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Carbon dioxide and hydrogen sulfide degassing and cryptic thermal input to Brimstone Basin, Yellowstone National Park, Wyoming

Brimstone Basin, a remote area of intense hydrothermal alteration a few km east of the Yellowstone Caldera, is rarely studied and has long been considered to be a cold remnant of an ancient hydrothermal system. A field campaign in 2008 confirmed that gas emissions from the few small vents were cold and that soil temperatures in the altered area were at background levels. Geochemical and isotopic evidence from gas samples ( 3 He/ 4 He ~ 3R A , δ 13 C-CO 2 ~ − 3‰) however, indicate continuing magmatic gas input to the system. Accumulation chamber measurements revealed a surprisingly large diffuse flux of CO 2 (~ 277 t d -1 ) and H 2 S (0.6 t d -1 ). The flux of CO 2 reduces the 18 O content of the overlying cold groundwater and related stream waters relative to normal meteoric waters. Simple isotopic modeling reveals that the CO 2 likely originates from geothermal water at a temperature of 93 ± 19 °C. These results and the presence of thermogenic hydrocarbons (C1:C2 ~ 100 and δ 13 C-CH 4 = − 46.4 to − 42.8‰) in gases require some heat source at depth and refute the assumption that this is a “fossil” hydrothermal system.

Wyoming↗

Introduction to the special issue on ‘Frontiers in gas geochemistry’

The study of the geochemistry of gases pervades the Earth and Environmental Sciences. This is due in no small measure to the well-established thermodynamic properties of gases which allow their application to a variety of processes occurring over a wide spectrum of natural conditions. In this respect, both major and associated minor gases have been proven useful: indeed, the trace gases have been particularly important given their role as sensitive geochemical tracers. Examples where gas geochemistry places key constraints on geochemical processes include the degassing history of the solid Earth to form the atmosphere and oceans, the origin and migration characteristics of hydrocarbon deposits, the scale of climate variability, the P–T characteristics of geothermal reservoirs, and the dynamics of the earthquake cycle and volcanic activity, to name but a few. This volume continues this rich tradition with an eclectic selection of papers aimed at exploring and exploiting gas geochemistry over a myriad set of research themes.

Chemical Geology↗

Geologic controls on thermal maturity patterns in Pennsylvanian coal-bearing rocks in the Appalachian basin

Thermal maturation patterns of Pennsylvanian strata in the Appalachian basin were determined by compiling and contouring published and unpublished vitrinite reflectance (VR) measurements. VR isograd values range from 0.6% in eastern Ohio and eastern Kentucky (western side of the East Kentucky coal field) to greater than 5.5% in eastern Pennsylvania (Southern Anthracite field, Schuylkill County), corresponding to ASTM coal rank classes of high volatile C bituminous to meta-anthracite. VR isograds show that thermal maturity of Pennsylvanian coals generally increases from west to east across the basin. The isograds patterns, which are indicative of maximum temperatures during burial, can be explained by variations in paleodepth of burial, paleogeothermal gradient, or a combination of both. However, there are at least four areas of unusually high-rank coal in the Appalachian basin that depart from the regional trends and are difficult to explain by depth of burial alone: 1) a west-northwestward salient centered in southwestern Pennsylvania; 2) an elliptically-shaped, northeast-trending area centered in southern West Virginia and western Virginia; 3) the eastern part of Black Warrior coal field, Alabama; and 4) the Pennsylvania Anthracite region, in eastern Pennsylvania. High-rank excursions in southwest Pennsylvania, the Black Warrior coal field, and the Pennsylvania Anthracite region are interpreted here to represent areas of higher paleo-heat flow related to syntectonic movement of hot fluids towards the foreland, associated with Alleghanian deformation. In addition to higher heat flow from fluids, the Pennsylvania Anthracite region also experienced greater depth of burial. The high-rank excursion in southwest Virginia was probably primarily controlled by overburden thickness, but may also have been influenced by higher geothermal gradients.

Appalachian basin↗

The petrology of dispersed organic matter in sedimentary rocks: Review and update

Organic petrology developed from coal petrology, and, in the 1960s, it began to be applied to the study of dispersed organic matter (DOM) in sedimentary rocks other than coal. Over the last few decades, the petrology of DOM has been used to characterize organic matter in sedimentary basins with an emphasis on fossil fuel resource exploration. Today, due to the global research shift on topics related to climate, organic petrology has expanded into new application areas, such as geothermal exploration, biological carbon storage (biochar), disposal, and management of radioactive waste. From the publication of the International Handbook of Coal Petrology (mid-20th century) to the present day, a large number of standards, books, and articles have been published as a result of the work of organic petrographers and petrologists around the world and efforts of the International Committee for Coal and Organic Petrology (ICCP) and The Society for Organic Petrology (TSOP) to promote the study of organic petrology. The current fundamentals and standards of organic petrology provide the international scientific community with well-informed guidance and recommendations to promote in-depth research. However, this information is currently widely scattered, leading to discrepancies in methodology and terminology. Therefore, this paper aims to present a comprehensive review of the main analytical standard test methods and techniques currently used in the petrology of DOM under reflected white light and UV and blue-light excitation, and to provide an efficient and well-defined reference guide. Furthermore, considering the important role of the ICCP in the development of organic petrology since the 1950s, a brief review of the ongoing activities of ICCP dealing with DOM is also presented.

International Journal of Coal Geology↗

Expanding the role of reactive transport models in critical zone processes

Models test our understanding of processes and can reach beyond the spatial and temporal scales of measurements. Multi-component Reactive Transport Models (RTMs), initially developed more than three decades ago, have been used extensively to explore the interactions of geothermal, hydrologic, geochemical, and geobiological processes in subsurface systems. Driven by extensive data sets now available from intensive measurement efforts, there is a pressing need to couple RTMs with other community models to explore non-linear interactions among the atmosphere, hydrosphere, biosphere, and geosphere. Here we briefly review the history of RTM development, summarize the current state of RTM approaches, and identify new research directions, opportunities, and infrastructure needs to broaden the use of RTMs. In particular, we envision the expanded use of RTMs in advancing process understanding in the Critical Zone, the veneer of the Earth that extends from the top of vegetation to the bottom of groundwater. We argue that, although parsimonious models are essential at larger scales, process-based models offer tools to explore the highly nonlinear coupling that characterizes natural systems. We present seven testable hypotheses that emphasize the unique capabilities of process-based RTMs for (1) elucidating chemical weathering and its physical and biogeochemical drivers; (2) understanding the interactions among roots, micro-organisms, carbon, water, and minerals in the rhizosphere; (3) assessing the effects of heterogeneity across spatial and temporal scales; and (4) integrating the vast quantity of novel data, including “omics” data (genomics, transcriptomics, proteomics, metabolomics), elemental concentration and speciation data, and isotope data into our understanding of complex earth surface systems. With strong support from data-driven sciences, we are now in an exciting era where integration of RTM framework into other community models will facilitate process understanding across disciplines and across scales.

Earth-Science Reviews↗

Sulfur cycle in the Valles Caldera volcanic complex, New Mexico – Letter 1: Sulfate sources in aqueous system, and implications for S isotope record in Gale Crater on Mars

Initial in situ sulfur (S) isotope measurements of the Martian bedrock in Gale Crater have revealed an unexpectedly wide range of δ 34 S values (−47 to +28%). Generally, it is unclear what processes could have contributed to these large isotope fractionations. Therefore, we studied S sources and aqueous SO 2− 4 cycling in the Valles Caldera volcanic complex, New Mexico to better understand S isotope fractionations related to S degassing, hydrothermal activity, and low-temperature processes in aqueous environment. Overall, our study demonstrates that volcanic systems show large spatial heterogeneity in δ 34 S. Magmatic S sources are obvious in steam-dominated H 2 S degassing and precipitation of secondary minerals from hydrothermal fluids with low δ 34 S values of +0.9 ±3%. Locally, however, hydrothermal processes have resulted in more negative δ 34 S values in sulfide minerals (−18 to −4%) and more positive δ 34 S values in sulfate minerals (−1 to +3%). Major aqueous SO 2− 4 sources are oxidation of H 2 S from modern hydrothermal gas emission, and oxidation and dissolution of sulfide and sulfate minerals present in the hydrothermally altered bedrock and crater-lake sediments. The δ 34 S of aqueous SO 2− 4 in surface water and groundwater varies widely (−8 to +5%) and is similar to major S endmembers that undergo oxidation and/or dissolution by active hydrological system. Minor SO 2− 4 contributions with more positive δ 34 S values (+9 to +14%) come from deeply circulating geothermal fluids and negligible amounts from atmospheric deposition (+5 to +7% in snow). Elevated SO 2− 4 contents are mainly associated with modern and past H 2 S emissions and oxidations near the surface. On regional scale, however, most of the intracaldera bedrock is S-depleted, thus the SO 2− 4 contents are usually low in the surface aquatic system and younger sedimentary lake deposits formed at times of negligible near surface hydrothermal activity. In general, magmatic-hydrothermal processes apparently cause the largest δ 34 S variation in S-bearing minerals on volcanic terrains. Therefore, we infer that the measured wide range of δ 34 S values in the Gale sediments by the Curiosity rover on Mars can be explained by S isotope composition of magmatic-hydrothermal sulfide and sulfate minerals that were present in the initial igneous/volcanic rocks prior to crater formation. Later aqueous processes involved oxidation and dissolution of S minerals initially present in these rocks and led to subsequent formation of diagenetic fluids and alteration products enriched in SO 2− 4 with relatively large δ 34 S variation. Additionally, physical erosion, transport and deposition of detrital hydrothermal S minerals from igneous/volcanic rocks might be in part responsible for the measured wide range of δ 34 S in Gale Crater. These unique S isotope results, measured in situ on another planet for the first time, imply the importance of magmatic-hydrothermal fluids in S transport on early Mars and their subsequent alteration in low-temperature aqueous environments.

New Mexico↗

Geochemical evidence for evolving Proterozoic crustal thickness and orogenic styles in southwestern Laurentia

It has long been challenging for researchers to track the crustal thickness and mode(s) of crustal modification in ancient convergent margins, limiting evaluation of the tectonic styles and processes that modify continental crust during orogenesis. We present trace element igneous geochemical crustal thickness proxies that quantitatively track the crustal thickness evolution of the long-lived Proterozoic active margin in the southwestern U.S.A. We integrate these results with geobarometric data to constrain the mode of crustal modification. The data indicate a complex record of crustal thickness change in space and time and evolving orogenic styles. Geochemical proxies at 1.84–1.72 Ga are consistent with 20–40 km thick magmatic arcs that were locally thickened to ∼50 km during ∼1.75 Ga tectonism. During the Yavapai orogeny, 1.72–1.69 Ga, a ∼200-km-wide belt of 50-60 km thick crust extended from southern California to northern Colorado and was rapidly thinned and exhumed by ∼1.68 Ga. Crustal thickening and thinning during the Yavapai orogeny largely occurred by shortening and exhumation, respectively, in the upper 25 km of the crust. Subsequent 1.68–1.60 Ga tectonism involved crustal growth, local crustal thickening, and low-P, high-T metamorphism, consistent with extensional accretionary orogenesis. The 1.47–1.37 Ga Picuris orogeny was associated with 50–60 km thick crust across much of the Southwest and involved crustal shortening with ∼10 km of magmatic underplating. Advective heat from the emplacement of ferroan granites in the mid-crust likely contributed to elevated geothermal gradients and rheologically weakened the crust. Our results suggest evolving orogenic styles in the Southwest from 1.75–1.69 Ga short-lived crustal thickening associated with terrane accretion to 1.69–1.60 Ga largely extensional accretionary orogenesis, and regional, long-lived crustal thickening at 1.47–1.37 Ga involving extensive basaltic underplating. Contrasting with some recent hypotheses, our data document a complex middle Proterozoic record for the Southwest that was not orogenically quiescent or tectonically stagnant but involved complex mountain building styles.

Earth and Planetary Science Letters↗

A new method of calculating electrical conductivity with applications to natural waters

A new method is presented for calculating the electrical conductivity of natural waters that is accurate over a large range of effective ionic strength (0.0004–0.7 mol kg −1 ), temperature (0–95 °C), pH (1–10), and conductivity (30–70,000 μS cm −1 ). The method incorporates a reliable set of equations to calculate the ionic molal conductivities of cations and anions (H + , Li + , Na + , K + , Cs + , NH 4 + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , F − , Cl − , Br − , SO 4 2- , HCO 3 - , CO 3 2- , NO 3 - , and OH − ), environmentally important trace metals (Al 3+ , Cu 2+ , Fe 2+ , Fe 3+ , Mn 2+ , and Zn 2+ ), and ion pairs (HSO 4 - , NaSO 4 - , NaCO 3 - , and ). These equations are based on new electrical conductivity measurements for electrolytes found in a wide range of natural waters. In addition, the method is coupled to a geochemical speciation model that is used to calculate the speciated concentrations required for accurate conductivity calculations. The method was thoroughly tested by calculating the conductivities of 1593 natural water samples and the mean difference between the calculated and measured conductivities was −0.7 ± 5%. Many of the samples tested were selected to determine the limits of the method and include acid mine waters, geothermal waters, seawater, dilute mountain waters, and river water impacted by municipal waste water. Transport numbers were calculated and H + , Na + , Ca 2+ , Mg 2+ , NH 4 + , K + , Cl − , SO 4 2- , HCO 3 - , CP 3 2- , F − , Al 3+ , Fe 2+ , NO 3 - , and substantially contributed (>10%) to the conductivity of at least one of the samples. Conductivity imbalance in conjunction with charge imbalance can be used to identify whether a cation or an anion measurement is likely in error, thereby providing an additional quality assurance/quality control constraint on water analyses.

Geochimica et Cosmochimica Acta↗

Ca, Sr, O and D isotope approach to defining the chemical evolution of hydrothermal fluids: example from Long Valley, CA, USA

We present chemical and isotopic data for fluids, minerals and rocks from the Long Valley meteoric-hydrothermal system. The samples encompass the presumed hydrothermal upwelling zone in the west moat of the caldera, the Casa Diablo geothermal field, and a series of wells defining a nearly linear, ∼16 km long, west-to-east trend along the likely fluid flow path. Fluid samples were analyzed for the isotopes of water, Sr, and Ca, the concentrations of major cations and anions, alkalinity, and total CO 2 . Water isotope data conform to trends documented in earlier studies, interpreted as indicating a single hydrothermal fluid mixing with local groundwater. Sr isotopes show subtle changes along the flow path, which requires rapid fluid flow and minimal reaction between the channelized fluids and the wallrocks. Sr and O isotopes are used to calculate fracture spacing using a dual porosity model. Calculated fracture spacing and temperature data for hydrothermal fluids indicate the system is (approximately) at steady-state. Correlated variations among total CO 2 , and the concentration and isotopic composition of Ca suggest progressive fluid degassing (loss of CO 2 ), which drives calcite precipitation as the fluid flows west-to-east and cools. The shifts in Ca isotopes require that calcite precipitated at temperatures of 150–180 °C is fractionated by ca. −0.3‰ to −0.5‰ relative to aqueous species. Our data are the first evidence that Ca isotopes undergo kinetic fractionation at high temperatures (>100 °C) and can be used to trace calcite precipitation along hydrothermal fluid flow paths.

California↗

Temperature-dependent variations in mineralogy, major element chemistry and the stable isotopes of boron, lithium and chlorine resulting from hydration of rhyolite glass: Constraints from hydrothermal experiments at 150 to 350°C and 25 MPa

Rhyolite-hosted hydrothermal systems in the continental crust contain valuable energy and mineral resources that make them of special interest across several scientific disciplines. Despite extensive research on these systems, the temperature-dependence of chemical reactions between host rocks and aqueous-rich fluids and the mineralogical transformations resulting from these reactions are not well quantified. To expand our understanding of the controlling processes operating in these systems, we carried out seven laboratory experiments in which rhyolite was reacted with deionized water at 150 °C to 350 °C and 25 MPa. An additional experiment at 200 °C was carried out to examine the effect of dissolved CO 2 on the reactions. The overarching goal of this experimental study was to provide new insights on the temperature-dependence of water-rock interaction in continental hydrothermal systems. We applied a wide range of chemical, isotopic and mineralogical methods to analyze the reacted rhyolite and waters, and the major observations are: (1) the rhyolite progressively hydrates with increasing temperature between 150 °C to a maximum of 8.2 wt% H 2 O at 275 °C; hydration then decreases until 350 °C in conjunction with the destruction of the rhyolite glass and crystallization of secondary mineral phases; (2) the ratio of molecular water (H 2 O m ) to hydroxyl (OH − ) of the water that is dissolved in the reacted rhyolite decreases from ∼7 at 150 °C to ∼4 at 250 °C; (3) the main secondary minerals formed are the zeolite ferrierite (T ≥ 275 °C); biotite, albite and cristobalite mainly form at higher experimental temperatures (T ≥ 300 °C); (4) the reacted waters are nearly saturated with respect to amorphous silica; (5) at temperatures ≥ 275 °C nearly all the chlorine is leached into solution; (6) fluorine leaching from the rhyolite gradually increases between 150 °C and 250 °C, but then gradually decreases at higher temperatures and is incorporated into a secondary mineral phase; (7) dissolved CO 2 in the water enhances alkali metal cation leaching from the rhyolite; and (8) calculated Na-K and silica geothermometer temperatures differ from the experimental temperatures by varying amounts. In addition, apart from some small lithium isotope fractionation at temperatures ≤ 250 °C, the stable isotopes of boron, lithium and chlorine do not fractionate during rhyolite-water reactions, and the stable isotope compositions of these species in the reacted water are similar to those in the reactant rhyolite. These results provide new insights for a broad range of applications, including quantifying processes involving rhyolite glass hydration (obsidian hydration dating, perlite formation and discriminating secondary from magmatic water in rhyolitic matrix-glass of volcanic pyroclasts), for geothermal energy and mineral deposit exploration and for monitoring volcanoes.

Geochimica et Cosmochimica Acta↗

Differential melt scaling for oblique impacts on terrestrial planets

Analytical estimates of melt volumes produced by a given projectile and contained in a given impact crater are derived as a function of impact velocity, impact angle, planetary gravity, target and projectile densities, and specific internal energy of melting. Applications to impact events and impact craters on the Earth, Moon, and Mars are demonstrated and discussed. The most probable oblique impact (45°) produces ∼1.6 times less melt volume than a vertical impact, and ∼1.6 and 3.7 times more melt volume than impacts with 30° and 15° trajectories, respectively. The melt volume for a particular crater diameter increases with planetary gravity, so a crater on Earth should have more melt than similar-size craters on Mars and the Moon. The melt volume for a particular projectile diameter does not depend on gravity, but has a strong dependence on impact velocity, so the melt generated by a given projectile on the Moon is significantly larger than on Mars. Higher surface temperatures and geothermal gradients increase melt production, as do lower energies of melting. Collectively, the results imply thinner central melt sheets and a smaller proportion of melt particles in impact breccias on the Moon and Mars than on Earth. These effects are illustrated in a comparison of the Chicxulub crater on Earth, linked to the Cretaceous–Tertiary mass extinction, Gusev crater on Mars, where the Mars Exploration Rover Spirit landed, and Tsiolkovsky crater on the Moon. The results are comparable to those obtained from field and spacecraft observations, other analytical expressions, and hydrocode simulations.

Icarus↗

High resolution identification and quantification of diffuse deep groundwater discharge in mountain rivers using continuous boat-mounted helium measurements

Discharge of deeply sourced groundwater to streams is difficult to locate and quantify, particularly where both discrete and diffuse discharge points exist, but diffuse discharge is one of the primary controls on solute budgets in mountainous watersheds. The noble gas helium is a unique identifier of deep groundwater discharge because groundwater with long residence times is commonly enriched in helium. In this study, a portable mass spectrometer was used to measure longitudinal variation in dissolved helium concentrations in two mountainous rivers at high spatial resolution not feasible with traditional sampling techniques. Helium profiles were then simulated using a mass-balance model to quantify longitudinal variation in groundwater discharge to the receiving rivers. Results indicate helium concentrations were enriched by multiple orders of magnitude above atmospheric equilibrium in both rivers and that this persisted for up to 18 km below observed pulse inputs in the Colorado River. Helium mass-balance models match observed longitudinal patterns with the exception of sharp initial increases in helium observed in the rivers. Increased longitudinal groundwater discharge rates correspond to mapped geologic structures in both watersheds that likely transport deep geothermal water. Models show variable sensitivity to spatial assignment of input variables representing the groundwater source, illustrating the importance of collecting data from discrete groundwater discharges where possible. The methodology shows promise for field experiments designed to assess air–water exchange rates and to quantify total groundwater discharge from a combination of discrete and diffuse sources.

Colorado, Utah↗

A joint Gaussian process model of geochemistry, geophysics, and temperature for groundwater TDS in the San Ardo Oil Field, California, USA

Decline in availability of fresh groundwater has expanded interest in brackish groundwater resources; however, the distribution of brackish groundwater is poorly understood. Water resources in sedimentary basins across the United States often overlie oil and gas development. Mapping of groundwater total dissolved solids (TDS) using data from oil well geophysical logs has become an important technique for identifying fresh and brackish groundwater. Existing geophysical log analysis methods use porosity and temperature to relate formation resistivity to TDS. Typically, natural geothermal gradients are used to estimate temperature at the location of collected resistivity. However, in thermally enhanced oil fields, steam is injected into the subsurface to mobilize high viscosity oil, creating variable temperature distributions. Furthermore, TDS derived from resistivity also depends on the fractions of dominant ions. Typically, chloride and bicarbonate fractions must be determined. It is also necessary to model TDS across many geologic units with heterogenous porosity distributions. Collectively, each quantity used to estimate TDS (resistivity, porosity, temperature, bicarbonate fraction) varies in space and time, and available data points are rarely collocated. Here, we present a new method of mapping groundwater TDS that continuously models each quantity together with a joint Gaussian process. This method enables mapping fresh and brackish water with practically available data. We apply this method to the San Ardo Oil Field in Monterey County, California, where steam injection occurs. In some areas of the aquifer system overlying the oil zone, the temperature is ∼75 °C, roughly twice the natural background value. Groundwater TDS is typically <1,500 mg/L in the aquifer and increases with depth to ∼9,000 mg/L in the oil-producing zone. A low-permeability clay layer delineates the fresh and brackish water, likely by inhibiting surface recharge from penetrating the deeper zones, allowing higher-TDS connate water to remain in place. Weaker lateral TDS trends may be controlled by recharge patterns associated with the Salinas River. Our model reveals with high certainty that groundwater has freshened in one localized part of the oil-producing zone and suggests with less certainty that more widespread freshening has also occurred. The lowering of TDS was possibly from decades of low-TDS steam injection and the associated fluid production and disposal operations.

California↗

Internal structure, fault rocks, and inferences regarding deformation, fluid flow, and mineralization in the seismogenic Stillwater normal fault, Dixie Valley, Nevada

Outcrop mapping and fault-rock characterization of the Stillwater normal fault zone in Dixie Valley, Nevada are used to document and interpret ancient hydrothermal fluid flow and its possible relationship to seismic deformation. The fault zone is composed of distinct structural and hydrogeological components. Previous work on the fault rocks is extended to the map scale where a distinctive fault core shows a spectrum of different fault-related breccias. These include predominantly clast-supported breccias with angular clasts that are cut by zones containing breccias with rounded clasts that are also clast supported. These are further cut by breccias that are predominantly matrix supported with angular and rounded clasts. The fault-core breccias are surrounded by a heterogeneously fractured damage zone. Breccias are bounded between major, silicified slip surfaces, forming large pod-like structures, systematically oriented with long axes parallel to slip. Matrix-supported breccias have multiply brecciated, angular and rounded clasts revealing episodic deformation and fluid flow. These breccias have a quartz-rich matrix with microcrystalline anhedral, equant, and pervasively conformable mosaic texture. The breccia pods are interpreted to have formed by decompression boiling and rapid precipitation of hydrothermal fluids whose flow was induced by coseismic, hybrid dilatant-shear deformation and hydraulic connection to a geothermal reservoir. The addition of hydrothermal silica cement localized in the core at the map scale causes fault-zone widening, local sealing, and mechanical heterogeneities that impact the evolution of the fault zone throughout the seismic cycle. ?? 2010.

Journal of Structural Geology↗

Thermal and chemical variations in subcrustal cratonic lithosphere: Evidence from crustal isostasy

The Earth's topography at short wavelengths results from active tectonic processes, whereas at long wavelengths it is largely determined by isostatic adjustment for the density and thickness of the crust. Using a global crustal model, we estimate the long-wavelength topography that is not due to crustal isostasy. Our most important finding is that cratons are generally depressed by 300 to 1500 m in comparison with predictions from pure crustal isostasy. We conclude that either: (1) cratonic roots may be 50 to 300 °C colder than previously suggested by thermal models, or (2) cratonic roots may be, on average, less depleted than suggested by studies of shallow mantle xenoliths. Alternatively, (3) some combination of these conditions may exist. The thermal explanation is consistent with recent geothermal studies that indicate low cratonic temperatures, as well as seismic studies that show very low seismic attenuation at long periods (150 s) beneath cratons. The petrologic explanation is consistent with recent studies of deep (>140 km) mantle xenoliths from the Kaapvaal and Slave cratons that show 1–2% higher densities compared with shallow (<140 km), highly depleted xenoliths.

LITHOS↗

Garnet lherzolites from Louwrensia, Namibia: Bulk composition and P/T relations

Bulk, mineral and trace element analyses of garnet lherzolite xenoliths from the Louwrensia kimberlite pipe, south-central Namibia, together with previously published Re-Os isotopic data [Chem. Geol. (2004)], form the most extensive set of chemical data for off-craton suites from southern Africa. The Louwrensia suite is similar to those from the Kaapvaal craton in that it includes both predominantly coarse-grained, equant-textured peridotites characterised by equilibration temperatures <1100 ??C and variably deformed peridotites, frequently sheared, with higher equilibration temperatures >1200 ??C. Redepletion ages range back to 2.1 Gy, concordant with the age of the crustal basement and about 1 Gy younger than the older peridotites of the adjacent Kaapvaal craton root. The coarse, low-temperature Louwrensia peridotites have an average Mg number for olivine of 91.6 in comparison to 92.6 for low-temperature peridotites from the craton. Orthopyroxene content averages 24 wt.% with a range of 11-40 wt.% for Louwrensia low-temperature peridotites, in comparison to a mean of 31.5 wt.% and a range of 11-44 wt.% for low-temperature peridotites from the Kaapvaal craton. Other major, minor and trace element concentrations in minerals forming Louwrensia lherzolites are more similar to values in corresponding Kaapvaal peridotite minerals than to those in lithospheric peridotites of Phanerozoic age as represented by off-craton basalt-hosted xenoliths and orogenic peridotites. Proportions of clinopyroxene and garnet in both the Louwrensia and Kaapvaal lherzolites overlap in the range up to 10 wt.% forming a trend extending towards pyrolite composition. Disequilibrium element partitioning between clinopyroxene and garnet for some incompatible trace elements is evidence that some of the trend is caused by enrichment following depletion. The disequilibrium is interpreted to have been caused by relatively recent growth of diopside, as previously suggested for cratonic peridotites. Attempts to constrain the depth of melting required to produce the Louwrensia peridotites suggests formation at pressures <3 GPa. Estimates of temperature and depth of equilibration for low-temperature Louwrensia lherzolites yield a trend that is in approximate agreement with the average geotherm for the Kaapvaal craton and may indicate that the lithospheric mantle beneath this region was at one time as thick as that beneath the craton (>200 km). Temperature-depth plots for the high-temperature Louwrensia rocks, however, form pronounced, apparent higher-temperature thermal anomalies at depths of 140 km and above. These anomalies are believed to reflect regional igneous activity, perhaps associated with thermal erosion of an originally thicker lithosphere, a short time prior to eruption. ?? 2004 Elsevier B.V. All rights reserved.

LITHOS↗

Timing of Precambrian melt depletion and Phanerozoic refertilization events in the lithospheric mantle of the Wyoming Craton and adjacent Central Plains Orogen

Garnet peridotite xenoliths from the Sloan kimberlite (Colorado) are variably depleted in their major magmaphile (Ca, Al) element compositions with whole rock Re-depletion model ages generally consistent with this depletion occurring in the mid-Proterozoic. Unlike many lithospheric peridotites, the Sloan samples are also depleted in incompatible trace elements, as shown by the composition of separated garnet and clinopyroxene. Most of the Sloan peridotites have intermineral Sm-Nd and Lu-Hf isotope systematics consistent with this depletion occurring in the mid-Proterozoic, though the precise age of this event is poorly defined. Thus, when sampled by the Devonian Sloan kimberlite, the compositional characteristics of the lithospheric mantle in this area primarily reflected the initial melt extraction event that presumably is associated with crust formation in the Proterozoic-a relatively simple history that may also explain the cold geotherm measured for the Sloan xenoliths. The Williams and Homestead kimberlites erupted through the Wyoming Craton in the Eocene, near the end of the Laramide Orogeny, the major tectonomagmatic event responsible for the formation of the Rocky Mountains in the late Cretaceous-early Tertiary. Rhenium-depletion model ages for the Homestead peridotites are mostly Archean, consistent with their origin in the Archean lithospheric mantle of the Wyoming Craton. Both the Williams and Homestead peridotites, however, clearly show the consequences of metasomatism by incompatible-element-rich melts. Intermineral isotope systematics in both the Homestead and Williams peridotites are highly disturbed with the Sr and Nd isotopic compositions of the minerals being dominated by the metasomatic component. Some Homestead samples preserve an incompatible element depleted signature in their radiogenic Hf isotopic compositions. Sm-Nd tie lines for garnet and clinopyroxene separates from most Homestead samples provide Mesozoic or younger "ages" suggesting that the metasomatism occurred during the Laramide. Highly variable Rb-Sr and Lu-Hf mineral "ages" for these same samples suggest that the Homestead peridotites did not achieve intermineral equilibrium during this metasomatism. This indicates that the metasomatic overprint likely was introduced shortly before kimberlite eruption through interaction of the peridotites with the host kimberlite, or petrogenetically similar magmas, in the Wyoming Craton lithosphere. ?? 2004 Elsevier B.V. All rights reserved.

LITHOS↗

The Homestead kimberlite, central Montana, USA: Mineralogy, xenocrysts, and upper-mantle xenoliths

The Homestead kimberlite was emplaced in lower Cretaceous marine shale and siltstone in the Grassrange area of central Montana. The Grassrange area includes aillikite, alnoite, carbonatite, kimberlite, and monchiquite and is situated within the Archean Wyoming craton. The kimberlite contains 25-30 modal% olivine as xenocrysts and phenocrysts in a matrix of phlogopite, monticellite, diopside, serpentine, chlorite, hydrous Ca-Al-Na silicates, perovskite, and spinel. The rock is kimberlite based on mineralogy, the presence of atoll-textured groundmass spinels, and kimberlitic core-rim zoning of groundmass spinels and groundmass phlogopites. Garnet xenocrysts are mainly Cr-pyropes, of which 2-12% are G10 compositions, crustal almandines are rare and eclogitic garnets are absent. Spinel xenocrysts have MgO and Cr2O3 contents ranging into the diamond inclusion field. Mg-ilmenite xenocrysts contain 7-11 wt.% MgO and 0.8-1.9 wt.% Cr2O3, with (Fe+3/Fetot) from 0.17-0.31. Olivine is the only obvious megacryst mineral present. One microdiamond was recovered from caustic fusion of a 45-kg sample. Upper-mantle xenoliths up to 70 cm size are abundant and are some of the largest known garnet peridotite xenoliths in North America. The xenolith suite is dominated by dunites, and harzburgites containing garnet and/or spinel. Granulites are rare and eclogites are absent. Among 153 xenoliths, 7% are lherzolites, 61% are harzburgites, 31% are dunites, and 1% are orthopyroxenites. Three of 30 peridotite xenoliths that were analysed are low-Ca garnet-spinel harzburgites containing G10 garnets. Xenolith textures are mainly coarse granular, and only 5% are porphyroclastic. Xenolith modal mineralogy and mineral compositions indicate ancient major-element depletion as observed in other Wyoming craton xenolith assemblages, followed by younger enrichment events evidenced by tectonized or undeformed veins of orthopyroxenite, clinopyroxenite, websterite, and the presence of phlogopite-bearing veins and disseminated phlogopite. Phlogopite-bearing veins may represent kimberlite-related addition and/or earlier K-metasomatism. Xenolith thermobarometry using published two-pyroxene and Al-in-opx methods suggest that garnet-spinel peridotites are derived from 1180 to 1390 ??C and 3.6 to 4.7 GPa, close to the diamond-graphite boundary and above a 38 mW/m2 shield geotherm. Low-Ca garnet-spinel harzburgites with G10 garnets fall in about the same T and P range. Most spinel peridotites with assumed 2.0 GPa pressure are in the same T range, possibly indicating heating of the shallow mantle. Four of 79 Cr diopside xenocrysts have P-T estimates in the diamond stability field using published single-pyroxene P-T calculation methods.

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