The timing of deformation can be constrained to sometime after intrusion of the diorite of Denny Creek and likely before the emplacement of the undeformed granite of Fairview Peak. Geochemistry of both whole-rock and zircon indicates that the older group of ca. 1,710-Ma plutons formed at shallower depths, and then they intruded the younger group of more deeply generated, commonly peraluminous and sodic plutons. Although absent in the Sawatch and Mosquito ranges, Mazatzal-age (ca. 1,680–1,620 Ma) plutonic rocks are present regionally. Inherited zircon components of Mazatzal-age were found as cores in some 1.4-Ga Sawatch and Mosquito Range zircons, indicating the likelihood of a relatively local source. These combined data suggest the possibility that all were produced within a continental-margin magmatic arc created as a result of southward-migrating (slab rollback?), north-dipping subduction to the south of the region. (3) Widespread Mesoproterozoic plutonism—with emplacement at various depths and exhibiting bimodal geochemistry—is recognized in 16 different samples. An older group of predominantly peraluminous, yet magnesian granitoids (e.g., granodiorite of Sayers, granite of Taylor River, and the St. Kevin Granite) were emplaced between ca. 1,450 and 1,425 Ma. These geochemical parameters suggest moderate degrees of partial melting in a low-pressure environment. Three younger metaluminous, but ferroan plutons (diorite of Grottos, diorite of Mount Elbert, and granodiorite of Mount Harvard), probably represent a final magmatic pulse at ca. 1,416 Ma. A comprehensive treatment of zircon REE and whole-rock trace-element behavior from Proterozoic rocks is scarce. Discriminant U/Yb versus Y diagrams using zircon data show that the Sawatch and Mosquito plutons are of continental origin, not oceanic. Additional bivariate diagrams incorporating cation ratio combinations of Gd, Ce, Yb, U, Th, Hf, and Eu offer refined insight into differences in fractionation trends and depth of magma generation for the various plutons. These interpretations, on the basis of zircon trace-element data, are mirrored in the whole-rock geochemistry data.

Colorado↗

High spatial resolution U-Pb geochronology and Pb isotope geochemistry of magnetite-apatite ore from the Pea Ridge iron oxide-apatite deposit, St. Francois Mountains, southeast Missouri, USA

The Pea Ridge iron oxide-apatite (IOA) deposit is one of the major rhyolite-hosted magnetite deposits of the St. Francois Mountains terrane, which is located within the Mesoproterozoic (1.5–1.3 Ga) Granite-Rhyolite province in the U.S. Midcontinent. Precise and accurate determination of the timing and duration of oreforming processes in this deposit is crucial for understanding its origin and placing it within a deposit-scale and regional geologic context. Apatite and monazite, well-established U-Pb mineral geochronometers, are abundant in the Pea Ridge orebody. However, the potential presence of multiple generations of dateable minerals, processes of dissolution-reprecipitation, and occurrence of micrometer-sized intergrowths and inclusions complicate measurements and interpretations of the geochronological results. Here, we employ a combination of several techniques, including ID-TIMS and high spatial resolution geochronology of apatite and monazite using LA-SC-ICPMS and SHRIMP, and Pb isotope geochemistry of pyrite and magnetite to obtain the first direct age constraints on the formation and alteration history of the Pea Ridge IOA deposit. The oldest apatite TIMS 207 Pb*/ 206 Pb* dates are 1471 ± 1 and 1468 ± 1 Ma, slightly younger than (but within error of) the ~1474 to ~1473 Ma U-Pb zircon ages of the host rhyolites. Dating of apatite and monazite inclusions within apatite provides evidence for at least one younger metasomatic event at ~1.44 Ga, and possibly multiple superimposed metasomatic events between 1.47 and 1.44 Ga. Lead isotop analyses of pyrite show extremely radiogenic 206 Pb/ 204 Pb ratios up to ~80 unsupported by in situ U decay. This excess radiogenic Pb in pyrite may have been derived from the spatially associated apatite as apatite recrystallized several tens of million years after its formation. The low initial 206 Pb/ 204 Pb ratio of ~16.5 and 207 Pb/ 204 Pb ratio of ~15.4 for individual magnetite grains indicate closed U-Pb system behavior in this mineral and are consistent with derivation of the Pb from a mantle-like source.

Missouri↗

U–Pb, Rb–Sr, and U-series isotope geochemistry of rocks and fracture minerals from the Chalk River Laboratories site, Grenville Province, Ontario, Canada

As part of the Geologic Waste Management Facility feasibility study, Atomic Energy of Canada Ltd. (AECL) is evaluating the suitability of the Chalk River Laboratories (CRL) site in Ontario, situated in crystalline rock of the southwestern Grenville Province, for the possible development of an underground repository for low- and intermediate-level nuclear waste. This paper presents petrographic and trace element analyses, U–Pb zircon dating results, and Rb–Sr, U–Pb and U-series isotopic analyses of gneissic drill core samples from the deep CRG-series characterization boreholes at the CRL site. The main rock types intersected in the boreholes include hornblende–biotite (±pyroxene) gneisses of granitic to granodioritic composition, leucocratic granitic gneisses with sparse mafic minerals, and garnet-bearing gneisses with variable amounts of biotite and/or hornblende. The trace element data for whole-rock samples plot in the fields of within-plate, syn-collision, and volcanic arc-type granites in discrimination diagrams used for the tectonic interpretation of granitic rocks. Zircons separated from biotite gneiss and metagranite samples yielded SHRIMP-RG U–Pb ages of 1472 ± 14 (2 σ ) and 1045 ± 6 Ma, respectively, in very good agreement with widespread Early Mesoproterozoic plutonic ages and Ottawan orogeny ages in the Central Gneiss Belt. The Rb–Sr, U–Pb, and Pb–Pb whole-rock errorchron apparent ages of most of the CRL gneiss samples are consistent with zircon U–Pb age and do not indicate substantial large-scale preferential element mobility during superimposed metamorphic and water/rock interaction processes. This may confirm the integrity of the rock mass, which is a positive attribute for a potential nuclear waste repository. Most 234 U/ 238 U activity ratios (AR) in whole rock samples are within errors of the secular equilibrium value of one, indicating that the rocks have not experienced any appreciable U loss or gain within the past 1 Ma. However, 234 U/ 238 U AR in fracture mineral samples collected down to borehole lengths of about 740 m deviate from the secular equilibrium value and 234 U/ 238 U model ages calculated for fracture mineral samples showing excess 234 U range from 593 to 1415 ka, thus providing evidence of fracture flow in the associated bedrock during the past 1.5 Ma. Rare earth element patterns are variable in fracture-filling calcites and Fe oxides/hydroxides but are similar to those observed in associated whole-rock samples. The observed Ce anomalies are very small ( Ce N / Ce N ∗ ≈ 1 "> CeN/CeN∗≈1 ), do not vary with depth, and, therefore, do not contain evidence that the studied fracture minerals precipitated from oxidizing waters at the conceptual depth of a repository.

Ontario↗

Mass fractionation of noble gases in synthetic methane hydrate: Implications for naturally occurring gas hydrate dissociation

As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings may presently be dissociating and releasing methane and other gases to the ocean-atmosphere system. A key challenge in assessing the impact of dissociating gas hydrates on global atmospheric methane is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sediments (some newly thawed), coal beds, and other sources. Carbon and deuterium stable isotopic fractionation during methane formation provides a first-order constraint on the processes (microbial or thermogenic) of methane generation. However, because gas hydrate formation and dissociation do not cause significant isotopic fractionation, a stable isotope-based hydrate-source determination is not possible. Here, we investigate patterns of mass-dependent noble gas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under laboratory conditions, we document complex noble gas fractionation patterns in the gases liberated during dissociation and explore the effects of aging and storage (e.g., in liquid nitrogen), as well as sampling and preservation procedures. The laboratory results confirm a unique noble gas fractionation pattern for gas hydrates, one that shows promise in evaluating modern natural gas seeps for a signature associated with gas hydrate dissociation.

Chemical Geology↗

The Spar Lake strata-Bound Cu-Ag deposit formed across a mixing zone between trapped natural gas and metals-bearing brine

Ore formation at the Spar Lake red bed-associated strata-bound Cu deposit took place across a mixing and reaction zone between a hot oxidized metals-transporting brine and a reservoir of “sour” (H 2 S-bearing) natural gas trapped in the host sandstones. Fluid inclusion volatile analyses have very high CH 4 concentrations (≥1 mol % in most samples), and a sample from the fringe of the deposit has between 18 and 36 mol % CH 4 . The ratio of CH 4 /CO 2 in fluid inclusions appears to vary regularly across the deposit, with the lowest CH 4 /CO 2 ratios from high-grade chalcocite-bearing ore, and the highest from the chalcopyrite-bearing fringe. The helium R/R a isotope ratios (0.23–0.98) and concentrations define a mixture between crustal and atmospheric helium. The volatiles in fluid inclusions (CH 4 , CO 2 , H 2 S, SO 2 , H 2 , H 2 O, and other organic gases) and values of f O 2 and temperature calculated from the volatiles data all show gradations across the deposit that are completely consistent with such a mixing and reaction zone. Other volatiles from the fluid inclusions (HCl, HF, 3 He, Msup>4 He, N 2 , Ar) characterize the brine and give evidence for only shallow crustal fluids with no magmatic influences. The brine entered the gas reservoir from below and along the axis of the deposit and migrated out along bedding to the southwest, northeast, and northwest. Metals-transporting brines may have been fed into the host sandstones from the East Fault, but that remains uncertain. Abundant ore-stage Fe and Mn calcite cements from the reduced fringe have δ 13 C values as low as −18.4‰, and many values less than −10‰, which indicate that significant carbonate was generated by oxidation of organic carbon from the natural gas. The zone of calcite cements with very low δ 13 C values approximately envelopes chalcocite-bearing ore. Sulfur isotope data of Cu, Pb, and Fe sulfides and barite indicate derivation of roughly half of the orebody sulfide directly from sour gas H 2 S. That sour gas H 2 S had developed in steps known from other sedimentary basins, starting with (1) bacterial sulfate reduction (BSR) of seawater sulfate having δ 34 S of about 20‰ and sequestering of the sulfide in organic matter in source rocks stratigraphically below the deposit host rocks, followed by (2) maturation of the sulfide-bearing organic matter into liquid petroleum with relatively homogeneous sulfide having δ 34 S of 5 ± 5‰, then by (3) thermal cracking of the oil to CH 4 and H 2 S with relatively homogeneous sulfide having δ 34 S closely distributed, about 6‰. The CH 4 and H 2 S migrated and were trapped in sandstones of the upper member of the Revett Formation, where they were later met by the 200°C metals-transporting brine. There was additional contribution of sulfide to ore from later thermochemical sulfate reduction (TSR) operating on sulfate δ 34 S of 20 to 29‰ in both formation waters and metals-transporting solutions. A large range of δ 34 S in sulfides resulted as the 6‰ sour gas sulfide was supplemented with varying proportions of 20 to 29‰ sulfide from TSR.

Economic Geology↗

Fluid geochemistry of Yucca Mountain and vicinity

Yucca Mountain, a site in southwest Nevada, has been proposed for a deep underground radioactive waste repository. An extensive database of geochemical and isotopic characteristics has been established for pore waters and gases from the unsaturated zone, perched water, and saturated zone waters in the Yucca Mountain area. The development of this database has been driven by diverse needs of the Yucca Mountain Project, especially those aspects of the project involving process modeling and performance assessment. Water and gas chemistries influence the sorption behavior of radionuclides and the solubility of the radionuclide compounds that form. The chemistry of waters that may infiltrate the proposed repository will be determined in part by that of water present in the unsaturated zone above the proposed repository horizon, whereas pore-water compositions beneath the repository horizon will influence the sorption behavior of the radionuclides transported toward the water table. However, more relevant to the discussion in this chapter, development and testing of conceptual flow and transport models for the Yucca Mountain hydrologic system are strengthened through the incorporation of natural environmental tracer data into the process. Chemical and isotopic data are used to establish bounds on key hydrologic parameters and to provide corroborative evidence for model assumptions and predictions. Examples of specific issues addressed by these data include spatial and temporal variability in net fluxes, the role of faults in controlling flow paths, fracture-matrix interactions, the age and origin of perched water, and the distribution of water traveltimes.

Nevada↗

Meteoric precipitation at Yucca Mountain, Nevada: Chemical and stable isotope analyses, 2006-09

Meteoric precipitation samples collected in 2006-09 at Yucca Mountain, Nevada, were analyzed for chemistry and stable isotope composition. Precipitation is the major source of infiltration to the unsaturated zone and of recharge to the saturated zone at Yucca Mountain. On February 28, 2005, seepage of water was observed about 40 to 80 meters below the ground surface within the Tiva Canyon Tuff in the South Ramp of the Exploratory Studies Facility tunnel within Yucca Mountain. This seepage was preceded by a 5-month period of above-average precipitation. Chemical and isotopic analysis of this seepage could not be used to estimate travel time, extent of water-rock interaction, and (or) evaporative water loss during percolation through the unsaturated zone due to the lack of corresponding chemical and isotopic analyses of precipitation inputs to the infiltration events that produced the seepage. In February 2006, collection of precipitation samples for chemical (major ions), delta oxygen-18 (&delta 18 O), and delta deuterium (&deltaD) analyses began at seven meteorological monitoring stations to provide baseline isotopic and chemical analyses. The sampling stations range in elevation from 1,131 to 1,562 meters. Each site has two collectors-one for chemical analysis and the other for isotopic analysis of precipitation. The collectors were sampled and emptied after each precipitation event. In 2006-09, 36 distinct precipitation events, with an average 3- to 4-day duration and an average 9.9 millimeters of accumulation, have been analyzed. The chemical composition of these samples of Yucca Mountain precipitation is relatively dilute but contains measurable and variable concentrations of Na + , Ca 2+ , NH + , NO 3 - , and SO 4 2- . Dust transported by typical winter storms and generated from soil carbonates is the main contributor to this precipitation chemistry. Elevated nitrate and ammonium concentrations may be linked to agriculture in the nearby Amargosa River valley to the south and west of Yucca Mountain. Cumulatively, &delta 18 O values range from 3.0 to -20.4 per mil (%o) and &deltaD values range from 10 to -14%o. Winter-season precipitation commonly has isotopically lighter compositions. The cumulative &delta18O plotted against &deltaD shows that precipitation samples define a line with slope of 6.4, less than the 8 of the Global Meteoric Water Line. This difference in slope, typical of arid environments, is chiefly the result of evaporation of falling raindrops due to warmer air temperatures. ;

Scientific Investigations Report↗

Observations of mass fractionation of noble gases in synthetic methane hydrate

As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings are presently dissociating and releasing methane and other gases to the oceanatmosphere system. A key challenge in assessing the susceptibility of gas hydrates to warming climate is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sublake and subseafloor sediments, coalbeds, and other sources. Carbon and deuterium stable isotopic data provide only a first-order characterization of methane sources, while gas hydrate can sequester any type of methane. Here, we investigate the possibility of exploiting the pattern of noble gas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under careful laboratory conditions, we document complex noble gas fractionation patterns in the gases liberated during dissociation and explore the effects of aging and storage (e.g., in liquid nitrogen), as well as sampling and preservation procedures. The laboratory results confirm a unique noble gas fractionation pattern for gas hydrates, one that shows promise in evaluating modern natural gas seeps for a signature associated with gas hydrate dissociation.

Conference Paper↗