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Approaches to surface complexation modeling of Uranium(VI) adsorption on aquifer sediments

Uranium(VI) adsorption onto aquifer sediments was studied in batch experiments as a function of pH and U(VI) and dissolved carbonate concentrations in artificial groundwater solutions. The sediments were collected from an alluvial aquifer at a location upgradient of contamination from a former uranium mill operation at Naturita, Colorado (USA). The ranges of aqueous chemical conditions used in the U(VI) adsorption experiments (pH 6.9 to 7.9; U(VI) concentration 2.5 · 10 −8 to 1 · 10 −5 M; partial pressure of carbon dioxide gas 0.05 to 6.8%) were based on the spatial variation in chemical conditions observed in 1999–2000 in the Naturita alluvial aquifer. The major minerals in the sediments were quartz, feldspars, and calcite, with minor amounts of magnetite and clay minerals. Quartz grains commonly exhibited coatings that were greater than 10 nm in thickness and composed of an illite-smectite clay with occluded ferrihydrite and goethite nanoparticles. Chemical extractions of quartz grains removed from the sediments were used to estimate the masses of iron and aluminum present in the coatings. Various surface complexation modeling approaches were compared in terms of the ability to describe the U(VI) experimental data and the data requirements for model application to the sediments. Published models for U(VI) adsorption on reference minerals were applied to predict U(VI) adsorption based on assumptions about the sediment surface composition and physical properties (e.g., surface area and electrical double layer). Predictions from these models were highly variable, with results overpredicting or underpredicting the experimental data, depending on the assumptions used to apply the model. Although the models for reference minerals are supported by detailed experimental studies (and in ideal cases, surface spectroscopy), the results suggest that errors are caused in applying the models directly to the sediments by uncertain knowledge of: 1) the proportion and types of surface functional groups available for adsorption in the surface coatings; 2) the electric field at the mineral-water interface; and 3) surface reactions of major ions in the aqueous phase, such as Ca 2+ , Mg 2+ , HCO 3 − , SO 4 2− , H 4 SiO 4 , and organic acids. In contrast, a semi-empirical surface complexation modeling approach can be used to describe the U(VI) experimental data more precisely as a function of aqueous chemical conditions. This approach is useful as a tool to describe the variation in U(VI) retardation as a function of chemical conditions in field-scale reactive transport simulations, and the approach can be used at other field sites. However, the semi-empirical approach is limited by the site-specific nature of the model parameters.

Geochimica et Cosmochimica Acta

Low strength of deep San Andreas fault gouge from SAFOD core

The San Andreas fault accommodates 28–34 mm yr −1 of right lateral motion of the Pacific crustal plate northwestward past the North American plate. In California, the fault is composed of two distinct locked segments that have produced great earthquakes in historical times, separated by a 150-km-long creeping zone. The San Andreas Fault Observatory at Depth (SAFOD) is a scientific borehole located northwest of Parkfield, California, near the southern end of the creeping zone. Core was recovered from across the actively deforming San Andreas fault at a vertical depth of 2.7 km (ref. 1 ). Here we report laboratory strength measurements of these fault core materials at in situ conditions, demonstrating that at this locality and this depth the San Andreas fault is profoundly weak (coefficient of friction, 0.15) owing to the presence of the smectite clay mineral saponite, which is one of the weakest phyllosilicates known. This Mg-rich clay is the low-temperature product of metasomatic reactions between the quartzofeldspathic wall rocks and serpentinite blocks in the fault 2,3 . These findings provide strong evidence that deformation of the mechanically unusual creeping portions of the San Andreas fault system is controlled by the presence of weak minerals rather than by high fluid pressure or other proposed mechanisms 1 . The combination of these measurements of fault core strength with borehole observations 1,4,5 yields a self-consistent picture of the stress state of the San Andreas fault at the SAFOD site, in which the fault is intrinsically weak in an otherwise strong crust.

California

Textural development of clayey and quartzofeldspathic fault gouges relative to their sliding behavior

Many of the secondary fault structures developed during triaxial friction experiments have been generally correlated with the structures of natural fault zones. Therefore, any physical differences that can be found between laboratory samples that slide stably and those that show stick-slip motion may help to identify the cause of earthquakes. We have examined petrographically the run products of many triaxial friction experiments using clayey and quartzofeldspathic gouges, which comprise the principal types of natural fault gouge material. The examined samples were tested under a wide range of temperature, confining and fluid pressure, and velocity conditions. The clayey and quartzofeldspathic gouges show some textural differences, owing to their different mineral contents and grain sizes and shapes. In the clayey gouges, for example, a clay mineral fabric and kink band sets are commonly developed, whereas in the quartzofeldspathic gouges fracturing and crushing of the predominately quartz and feldspar grains are important processes. For both types of gouge, however, and whatever the pressure-temperature-velocity conditions of the experiments, the transition from stable sliding to stick-slip motion is correlated with: (i) a change from pervasive deformation of the gouge layer to localized slip in subsidiary shears; and (ii) an increase in the angle betweem the shears that crosscut the gouge layer (Riedel shears) and ones that form along the gouge-rock cylinder boundaries (boundary shears). This suggests that the localization of shear within a fault zone combined with relatively high Riedel-shear angles are somehow connected with earthquakes. Secondary fracture sets similar to Riedel shears have been identified at various scales in major strike-slip faults such as the San Andreas of the western United States (Wallace, 1973) and the Luhuo and Fuyun earthquake faults of China (Deng and Zhang, 1984; Deng et al. , 1986). The San Andreas also contains locked and creeping sections that correspond to the stick-slip and stably sliding experimental samples, respectively. We plan to study the physical structure of the San Andreas fault, to see if the experimentally observed differences related to sliding behavior can also be distinguished in the field.

Physics and Chemistry of the Earth

Injection of treated wastewater for ground-water recharge in the Palo Alto Baylands, California, hydraulic and chemical interactions — Preliminary report

An injection-extraction well network in the Palo Alto Baylands along the San Francisco Bay, California, was designed to flush the shallow aquifer system of saline water and prevent further inland saline contamination. Clogging processes and solution migration in the vicinity of one injection well were studied. Cyclic evaporative concentration of bay water and infiltration have generated a concentrated ground-water brine. Montmorillonite and illite are the primary clay minerals present in the shallow aquifer system. X-ray diffraction analysis of these clays showed a marked increase in the d-spacing of the crystal lattice when native hypersaline pure water was replaced by injection water. Chloride:magnesium and chloride:potassium ratios in the aquifer system changed during injection, most likely due to ionic exchange reaction. Similar variations in chloride:boron, chloride:iron, and chloride:manganese ratios probably resulted from reduction-oxidation reactions. Ground-water quality appears to have been chiefly affected by the processes of dilution and dispersion. Extraction pump test data yielded a transmissivity value of 960 feet squared per day and a storage coefficient of 0.0005. Vertical permeability of the upper confining layer is 0.08 feet per day.

California

Integrating soils and geomorphology in mountains - An example from the Front Range of Colorado

Soil distribution in high mountains reflects the impact of several soil-forming factors. Soil geomorphologists use key pedological properties to estimate ages of Quaternary deposits of various depositional environments, estimate long-term stability and instability of landscapes, and make inferences on past climatic change. Once the influence of the soil-forming factors is known, soils can be used to help interpret some aspects of landscape evolution that otherwise might go undetected. The Front Range of Colorado rises from the plains of the Colorado Piedmont at about 1700 m past a widespread, dissected Tertiary erosion surface between 2300 and 2800 m up to an alpine Continental Divide at 3600 to over 4000 m. Pleistocene valley glaciers reached the western edge of the erosion surface. Parent rocks are broadly uniform (granitic and gneissic). Climate varies from 46 cm mean annual precipitation (MAP) and 11 ??C mean annual temperature (MAT) in the plains to 102 cm and -4 ??C, respectively, near the range crest. Vegetation follows climate with grassland in the plains, forest in the mountains, and tundra above 3450 m. Soils reflect the bioclimatic transect from plains to divide: A/Bw or Bt/Bk or K (grassland) to A/E/Bw or Bt/C (forest) to A/Bw/C (tundra). Corresponding soil pH values decrease from 8 to less than 5 with increasing elevation. The pedogenic clay minerals dominant in each major vegetation zone are: smectite (grassland), vermiculite (forest), and 1.0-1.8 nm mixed-layer clays (tundra). Within the lower forested zone, the topographic factor (aspect) results in more leached, colder soils, with relatively thin O horizons, well-expressed E horizons and Bt horizons (Alfisols) on N-facing slopes, whereas soils with thicker A horizons, less developed or no E horizons, and Bw or Bt horizons (Mollisols) are more common on S-facing slopes. The topographic factor in the tundra results in soil patterns as a consequence of wind-redistributed snow and the amount of time it lingers on the landscape. An important parent material factor is airborne dust, which results in fine-grained surface horizons and, if infiltrated, contributes to clay accumulation in some Bt horizons. The time factor is evaluated by soil chronosequence studies of Quaternary deposits in tundra, upper forest, and plains grassland. Few soils in the study area are >10,000 years old in the tundra, >100,000 years old in the forest, and >2 million years old in the grassland. Stages of granite weathering vary with distance from the Continental Divide and the best developed is grus near the sedimentary/granitic rock contact just west of the mountain front. Grus takes a minimum of 100,000 years to form. Some of the relations indicated by the soil map patterns are: (1) parts of the erosion surface have been stable for 100,000 years or more; (2) development of grus near the mountain front could be due in part to pre-Pennsylvanian weathering; (3) a few soil properties reflect Quaternary paleoclimate; and (4) a correlation between soil development in the canyons and stream incision rates. ?? 2003 Elsevier Science B.V. All rights reserved.

Geomorphology

Mineralogy and petrology of the Cretaceous- Tertiary boundary clay bed and adjacent clay-rich rocks, Raton Basin, New Mexico and Colorado.

The Cretaceous-Tertiary (K-T) boundary is preserved in a sequence of coal-bearing, fluvial rocks in the lower part of the Raton Formation (Late Cretaceous and Paleocene) at several sites in the east-central part of the Raton Basin. The K-T boundary occurs at the top of a kaolinitic claystone layer, commonly referred to as the "boundary clay layer," in an interval of coal and carbonaceous shale. The boundary is defined by the disappearance of certain fossil-pollen taxa. The boundary clay layer also contains shocked quartz grains and abundance anomalies of iridium, chromium, and other elements. Each of these characteristics support the hypothesis of an asteroid impact at the end of the Cretaceous. Small goyazite spheres were also found in the boundary clay bed; however, their origin is uncertain. X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and thin-section petrography have shown that the boundary clay bed exhibits unique mineralogic and petrologic characteristics not possessed by other clay-rich beds in coal-bearing rocks of the Raton Basin. The boundary clay bed is composed primarily of well-crystallized kaolinite but also contains subordinate, randomly interstratified, mixed-layer illite/smectite, both of which appear to have been formed by the alteration of vitreous material in a coal-swamp environment. The bulk mineralogy of the boundary clay bed is similar to that of other kaolinite-rich clay beds (tonsteins) that altered in coal swamps from airfall volcanic ash. The alteration process and diagenetic products of the host material in the boundary clay bed, however, differed from those of the tonsteins, resulting in a unique petrographic fabric. The boundary clay bed is characterized by an overall imbricate fabric that may reflect an original vitreous material that included shards, bubbles, and spheres. The original fallout material of the boundary clay bed first altered to "cabbage-like" microspherules, indicating a halloysite or allophane precursor, and then to well-crystallized kaolinite; the well-crystallized kaolinite is the diagenetic stable phase for these rocks at their maximum burial conditions. In comparison, the vitreous components of the tonsteins were altered directly to coarse vermicular and platey kaolinite. Alteration of the original fallout material in the boundary bed was probably rapid, leading to hydrated, disordered, fine-grained clay minerals that formed into curled spherical or tubular shapes. The factors that produced these unique fabrics in the boundary clay bed existed at all K-T sites in the Raton Basin and were much different from those that formed the coarse platey and vermicular fabrics of ordinary tonsteins. The distinctive character of the boundary clay may be due to the unique nature and chemistry of the fallout material and (or) physical or chemical conditions existing shortly after its deposition.

Journal of Sedimentary Petrology

Evaluation of chemical and hydrologic processes in the eastern Snake River Plain Aquifer based on results from geochemical modeling, Idaho National Laboratory, eastern Idaho

Nuclear research activities at the U.S. Department of Energy (DOE) Idaho National Laboratory (INL) produced liquid and solid chemical and radiochemical wastes that were disposed to the subsurface resulting in detectable concentrations of some waste constituents in the eastern Snake River Plain (ESRP) aquifer. These waste constituents may affect the water quality of the aquifer and may pose risks to the eventual users of the aquifer water. To understand these risks to water quality the U.S. Geological Survey, in cooperation with the DOE, conducted geochemical mass-balance modeling of the ESRP aquifer to improve the understanding of chemical reactions, sources of recharge, mixing of water, and groundwater flow directions in the shallow (upper 250 feet) aquifer at the INL. Modeling was conducted using the water chemistry of 127 water samples collected from sites at and near the INL. Water samples were collected between 1952 and 2017 with most of the samples collected during the mid-1990s. Geochemistry and isotopic data used in geochemical modeling consisted of dissolved oxygen, carbon dioxide, major ions, silica, aluminum, iron, and the stable isotope ratios of hydrogen, oxygen, and carbon. Geochemical modeling results indicated that the primary chemical reactions in the aquifer were precipitation of calcite and dissolution of plagioclase (An 60 ) and basalt volcanic glass. Secondary minerals other than calcite included calcium montmorillonite and goethite. Reverse cation exchange, consisting of sodium exchanging for calcium on clay minerals, occurred near site facilities where large amounts of sodium were released to the ESRP aquifer in wastewater discharge. Reverse cation exchange acted to retard the movement of wastewater-derived sodium in the aquifer. Regional groundwater inflow was the primary source of recharge to the aquifer underlying the Northeast and Southeast INL Areas. Birch Creek (BC), the Big Lost River (BLR), and groundwater from BC valley provided recharge to the North INL Area, and the BLR and groundwater from BC and Little Lost River (LLR) valleys provided recharge to the Central INL Area. The BLR, groundwater from the BLR and LLR valleys and the Lost River Range, and precipitation provided recharge to the Northwest and Southwest INL Areas. The primary source of recharge west and southwest of the INL was groundwater inflow from BLR valley. Upwelling geothermal water was a small source of recharge at two wells. Aquifer recharge from surface water in the northern, central, and western parts of the INL indicated that the aquifer in these areas was a dynamic, open system, whereas the aquifer in the eastern part of the INL, which receives little recharge from surface water, was a relatively static and closed system. Sources of recharge identified from isotope ratios and geochemical modeling (major ion concentrations) were nearly identical for the North, Northeast, Southeast, and Central INL Areas, which indicated that both methods probably accurately identified the sources of recharge in these areas. Conversely, isotope ratios indicated that the BLR and groundwater from the LLR valley provided most recharge to the western parts of the Northwest and Southwest INL Areas, whereas geochemical modeling results indicated a smaller area of recharge from the BLR and groundwater from the LLR valley, a larger area of recharge from the Lost River Range, and recharge of groundwater from the BLR valley that extended to the west INL boundary. The results from geochemical modeling probably were more accurate because major ion concentrations, but not isotope ratios, were available to characterize groundwater from the BLR valley and the Lost River Range. Sources of recharge identified with a groundwater flow model (using particle tracking) and geochemical modeling were similar for the Northeast and Southeast INL Areas. However, differences between the models were that the geochemical model represented (1) recharge of groundwater from the Lost River Range in the western part of the INL, whereas the flow model did not, (2) recharge of groundwater from the BC and BLR valleys extending farther south and east, respectively, than the flow model, and (3) more recharge from the BLR in the Southwest INL Area than the flow model. Mixing of aquifer water beneath the INL included (1) mixing of regional groundwater and water from the BC valley in the Northeast and Southeast INL Areas and (2) mixing of surface water (primarily from the BLR) and groundwater across much of the North, Central, Northwest, and Southwest INL Areas. Localized recharge from precipitation mixed with groundwater in the Northwest and Southwest INL Areas, and localized upwelling geothermal water mixed with groundwater in the Central and Northeast INL Areas. Flow directions of regional groundwater were south in the eastern part of the INL and south-southwest at downgradient locations. Groundwater from the BC and LLR valleys initially flowed southeast before changing to south-southwest flow directions that paralleled regional groundwater, and groundwater from the BLR valley initially flowed south before changing to a southsouthwest direction. Wastewater-contaminated groundwater flowed south from the Idaho Nuclear Technology and Engineering Center (INTEC) infiltration ponds in a narrow plume, with the percentage of wastewater in groundwater decreasing due to dilution, dispersion, and (or) degradation from about 60‒80 percent wastewater 0.7‒0.8 mile (mi) south of the INTEC infiltration ponds to about 1.4 percent wastewater about 15.5 mi south of the INTEC infiltration ponds. Wastewater contaminated groundwater flowed southeast and then southwest from the Naval Reactors Facility industrial waste ditch, with the percentage of wastewater in groundwater decreasing from about 100 percent wastewater adjacent to the waste ditch to about 2 percent wastewater about 0.6 mi south of the waste ditch.

Idaho

Nickeliferous laterites in southwestern Oregon and northwestern California

Deposits of ferruginous nickeliferous lateritic soils formed by weathering in place of ultramafic rocks occur at several places in northwestern California and southwestern Oregon, mostly in the Klamath Mountains province. Most of the deposits have been derived from relatively fresh peridotite, although at least one deposit was formed on serpentinite. The accumulations of lateritic soil are on flat-lying to gently sloping surfaces in a terrain that has been extensively dissected and deeply entrenched.The thickness of the deposits ranges from a few feet to more than 50 feet, and may vary widely in any given deposit, for the bedrock surface is commonly highly irregular. The deposit at Nickel Mountain, Oregon, is unique, because it is the only one in which the nickel silicate, garnierite, is plentiful. At Nickel Mountain, garnierite, accompanied by abundant microcrystalline quartz, occurs in veinlike bodies and boxworks that lie at the base of the soil zone and persist in depth along joints and fractures into the underlying slightly weathered or fresh peridotite.Mineralogical studies and chemical analyses show that weathering of the ultramafic rocks destroyed olivine and much of the orthopyroxene and serpentine minerals. Secondary minerals formed are predominantly hydrated ferric oxides (goethite); minor amounts of a montmorillonite mineral, chlorite, and talc were also identified. The kaolin group and bauxite minerals were not found. Except for garnierite at the Nickel Mountain deposit, no nickel-bearing mineral was identified. Nickel may occur, however, in montmorillonite, chlorite, and talc where it substitutes for Mg to a limited extent; in serpentine minerals that were not destroyed by weathering; and possibly in combination with ferric hydroxides. Cobalt may also occur in the clay minerals and probably is associated with trace amounts of manganese oxide or hydroxides.The lateritic soils in northwestern California and southwestern Oregon are similar to soils formed by lateritic weathering of ultramafic rocks in Cuba, the Philippines, New Caledonia, and other tropical regions of the world. They have, however, a higher content of SiO 2 and MgO, and a lower content of Fe 2 O 3 than deposits formed in tropical climates. The California and Oregon deposits are considerably smaller and lower in average metal content which, because they are widely scattered in a rugged, relatively isolated terrain, makes them unpromising as likely reserves for commercial exploitation in the foreseeable future.Most of the deposits are regarded as having been formed by chemical weathering in a climate having alternating wet and dry seasons, probably similar to that prevailing today. Their age is uncertain but may range from post-Miocene to Pleistocene.

California, Oregon

Substrate Geochemistry and Soil Development in Boreal Forest and Tundra Ecosystems in the Yukon-Tanana Upland and Seward Peninsula, Alaska

We report on soil development as a function of bedrock type and the presence of loess in two high latitude ecosystems (boreal forest and tundra) and from two regions in Alaska?the Yukon-Tanana Upland (YTU, east-central Alaska) and the Seward Peninsula (SP, far-west coastal Alaska). This approach to the study of 'cold soils' is fundamental to the quantification of regional geochemical landscape patterns. Of the five state factors in this study, bedrock and biota (ecosystem; vegetation zone) vary whereas climate (within each area) and topography are controlled. The influence of time is assumed to be controlled, as these soils are thousands of years old (late Quaternary to Holocene). The primary minerals in soils from YTU, developed over loess and crystalline bedrock (metamorphic and intrusive), are quartz, plagioclase, and 2:1 clays; whereas in the SP, where loess and metasedimentary bedrock (schist and quartzite) predominate, they are quartz and muscovite. The A horizon of both regions is rich in peat. Examination of the ratio of mobile (K2O, CaO, and Fe2O3) to immobile (TiO2) major oxides, within each region, shows that very little difference exists in the chemical weathering of soils developed between the two ecosystems examined. Differences were observed between tundra soils developed in the two regions. These differences are most probably due to the dissimilarity in the geochemical importance of both loess and bedrock. A minimal loss of cadmium with soil depth is seen for soils developed over YTU crystalline bedrock in the boreal forest environments. This trend is related to the mobility of cadmium in these soils as well as to its biogenic cycling. Major differences were observed in the proportion of cadmium and zinc among the A, B, and C horizon material sequestered in various soil fractions as measured by sequential soil extractions. These trends followed such variables as the decrease with depth in organic matter, the change in clay minerals, and the change in the proportion of oxides/hydroxides. An analysis of the bulk soil mineralogy and the relation between CaO and MgO and Al2O3 and Fe2O3 indicates that the silty textured soils of the YTU are predominantly eolian (that is, of late Tertiary or Quaternary age) but not broad-regional in origin. Their composition instead is probably the result of locally derived dusts as well as input from long-term, in-place bedrock weathering.

Scientific Investigations Report

Non-radiometric borehole geophysical detection of geochemical halos surrounding sedimentary uranium deposits

Roll-type uranium deposits are formed by the concentration of uranium by ground water in geochemical cells. Non-uranium minerals having different solubilities may be deposited ahead of or behind the uranium minerals, forming halos that surround the ore. In addition, oxidizing and reducing environmental conditions may cause zones of mineral alteration to develop beyond the limits of the uranium deposit. Certain physical property anomalies that are commonly associated with halos can be detected by relatively fast and inexpensive borehole geophysical measurements made either in individual holes, or between two adjacent holes. Borehole measurements that have been found to be useful include electrical resistivity, induced polarization, and magnetic susceptibility. Electrical resistivity is increased by the presence of calcite and other cementing minerals that sometimes create permeability barriers in the neighborhood of uranium deposits. Induced polarization (IP) response is increased by sulfide and clay minerals that are commonly found in anomalous concentrations near roll-type deposits. Magnetic susceptibility is usually decreased by the oxidation of magnetite to hematite or limonite in the zone of chemical alteration that is left as a trail behind roll fronts. Borehole measurements of electrical resistivity, induced polarization and magnetic susceptibility were made in the vicinity of a uranium roll-type deposit in south Texas. Results indicate that mineral halos can be detected by borehole measurements made. in wide-spaced drill holes, and that the total amount of drilling needed to find a deposit can be reduced substantially by this exploration approach.

Open-File Report

Influence of natural organic matter on the adsorption of metal ion onto clay particles

The influence of natural organic matter (NOM) on the adsorption of Al, Fe, Zn, and Pb onto clay minerals was investigated. Adsorption experiments were carried out at pH = 5 and pH = 7 in the presence and absence of NOM. In general, the presence of NOM decreased the adsorption of metal ions onto the clay particles. Al and Fe were strongly influenced by NOM, whereas Zn and Pb adsorption was only slightly altered. The interaction of the metal ions with the minerals and the influence of NOM on this interaction was investigated by coupling SdFFF with an inductively coupled plasma mass spectrometer (ICPMS) or an inductively coupled plasma atomic emission spectrometer (ICPAES). Quantitative atomization of the clay particles in the ICP was confirmed by comparing elemental content determined by direct injection of the clay into the ICPMS with values from acid digestion. Particle sizes of the clays were found to be between 0.1 and 1 μm by sedimentation field-flow fractionation (SdFFF) with UV detection. Aggregation of particles due to metal adsorption was observed using SdFFF-ICPMS measurements. This aggregation was dependent on the specific metal ion and decreased in the presence of NOM and at higher pH value.

Environmental Science & Technology

Stepped-combustion 14C dating of sediment: A comparison with established techniques

Radiocarbon dating of bulk sediment has long been used as a method of last resort when reliable wood, charcoal, or plant macrofossils are not available for analysis. Accurate dating of sediment is complicated by the presence of multiple organic carbon fractions, each with a potentially different 14 C activity. Additionally, the presence of carbon bound by clay minerals can significantly reduce the accuracy of a sediment age determination, with the oldest 14 C ages seen in samples with the highest clay content (Scharpenseel and Becker-Heidmann 1992).

Radiocarbon

Hydrothermal alteration at the Lonar Lake impact structure, India: Implications for impact cratering on Mars

The 50,000 year old, 1.8 km diameter Lonar crater is one of only two known terrestrial craters to be emplaced in basaltic target rock (the 65 million year old Deccan Traps). The composition of the Lonar basalts is similar to martian basaltic meteorites, which establishes Lonar as an excellent analogue for similarly sized craters on the surface of Mars. Samples from cores drilled into the Lonar crater floor show that there are basaltic impact breccias that have been altered by post‐impact hydrothermal processes to produce an assemblage of secondary alteration minerals. Microprobe data and X‐ray diffraction analyses show that the alteration mineral assemblage consists primarily of saponite, with minor celadonite, and carbonate. Thermodynamic modeling and terrestrial volcanic analogues were used to demonstrate that these clay minerals formed at temperatures between 130°C and 200°C. By comparing the Lonar alteration assemblage with alteration at other terrestrial craters, we conclude that the Lonar crater represents a lower size limit for impact‐induced hydrothermal activity. Based on these results, we suggest that similarly sized craters on Mars have the potential to form hydrothermal systems, as long as liquid water was present on or near the martian surface. Furthermore, the Fe‐rich alteration minerals produced by post‐impact hydrothermal processes could contribute to the minor iron enrichment associated with the formation of the martian soil.

Lonar Lake; Mars

Chromium geochemistry of serpentinous sediment in the Willow core, Santa Clara County, California

A preliminary investigation of Cr geochemistry in serpentinous sediment completed for a multiple-aquifer ground-water monitoring well (Willow core of Santa Clara County, CA) determined sediment at depths >225 meters contains Cr concentrations ranging from 195 to 1155 mg/kg. Serpentinous sediment from this site is a potential source of non-anthropogenic Cr contamination. Chromium-bearing minerals such as Cr-spinel appear to be the main source of Cr in the sediment; however, Cr-bearing silicates and clay minerals are additional Cr sources. Aqueous Cr concentrations in the sediment are <4.6 mg/L; however, the valence of Cr was not identified in the solutions or in the sediment. Although there is no indication of Cr(VI) contamination derived from the serpentinous sediment, elevated Cr concentrations in the sediment, the observed ‘dissolution’ textures of the Cr-bearing minerals, the estimated redox environment, and water chemistry indicate the formation of Cr(VI) is potentially favorable.

California

Chapter 14 Rex Chert member of the Permian Phosphoria Formation: Composition, with emphasis on elements of environmental concern

We present bulk chemical and mineralogical compositions, as well as petrographic and outcrop descriptions, of rocks collected from three measured outcrop sections of the Rex Chert Member of the Phosphoria Formation in southeast Idaho. The three measured sections were chosen from 10 outcrops of Rex Chert that were described in the field. The Rex Chert overlies the Meade Peak Phosphatic Shale Member of the Phosphoria Formation, the source of phosphate ore in the region. Rex Chert removed as overburden constitutes part of the material transferred to waste-rock piles during phosphate mining. It is also used to surface roads in the mining district. It has been proposed that the chert be used to cap and isolate waste piles, thereby inhibiting the leaching of potentially toxic elements into the environment. The rock samples studied here are from individual chert beds representative of each stratigraphic section sampled. The Cherty Shale Member of the Phosphoria Formation that overlies the Rex Chert in measured section 1 and the upper Meade Peak and the transition zone to the Rex Chert in section 7 were also described and sampled. The cherts are predominantly spiculite composed of granular and mosaic quartz, and sponge spicules, with various but minor amounts of other fossils and detrital grains. The Cherty Shale Member and transition rocks between the Meade Peak and Rex Chert are siliceous siltstones and argillaceous cherts with ghosts of sponge spicules and somewhat more detrital grains than the chert. The dominant mineral is quartz. Carbonate beds are rare in each section and are composed predominantly of calcite and dolomite in addition to quartz. Feldspar, mica, clay minerals, calcite, dolomite, and carbonate fluorapatite are minor to trace minerals in the chert. The concentration of SiO 2 in the chert averages 94.6 wt.%. Organic-carbon content is generally very low, but can be as much as 1.8% in Cherty Shale Member samples and as much as 3.3% in samples from the transition between the Meade Peak and Rex Chert. Likewise, phosphate (P 2 O 5 ) is generally low in the chert, but can be as much as 3.1% in individual chert beds. Selenium concentrations in Rex Chert and Cherty Shale Member samples vary from <0.2 to 138 ppm, with a mean concentration of 7.0 ppm. This mean Se content is heavily dependent on two values of 101 and 138 ppm for siliceous siltstone from the lower part of the Rex Chert, which contains rocks that are transitional in character between the Meade Peak and Rex Chert Members. Without those two samples, the mean Se concentration is < 1.0 ppm. Other elements of environmental interest, As, Cr, V, Zn, Hg, and Cd, generally occur in concentrations near or below that in average continental shale. Stratigraphic changes, equivalent to temporal changes in the depositional basin, in chemical composition of rocks are notable either as uniform changes through the sections or as distinct differences in the mean composition of rocks that comprise the upper and lower halves of the sections. Q-mode factors are interpreted to represent the following rock and mineral components: chert-silica component consisting of Si (±Ba); phosphorite-carbonate fluorapatite component composed of P, Ca, As, Y, V, Cr, Sr, and La (± Fe, Zn, Cu, Ni, Li, Se, Nd, Hg); shale component composed of Al, Na, Zr, K, Ba, Li, and organic C (± Ti, Mg, Se, Ni, Fe, Sr, V, Mn, Zn); carbonate component (dolomite, calcite, silicified carbonates) composed of carbonate C, Mg, Ca, and Si (±Mn); and, tentatively, organic matter-hosted elements (and/or sulfide-sulfate phases) composed of Cu (± organic C, Zn, Mn, Si, Ni, Hg, Li). Selenium shows a dominant association with organic matter and to lesser degrees associations with other shale components and carbonate fluorapatite. Consideration of larger numbers of factors in Q-mode analysis indicates that native Se (a factor containing Se (± Ba)) may also comprise a minor component of the Se complement. Comparison of our data with those from newly exposed outcrops in active phosphate mines indicates that weathering of typical Rex Chert outcrops likely plays an important role in removing environmentally sensitive elements.

Idaho

Smectite-rich horizons in Inceptisols trigger shallow landslides in tropical granitic terranes

Puerto Rico was affected by >70,000 landslides in the wake of 2017 Hurricane Maria, and landslide prevalence was especially high in the Utuado region in the Cordillera Central. Landslide density was highest where soil parent material is granodiorite; landslide slip surfaces tended to be shallow (<60 cm), and often were mobilized rapidly and with long runout distances. This study combines field observations with soil mineralogy (bulk and clay fractions), soil geochemistry (bulk fraction), and soil strength as determined by field cone penetrometer testing (CPT) to test the hypothesis that clay-rich subsoil horizons function as slip planes when water-logged. Soil pits were excavated to depths of ∼200 cm in Ultisols on an undulating plateau and to ∼100 cm in Inceptisols on steep slopes (36-43 o ) that flank the plateau and cone penetrometer tests (CPT) were done within 2 m of the soil pit. Six pits were located adjacent to scarps from previous landslides, enabling analysis of soil profiles downward through extrapolated slip surfaces. Results from X-ray diffraction (XRD), X-ray fluorescence (XRF) and thermogravimetric analysis (TGA) indicate that soils are heterogeneous, often with subsoil horizons enriched in clay minerals and immobile elements (Al, Fe, Ti). Inceptisols on steep slopes often contain smectite-rich horizons at 30–60 cm depth that appear to function as slip surfaces; in other Inceptisols, such horizons are not present and landslide susceptibility is potentially lower. In Ultisols, soil mineralogy is dominated by kaolinite with minor halloysite, and increased kaolinite content at soil depths ≥80 cm at some sites suggests potential slip surfaces enhancing probability of landslides. The origin of clay-rich horizons appears to be (1) fractures in granodiorite that facilitate water flow and leaching, accelerating mineral dissolution during early weathering stages, and (2) smectite-rich buried soils under permeable colluvium likely deposited by a prior mass wasting event. Where clay-rich layers occur beneath more-permeable horizons, rapid infiltration then absorption of water in clay-rich subsoil horizons causes decreased shear strength and increased landslide susceptibility.

Puerto Rico

Geochemical and mineralogical study of the Red Mountain porphyry copper-molybdenum deposit and vicinity, Santa Cruz County, Arizona

The Red Mountain porphyry copper-molybdenum deposit (Cu-Mo deposit or PCD) is located in the northern part of the Patagonia Mountains, Santa Cruz County, Arizona. Extensive core drilling has delineated a large, deep-seated, structurally intact mineral system that extends from the present surface to depths of more than 1,765 meters. This system is hosted in a thick complex of predominantly felsic to andesitic volcanic rocks of the Cretaceous Period. This complex was intruded by scattered bodies of the Tertiary Period that are predominantly quartz monzonite porphyry; no major associated source intrusion has yet been found at depth. A total of 818 samples of core were analyzed for as many as 44 elements. The abundances and distributions at depth of at least 17 of these elements (silver [Ag], arsenic [As], gold [Au], boron [B], bismuth [Bi], copper [Cu], mercury [Hg], potassium [K], molybdenum [Mo], lead [Pb], sulfur [S], antimony [Sb], tin [Sn], tellurium [Te], thallium [Tl], tungsten [W], and zinc [Zn]) are related mostly to events that generated the Red Mountain system. Many of these same samples were also analyzed by X-ray diffraction for a suite of minerals. The multielement and mineralogical analyses of the core samples provide important information about the concentrations, associations, and distributions of select elements and minerals, including zoning patterns that may not be apparent from visual examination of core samples. The distributions of selected elements and minerals in these samples reveal an unusually complete mineral system that extends from a typical PCD with potassic alteration at depth to peripheral zones of phyllic and advanced argillic alteration as well as a copper-rich supergene enriched zone and the remnants of a leached cap. R-mode factor analysis was run with 34 elements for a set of samples from the deep part of the hypogene Cu-Mo deposit and another set from the part of the supergene zone with the highest copper enrichment. For the hypogene zone dataset, five factors are related to the PCD: (1) Ag, Cu, Mo, S, and Te; (2) As, B, Hg, and Sb; (3) Au and sodium (Na); (4) manganese (Mn), Pb, and Zn; and (5) K and Tl. For the supergene dataset, the deposit-related factors include (1) Cu, Mo, S, and Te; (2) Ag, As, Hg, Pb, Sb, and Tl; (3) Au and Na; and (4) K and rubidium (Rb). The changes in element associations between the two datasets indicate that some of these new associations are a result of formation of several suites of hypogene minerals in the deep part of the deposit and different hypogene mineral suites in the peripheral part of the deposit. Some changes may be because of the effects of supergene processes. Zones containing deposit-related elements and minerals common to many PCDs are present at Red Mountain. These zones include a crude, inverted cup-shaped shell containing anomalous copper accompanied by high concentrations of Ag, Au, K, Mo, total S, sulfate S, Sb, Te, and Tl, as well as local concentrations of As, B, Hg, Pb, and Zn. Hydrothermal minerals spatially associated with the deep hypogene Cu-Mo deposit include chalcopyrite, molybdenite, pyrite, plagioclase, orthoclase, biotite, magnetite, calcite, quartz, and anhydrite. Many of the hydrothermally deposited elements that are spatially related to the deposit are also concentrated in zones above the deep part of the deposit, including Ag, As, K, Pb, Sb, Te, Tl, and Zn. These elements are concentrated either (1) in generally wide, flat zones present in the upper part of the system or (2) in crudely arcuate peripheral zones found mainly in the middle part of the system and surrounding the deep part of the deposit. Near-surface, restricted hypogene anomalies are present for bismuth, mercury, tin, and tungsten. The upper part of the deposit has been subjected to supergene enrichment and weathering. Deposit-related elements that remain anomalous in this area include Ag, As, Au, B, Bi, cobalt (Co), Cu, Hg, Mo, Pb, S, Sb, Sn, Te, Tl, uranium (U), and W. These positive concentrations indicate that, with the exception of copper and possibly mercury and uranium, these elements had relatively low chemical mobilities in the supergene enrichment and later weathering environments at Red Mountain. Most may have been deposited during one or more hypogene events and then redistributed locally during later events. Zinc is the only deposit-related element that has clearly been depleted as a result of supergene and (or) weathering events. Minerals that are common in the unweathered upper part of the system include chalcocite, pyrite, quartz, sericite, alunite, and pyrophyllite, as well as less common covellite, enargite, tennantite, tourmaline, barite, anglesite, and other sulfide or sulfate minerals. Subsequent to formation of the Red Mountain Cu-Mo deposit and supergene enrichment, chemical weathering produced an area of pervasive hematite and other iron oxides in the near-surface part of the deposit to form a leached cap. These iron-rich minerals formed primarily as a result of the oxidation of pyrite. This event was accompanied by losses of cobalt, mercury, magnesium, and zinc, as well as destruction of sericite, plagioclase, pyrite, clay minerals, and pyrophyllite. A total of 122 rock samples, 119 soil samples, and samples of three plant species (57 mesquite, 108 oak, and 68 juniper) were collected over and around Red Mountain. For the rock and soil samples, the distributions of anomalous Ag, As, Bi, Cu, Fe, Mo, Pb, Sb, Te, and Tl best delineated the exposed part of the deposit. The highest concentrations of many of these elements are centered on one or both of two main areas with exposures of quartz monzonite porphyry. The high concentrations of arsenic in the deposit area (as much as 390 parts per million (ppm) in rock and 1,500 ppm in soil) and of lead (as much as 2,370 ppm in rock and 1,490 ppm in soil) are particularly noteworthy. The concentrations of various elements in the plant ash vary widely among the three species and are species dependent. Many of the deposit-related elements are either nonessential for plant growth or are considered toxic at certain concentration ranges. In spite of this, the distributions of potentially toxic Ag, As, Bi, Cd, Cu, Mo, Pb, Sb, selenium (Se), and Zn produce deposit-related anomalies for one or more of the three species. Vegetation sampling offered no advantage over rock or soil sampling as an exploration tool. From an environmental standpoint, however, the plant analyses provide baseline data for both essential and nonessential elements that might be useful, for example, for selecting native plant species for revegetating mine waste areas. The exposed part of the Red Mountain deposit has not been greatly disturbed as a result of mining and other activities. However, some of the rock, soil, and plant samples that were collected near the Harshaw Creek and Alum Gulch drainages, which are peripheral to Red Mountain, are also anomalous for various deposit-related elements. These anomalies are probably the result of dispersion of stream sediments contaminated with material from past mining.

Arizona

Morphology and genesis of carbonate soils on the Kyle Canyon fan, Nevada, U.S.A.

The physical and chemical properties of soils formed in an arid climate on calcareous alluvium of the Kyle Canyon alluvial fan, southern Nevada, were studied in order to infer the rates and relative importance of various soil-forming processes. These studies included field and microscopic observations and analyses of thin sections, major oxides, extractable iron, and clay minerals. The results are interpreted to reflect five major pedogenic processes: (1) The calcic horizons and calcretes of Kyle Canyon soils form by precipitation of CaCO 3 , derived from eolian dust and alluvium, as clast coats, matrix cement, and massive layers. (2) The A and uppermost B horizons are essentially dust-derived, for they contain large amounts of detrital material not present in the alluvial parent material, and their major-oxide content is similar to that of modern dust. (3) Clay particles are translocated from A into B horizons. (4) Iron-bearing minerals in the near-surface B horizons are slowly oxidized. (5) Carbonate and aluminosilicate grains are both displaced and replaced by pedogenic CaCO 3 ; the silica released by replacement of aluminosilicates may be locally precipitated as amorphous or opaline silica and (or) incorporated into newly formed palygorskite and sepiolite. Rates of soil development at Kyle Canyon are approximate due to uncertainties in age estimates. Some soil field properties change at rates that are similar to rates for soils formed in rhyolitic parent material near Mercury, Nevada. The rate of accumulation of CaCO 3 (3–5 g m −2 yr −1 ) at Kyle Canyon is an order of magnitude faster than that near Mercury, but is comparable to rates calculated for soils in southern New Mexico and Utah.

Nevada