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Leonid A. Neymark

Publications and source records attributed to Leonid A. Neymark.

At least 19 recordsLinked to original sources

The Coles Hill uranium deposit, Virginia, USA: Geology, geochemistry, geochronology, and genetic model

The Coles Hill uranium deposit with an indicated resource of about 130 million lbs. of U 3 O 8 is the largest unmined uranium deposit in the United States. The deposit is hosted in the Taconian (approximately 480 – 450 Ma) Martinsville igneous complex, which consists of the Ordovician Leatherwood Granite (granodiorite) and Silurian Rich Acres Formation (diorite). The host rock was metamorphosed to orthogneiss during the Alleghanian orogeny (approximately 325 – 260 Ma) when it also underwent dextral strike-slip movement along the Brookneal shear zone. During the Triassic, extensional tectonics led to the development of the Dan River Basin that lies east of Coles Hill. The mineralized zone is hosted in brittle structures in the footwall of the Triassic Chatham fault that forms the western edge of the basin. Within brittle fracture zones, uranium silicate and uranium-bearing fluorapatite with traces of brannerite form veins and breccia fill with chlorite, quartz, calcite, titanium oxide, pyrite, and calcite. Uranium silicates also coat and replace primary titanite, zircon, ilmenite, and sulfides. Sodium metasomatism preceded and accompanied uranium mineralization, pervasively altering host rock, and forming albite from primary feldspar, depositing limpid albite rims on feldspar, altering titanite to titanium oxide and calcite and forming riebeckite. Various geothermometers suggest temperatures of less than approximately ~200°C during mineralization. In situ U-Pb analyses of titanite, Ti-oxide, and apatite, and Rb/Sr and U/Pb isotope-systematics of whole rock samples resolve the timing of geologic processes affecting Coles Hill. The host Leatherwood granite containing primary euhedral titanite is dated at 450 – 445 Ma, in agreement with previously obtained ages from zircon in the Martinsville igneous complex. A regional metamorphic event at 330 – 310 Ma formed anhedral titanite and some apatite, re-equilibrated whole rock Rb/Sr and U-Pb isotopes and is interpreted to have coincided with movement along the Brookneal shear zone. During shearing and metamorphism primary refractory uranium-bearing minerals including titanite, zircon, and uranothorite were recrystallized and uranium was liberated and incorporated locally into hematite, clay, and other fine-grained minerals. Uranium mineralization was accompanied by a metasomatic episode between 250 and 200 Ma that reset the Rb-Sr and U-Pb isotope systems, forming titanite and apatite that are associated and in places intimately intergrown with uranium silicate dating mineralization. This event coincides with rifting that formed the Dan River Basin and was a precursor to the breakup of Pangea. Based on the close spatial and temporal association of uranium with apatite, we conclude that uranium was carried as a uranyl-phosphate complex. The release of calcium during sodium metasomatic alteration of primary calcic feldspar and titanite in the host rock initiated successive reactions in which uranium and phosphate in mineralizing fluids combined with calcium to form U-enriched fluorapatite. Excess uranium was locally reduced by coupled redox reactions involving ferrous iron and sulfide minerals in the host rock, forming uranium silicates. Based on the deposit mineralogy, oxygen isotope geochemistry and trace element characteristics of uranium silicate and gangue minerals the primary mineralizing fluids likely included connate and/or meteoric water sourced from the local Dan River Basin. High heat flow related to Mesozoic rifting may have driven these (P-Na-F-rich) brines through local aquifers and into basin margin faults, transporting uranium from the basin or mobilizing uranium from previously formed U-minerals in the Brookneal shear zone, or from U-enriched older basement rock.

Virginia↗

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↗

Petrology and geochronology of 1.48 to 1.45 Ga igneous rocks in the St. Francois Mountains terrane, southeast Missouri

The igneous geology of the St. Francois Mountains terrane in southeast Missouri is dominated by the products of 1.48 to 1.45 billion year old volcanic and plutonic magmatism but also includes volumetrically minor, compositionally bimodal contributions added during plutonism between 1.34 and 1.27 billion years ago. The 1.48 to 1.45 billion year old igneous rocks in the St. Francois Mountains terrane are bimodally distributed between volumetrically dominant felsic rocks and volumetrically minor rocks with mafic to intermediate compositions. All of these rocks are ferroan, which like most of their trace element abundances, suggests a genesis associated with farfield intraplate extensional tectonism and decompression-related magmatism. The diversity of compositions among 1.48 to 1.45 billion year old igneous rocks in the St. Francois Mountains terrane probably reflects mixtures of mantle-derived mafic inputs and low-degree partial melting of more evolved crustal protoliths. Newly determined ages define essentially continuous magmatism during the 30-million-year period between 1.48 and 1.45 billion years ago. The products of this magmatism are essentially coeval, whether intrusive or extrusive or having mafic, intermediate, or felsic compositions. In addition, the iron oxide-apatite (for example, Pea Ridge) and likely the iron oxide-copper gold (Boss) deposits in the St. Francois Mountains terrane have ages coincident with this magmatic episode. Spatial and temporal relations between 1.48 to 1.45 billion year old igneous rocks in the St. Francois Mountains terrane and the mineral deposits they host suggest the associated magmatic and mineralization processes are also genetically related. Geochemical, petrographic, geochronologic, and terrane-wide physical characteristics of the 1.48 to 1.45 billion year old igneous rocks in the St. Francois Mountains terrane are consistent with an origin involving extension well inboard from the margin of the Laurentian craton, associated mantle upwelling, lower crustal melting in response to mantle-derived thermal inputs, and mixing of mantle- and juvenile lower crustal-derived melts. Significant major and trace element compositional dispersion characteristics of these rocks likely reflect midcrustal magma reservoir fractionation of their principal rock-forming minerals. The resultant magmas constitute a series of variably hybridized reservoirs, emplaced at upper levels in the crust, that form a series of plutonic and associated eruptive products.

Missouri↗

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↗

Combined radiogenic (87Sr/86Sr, 234U/238U) and stable (δ88Sr) isotope systematics as tracers of anthropogenic groundwater contamination within the Williston Basin USA

The Williston Basin has produced oil and gas from conventional structural and stratigraphic traps for more than 60 years. The advent of horizontal drilling and hydraulic fracturing of shale in the Devonian-Mississippian Bakken Formation has increased the production of oil in this basin from areas that partially overlap the prairie pothole region of North America. Massive scale of oil production in the Williston Basin increases the risk of accidental releases of coproduced formation water (brine) into the environment. The prairie pothole region is named for a multitude of small lakes and wetlands that provide critical habitat for waterfowl and other wildlife. The increased risks raise the importance of developing robust tracers that can identify the source(s) and quantity of contamination of this premier wetland ecosystem. Radiogenic 87 Sr/ 86 Sr and 234 U/ 238 U isotope tracers are widely used in hydrological studies to detect potential sources of groundwater contamination. Here, we used paired 87 Sr/ 86 Sr and δ 88 Sr values in wetland water, which is essentially shallow groundwater at the Goose Lake and Fuller sites in Montana and North Dakota where produced water contamination was previously established. We also analyzed brines from the Bakken Formation and Mississippian Charles Formation to evaluate potential sources of contamination. This is the first attempt to combine these isotope tracers to estimate a magnitude of groundwater contamination by the oil-field produced water. Moreover, because U +6 is soluble in water under subaerial oxidizing conditions and the U +4 content is orders of magnitude lower (pg/g levels) in reducing brines, the 234 U/ 238 U isotope tracer is insensitive to brine contamination. However, it elucidates potential variability of uncontaminated end-members and, therefore, helps to improve the accuracy of estimated degrees of brine contamination based on binary mixing relationships. In addition, U isotopes in groundwater have a potential for detecting some U-rich anthropogenic contaminants (e.g., phosphate fertilizers). Using these isotopic systematics we confirm previous conclusions that surface water and shallow groundwater in two studied sites are variably contaminated by produced water and estimate the degree of the contamination at ∼7% in a sample collected close to a brine tank and <0.5% in most other samples. The U isotope analyses in combination with the Sr isotope results help outline variable groundwater pathways and uncontaminated end-members. Also, U isotopes show no appreciable groundwater contamination from U-enriched P-fertilizers. Our study in the Williston Basin demonstrates the potential of using combined radiogenic ( 87 Sr/ 86 Sr, 234 U/ 238 U) and non-traditional stable (δ 88 Sr) isotopic systematics as tracers of anthropogenic contamination in surface and groundwater systems.

Montana, North Dakota↗

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↗

Chapter 5: Impact of sedimentary-exhalative hydrothermal systems on marine chemistry and mass extinctions: Applications for ore genesis research and mineral exploration

Times of metal-rich brine discharge into ancient ocean basins, associated with the formation of sedimentary-exhalative (sedex) Zn-Pb-Ba ore deposits, coincided with short-duration positive excursions (“spikes”) in the global marine Sr isotope record. While these spikes are unexplained by conventional oceanic models, chronostratigraphic correlations, combined with mass balance evidence and oceanographic modeling, suggest that the flux of radiogenic Sr from sedex brines during ore formation is sufficient to explain these previously enigmatic 87 Sr/ 86 Sr spikes. We review existing 87 Sr/ 86 Sr data and present new data as verification of these global 87 Sr/ 86 Sr spikes and their correlations with the formation of giant sedex ore deposits. Major events include an 1 ×10 −4 (~0.7078–~0.7079) excursion contemporaneous with formation of the Rammelsberg deposit at ~389 Ma; spikes on the order of 1 to 3 × 10 −4 , coeval with formation of the Meggen deposit at ~381 Ma, several ore deposits in the Macmillan Pass district at ~379 to 375 Ma, and the Silvermines deposits at ~352 Ma; and two >6 × 10 −4 spikes coincident with formation of the giant Navan deposit at ~346 Ma and Red Dog deposits at ~337 Ma. Moreover, the timing of peak 87 Sr/ 86 Sr spikes correlates with global δ 13 C and δ 18 O spikes, deposition of metal-rich black shales and ironstones, metal-induced malformation (teratology) of marine organisms, and mass extinctions. The relationships among these features were poorly understood, but our new model explains how the flux of key biolimiting nutrients and metals contained in sedex brines, demonstrably equivalent to or exceeding that of the total modern riverine flux to the ocean, spurred ocean eutrophication, which, ultimately, through a series of positive feedback mechanisms, may have triggered global chemical and biological events. If, as we hypothesize, sedex hydrothermal systems are recorded in the global marine isotopic, geologic, and biological records, our findings define a new approach to the study of and exploration for sedex deposits. We demonstrate that fluid inclusion solute chemistry and isotopic and stratigraphic studies of sedex deposits, coupled with chronostratigraphic correlation and high-resolution 87 Sr/ 86 Sr isotope chemostratigraphy, can be used to answer long-standing questions about geologic processes responsible for formation of these extraordinary deposits. This approach provides evidence for the age, duration, and fluxes of fluids and metals vented into the ocean by these giant hydrothermal systems. Accordingly, the marine 87 Sr/ 86 Sr curve constitutes a global exploration tool that could be applied to assess the mineral potential of sedimentary basins. To illustrate the potential of this tool to identify favorable stratigraphic ages and basins with potential for undiscovered giant sedex deposits, we highlight several spikes, on par with those characteristic of the Red Dog and Navan deposits, which have not been correlated with known metal deposits. Given these strong temporal correlations, mass balance estimates, and results of ocean chemistry modeling, our study suggests that further work is warranted to determine the extent to which periodic venting of hydrothermal basinal brines into the ocean has influenced the evolution of marine chemistry. Ultimately, these global signatures can be applied to the study of and exploration for sedex deposits.

Book chapter↗

Evaluation of laser ablation double-focusing SC-ICPMS for “common” lead isotopic measurements in silicate glasses and mineral

An analytical method for the in situ measurement of “common” Pb isotope ratios in silicate glasses and minerals using a 193-nm excimer laser ablation (LA) system with a double-focusing single-collector (SC)-ICPMS is presented and evaluated as a possible alternative to multiple-collector (MC)-ICPMS. This LA-SC-ICPMS technique employs fast-scanning ion deflectors to sequentially place a series of flat-topped isotope peaks into a single ion-counting detector at a fixed accelerating voltage and magnetic field strength. Reference materials (including NIST, MPI-DING, and USGS glasses) are used to identify two analytical artifacts on the Pb isotope ratios (expressed here as heavier/lighter isotopes) when corrected for mass bias relative to NIST SRM610. The first artifact is characterized by anomalously low Pb isotope ratios (~0.1%/AMU) when SRM610 is analyzed in raster mode as an unknown at small spot sizes (<25 µm), which may indicate that (1) SRM610 is isotopically heterogeneous on a small length scale and/or (2) there is a non-spectral matrix effect on the Pb isotope ratios related to differences in spot size. The second artifact is characterized by anomalously high Pb isotope ratios (<0.1%/AMU) for NIST SRM612 (in raster mode) and some Fe-rich glass reference materials (BCR-2G, GOR132-G, and T1-G). These offsets are thought to be caused by one or more non-spectral matrix effects related to differences in the ablation behavior, composition, or physical properties of these reference materials compared to the bracketing SRM610 standard. The precision (±2SD) of our LA-SC-ICPMS Pb isotopic measurements is similar to ( 207 Pb/ 206 Pb and 208 Pb/ 206 Pb, or 20X Pb/ 206 Pb) or better than ( 206 Pb/ 204 Pb, 207 Pb/ 204 Pb, and 208 Pb/ 204 Pb, or 20X Pb/ 204 Pb) a series of published studies that used a different type of SC-ICPMS and obtained a factor of ~3-4 higher sensitivity for Pb. An increase in the sensitivity of our LA-SC-ICPMS would likely improve the precision of the 20X Pb/ 206 Pb and 20X Pb/ 204P b ratios for low-Pb materials (<5 ppm), possibly making the technique broadly similar to LA-MC-ICPMS (particularly compared to methods that rely upon at least one ion-counting detector). Further improvement in the precision of the 20X Pb/ 206 Pb and 20X Pb/ 204 Pb ratios for high-Pb materials (>5 ppm) by LA-SC-ICPMS is unlikely, and in this case, LA-MC-ICPMS remains the preferable analytical technique.

Journal of Analytical Atomic Spectrometry↗

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↗

Isotope hydrology of the Chalk River Laboratories site, Ontario, Canada

This paper presents results of hydrochemical and isotopic analyses of groundwater (fracture water) and porewater, and physical property and water content measurements of bedrock core at the Chalk River Laboratories (CRL) site in Ontario. Density and water contents were determined and water-loss porosity values were calculated for core samples. Average and standard deviations of density and water-loss porosity of 50 core samples from four boreholes are 2.73 &plusmn; 12 g/cc and 1.32 &plusmn; 1.24 percent. Respective median values are 2.68 and 0.83 indicating a positive skewness in the distributions. Groundwater samples from four deep boreholes were analyzed for strontium (87Sr/86Sr) and uranium (234U/238U) isotope ratios. Oxygen and hydrogen isotope analyses and selected solute concentrations determined by CRL are included for comparison. Groundwater from borehole CRG-1 in a zone between approximately +60 and &minus;240 m elevation is relatively depleted in &delta;18O and &delta;2H perhaps reflecting a slug of water recharged during colder climatic conditions. Porewater was extracted from core samples by centrifugation and analyzed for major dissolved ions and for strontium and uranium isotopes. On average, the extracted water contains 15 times larger concentration of solutes than the groundwater. 234U/238U and correlation of 87Sr/86Sr with Rb/Sr values indicate that the porewater may be substantially older than the groundwater. Results of this study show that the Precambrian gneisses at Chalk River are similar in physical properties and hydrochemical aspects to crystalline rocks being considered for the construction of nuclear waste repositories in other regions.

Applied Geochemistry↗

A millennial-scale record of Pb and Hg contamination in peatlands of the Sacramento-San Joaquin Delta of California, USA

In this paper, we provide the first record of millennial patterns of Pb and Hg concentrations on the west coast of the United States. Peat cores were collected from two micro-tidal marshes in the Sacramento-San Joaquin Delta of California. Core samples were analyzed for Pb, Hg, and Ti concentrations and dated using radiocarbon, 210Pb, and 137Cs. Pre-anthropogenic concentrations of Pb and Hg in peat ranged from 0.60 to 13.0 &micro;g g-1and from 6.9 to 71 ng g-1, respectively. For much of the past 6000+ years, the Delta was free from anthropogenic pollution, however, beginning in ~1425 CE, Hg and Pb concentrations, Pb/Ti ratios, Pb enrichment factors (EFs), and HgEFs all increased. Pb isotope compositions of the peat suggest that this uptick was likely caused by smelting activities originating in Asia. The next increases in Pb and Hg contamination occurred during the California Gold Rush (beginning ~1850 CE), when concentrations reached their highest levels (74 &micro;g g-1 Pb, 990 ng g-1 Hg; PbEF = 12 and HgEF = 28). Lead concentrations increased again beginning in the ~1920s with the incorporation of Pb additives in gasoline. The phase-out of lead additives in the late 1980s was reflected in Pb isotope ratios and reductions in Pb concentrations in the surface layers of the peat. The rise and fall of Hg contamination was also tracked by the peat archive, with the highest Hg concentrations occurring just before 1963 CE and then decreasing during the post-1963 period. Overall, the results show that the Delta was a pristine region for most of its ~6700-year existence; however, since ~1425 CE, it has received Pb and Hg contamination from both global and regional sources.

California↗

40Ar/39Ar Geochronology, Isotope Geochemistry (Sr, Nd, Pb), and petrology of alkaline lavas near Yampa, Colorado: migration of alkaline volcanism and evolution of the northern Rio Grande rift

Volcanic rocks near Yampa, Colorado (USA), represent one of several small late Miocene to Quaternary alkaline volcanic fields along the northeast margin of the Colorado Plateau. Basanite, trachybasalt, and basalt collected from six sites within the Yampa volcanic field were investigated to assess correlations with late Cenozoic extension and Rio Grande rifting. In this paper we report major and trace element rock and mineral compositions and Ar, Sr, Nd, and Pb isotope data for these volcanic rocks. High-precision 40Ar/39Ar geochronology indicates westward migration of volcanism within the Yampa volcanic field between 6 and 4.5 Ma, and the Sr, Nd, and Pb isotope values are consistent with a primary source in the Proterozoic subcontinental lithospheric mantle. Relict olivine phenocrysts have Mg- and Ni-rich cores, whereas unmelted clinopyroxene cores are Na and Si enriched with finely banded Ca-, Mg-, Al-, and Ti-enriched rims, thus tracing their crystallization history from a lithospheric mantle source region to one in contact with melt prior to eruption. A regional synthesis of Neogene and younger volcanism within the Rio Grande rift corridor, from northern New Mexico to southern Wyoming, supports a systematic overall southwest migration of alkaline volcanism. We interpret this Neogene to Quaternary migration of volcanism toward the northeast margin of the Colorado Plateau to record passage of melt through subvertical zones within the lithosphere weakened by late Cenozoic extension. If the locus of Quaternary alkaline magmatism defines the current location of the Rio Grande rift, it includes the Leucite Hills, Wyoming. We suggest that alkaline volcanism in the incipient northern Rio Grande rift, north of Leadville, Colorado, represents melting of the subcontinental lithospheric mantle in response to transient infiltration of asthenospheric mantle into deep, subvertical zones of dilational crustal weakness developed during late Cenozoic extension that have been migrating toward, and subparallel to, the northeast margin of the Colorado Plateau since the middle Miocene. Quaternary volcanism within this northern Rio Grande rift corridor is evidence that the rift is continuing to evolve.

Colorado↗

Precise determination of δ 88 Sr in rocks, minerals, and waters by double-spike TIMS: A powerful tool in the study of chemical, geologic, hydrologic and biologic processes

We present strontium isotopic ( 88 Sr/ 86 Sr and 87 Sr/ 86 Sr) results obtained by 87 Sr– 84 Sr double spike thermal ionization mass-spectrometry (DS-TIMS) for several standards as well as natural water samples and mineral samples of abiogenic and biogenic origin. The detailed data reduction algorithm and a user-friendly Sr-specific stand-alone computer program used for the spike calibration and the data reduction are also presented. Accuracy and precision of our δ 88 Sr measurements, calculated as permil (‰) deviations from the NIST SRM-987 standard, were evaluated by analyzing the NASS-6 seawater standard, which yielded δ 88 Sr = 0.378 ± 0.009‰. The first DS-TIMS data for the NIST SRM-607 potassium feldspar standard and for several US Geological Survey carbonate, phosphate, and silicate standards (EN-1, MAPS-4, MAPS-5, G-3, BCR-2, and BHVO-2) are also reported. Data obtained during this work for Sr-bearing solids and natural waters show a range of δ 88 Sr values of about 2.4‰, the widest observed so far in terrestrial materials. This range is easily resolvable analytically because the demonstrated external error (±SD, standard deviation) for measured δ 88 Sr values is typically ≤0.02‰. It is shown that the “true” 87 Sr/ 86 Sr value obtained by the DS-TIMS or any other external normalization method combines radiogenic and mass-dependent mass-fractionation effects, which cannot be separated. Therefore, the “true” 87 Sr/ 86 Sr and the δ 87 Sr parameter derived from it are not useful isotope tracers. Data presented in this paper for a wide range of naturally occurring sample types demonstrate the potential of the δ 88 Sr isotope tracer in combination with the traditional radiogenic 87 Sr/ 86 Sr tracer for studying a variety of biological, hydrological, and geological processes.

Journal of Analytical Atomic Spectrometry↗

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 &#x2217; &#x2248; 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↗

234U/238U and δ87Sr in peat as tracers of paleosalinity in the Sacramento-San Joaquin Delta of California, USA

The purpose of this study was to determine the history of paleosalinity over the past 6000+ years in the Sacramento-San Joaquin Delta (the Delta), which is the innermost part of the San Francisco Estuary. We used a combination of Sr and U concentrations, d87Sr values, and 234U/238U activity ratios (AR) in peat as proxies for tracking paleosalinity. Peat cores were collected in marshes on Browns Island, Franks Wetland, and Bacon Channel Island in the Delta. Cores were dated using 137Cs, the onset of Pb and Hg contamination from hydraulic gold mining, and 14C. A proof of concept study showed that the dominant emergent macrophyte and major component of peat in the Delta, Schoenoplectus spp., incorporates Sr and U and that the isotopic composition of these elements tracks the ambient water salinity across the Estuary. Concentrations and isotopic compositions of Sr and U in the three main water sources contributing to the Delta (seawater, Sacramento River water, and San Joaquin River water) were used to construct a three-end-member mixing model. Delta paleosalinity was determined by examining variations in the distribution of peat samples through time within the area delineated by the mixing model. The Delta has long been considered a tidal freshwater marsh region, but only peat samples from Franks Wetland and Bacon Channel Island have shown a consistently fresh signal (<0.5 ppt) through time. Therefore, the eastern Delta, which occurs upstream from Bacon Channel Island along the San Joaquin River and its tributaries, has also been fresh for this time period. Over the past 6000+ years, the salinity regime at the western boundary of the Delta (Browns Island) has alternated between fresh and oligohaline (0.5-5 ppt).

California↗