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USGS2024

Geological context and significance of the clay-sulfate transition region in Mount Sharp, Gale crater, Mars: An integrated assessment based on orbiter and rover data

On Mars, phyllosilicate (“clay”) minerals are often associated with older terrains, and sulfate minerals are associated with younger terrains, and this dichotomy is taken as evidence that Mars’ surface dried up over time. Therefore, in situ investigation of the Mount Sharp strata in Gale crater, which record a shift from dominantly clay-bearing to sulfate-bearing minerals, as seen in visible−near-infrared orbital reflectance spectra, is a key science objective for the Mars Science Laboratory (MSL) Curiosity rover mission. Here, we present regional (orbiter-based) and in situ (rover-based) evidence for a low-angle erosional unconformity that separates the lacustrine and marginal lacustrine deposits of the Carolyn Shoemaker formation from the dominantly eolian deposits of the lower Mirador formation within the orbitally defined clay-sulfate transition region. The up-section record of wetter (Carolyn Shoemaker formation) to drier (lower Mirador formation) depositional conditions is accompanied by distinct changes in diagenesis. Clay minerals occur preferentially within the Carolyn Shoemaker formation and are absent within the lower members of the Mirador formation. At and above the proposed unconformity, strata are characterized by an increase in diagenetic nodules enriched in X-ray amorphous Mg-sulfate. Early clay formation in the Carolyn Shoemaker formation may have created a hydraulic barrier such that later migrating magnesium- and sulfur-rich fluids accumulated preferentially within the lower members of the Mirador formation. The proposed unconformity may have also acted as a fluid conduit to further promote Mg-sulfate nodule formation at the Carolyn Shoemaker−Mirador formation boundary. These results confirm an association of the clay-sulfate transition with the drying of depositional environments, but they also suggest that at least some orbital sulfate signatures within the region are not time-congruent with the environmental signals extracted from primary sedimentology. Our findings highlight that complex interactions among primary depositional environment, erosion, and diagenesis contribute to the transition in clay-sulfate orbital signatures observed in the stratigraphy of Mount Sharp.

GSA Bulletin↗

USGS1961

Origin of Pennsylvanian underclay and related seat rocks

Seat rocks, including underclay, underlie coal beds and show features such as roots, profiles similar to water-logged soils, lack of bedding, soil-like fracture, and gradation into normally bedded sedimentary rocks indicating that they were once soils. Coarse-grained seat rocks range from argillaceous to nearly pure quartz sandstone (ganister). Seat rocks composed of clay-sized particles (underclays) range from mixtures of illite, mixed-layer clay, and kaolinite to essentially pure kaolinite. Variations in the quartz or kaolinite content suggest that there are degrees of alteration in the formation of a seat rock and that all kinds of seat rock were formed by leaching of the substratum in a swamp. The increasing crystallinity of the clay minerals from plastic underclays to semiflint clay to flint clay and the corresponding increase in titanium support this conclusion. These two features suggest strongly that flint clays formed in place in an acidic swamp environment. The Olive Hill clay shows residual acidity. Seat rocks are affected by the chemical environments in the swamp before peat accumulation, during peat accumulation, and during coalification. Kaolinite is forming in present-day swamps and in wet acidic soils in Hawaii and probably formed in late Paleozoic swamps. The facts can be interpreted to show that all kinds of seat rocks could have formed in Pennsylvanian swamps and probably most did.

Geological Society of America Bulletin↗

USGS1979

Clay mineralogy of Pleistocene Lake Tecopa, Inyo County, California

Pleistocene Lake Tecopa in southeastern Inyo County, Calif., was formed when the Amargosa River was blocked at the southern end of its valley. The lake acted as a settling basin for detrital material being transported by the river. This detritus consisted of clays, quartz, feldspars, and micas which became mudstones and siltstones. These mudstones and siltstones, much eroded and dissected after the draining of the lake, extend over the entire basin and are interbedded with tuffs formed by the intermittent deposition of volcanic ashfalls in the former lake waters. These lightcolored mudstones and siltstones are tough and well indurated and break with a conchoidal fracture. The predominant clay mineral in these detrital beds is a lithiumbearing saponite, which is found not only in the lake beds but also in the area beyond the boundaries of the lake, especially in fluvial deposits in the drainage basin of the Amargosa River to the north. This saponite does not contain enough lithium to be classified as a hectorite, and we have observed no indications that this clay consists of a mixture of two phases, such as hectorite and a diluent. Some authigenic dioctahedral montmorillonite, found only in small quantities close to the tuffs, was formed by alteration of the volcanic glass of the tuffs and was then admixed with the overlying or underlying detrital clays. The only authigenic clay-type mineral found in any significant quantity is sepiolite, found near the edges of the lake basin and stratigraphically located mainly within a meter of the two uppermost tuffs. This sepiolite probably was precipitated when silica became available to the magnesium-bearing lake water through dissolution of the volcanic ash. Precipitation of sepiolite probably did not occur within the tuffs owing to the presence of alumina in solution. Zeolites were produced there and sepiolite formed outside the margins of the tuffs. Also formed by the high-pH lake waters were water-soluble minerals, which were found widely dispersed in crusts or streaks on the clays. Much of the calcite was likely precipitated from the lake waters, especially near the north end of the lake where calciumbearing fresh water came into contact with the C02-rich lake waters. Magadiite, a sodium silicate mineral reported only twice previously in the United States, was found in small quantities in the southern end of the basin. This mineral is indicative of a minimum pH of 8.5. The authigenic minerals formed in the lake reflect the presence of silica-rich tuffs and the high-pH, alkaline character of the lake waters.

Professional Paper↗

USGS2011

An approach to modeling coupled thermal-hydraulic-chemical processes in geothermal systems

Interactions between hydrothermal fluids and rock alter mineralogy, leading to the formation of secondary minerals and potentially significant physical and chemical property changes. Reactive transport simulations are essential for evaluating the coupled processes controlling the geochemical, thermal and hydrological evolution of geothermal systems. The objective of this preliminary investigation is to successfully replicate observations from a series of hydrothermal laboratory experiments [Morrow et al., 2001] using the code TOUGHREACT. The laboratory experiments carried out by Morrow et al. [2001] measure permeability reduction in fractured and intact Westerly granite due to high-temperature fluid flow through core samples. Initial permeability and temperature values used in our simulations reflect these experimental conditions and range from 6.13 × 10−20 to 1.5 × 10−17 m2 and 150 to 300 °C, respectively. The primary mineralogy of the model rock is plagioclase (40 vol.%), K-feldspar (20 vol.%), quartz (30 vol.%), and biotite (10 vol.%). The simulations are constrained by the requirement that permeability, relative mineral abundances, and fluid chemistry agree with experimental observations. In the models, the granite core samples are represented as one-dimensional reaction domains. We find that the mineral abundances, solute concentrations, and permeability evolutions predicted by the models are consistent with those observed in the experiments carried out by Morrow et al. [2001] only if the mineral reactive surface areas decrease with increasing clay mineral abundance. This modeling approach suggests the importance of explicitly incorporating changing mineral surface areas into reactive transport models.

Conference Paper↗

USGS2024

Reassessment of the volkonskoite-chromian smectite nomenclature problem.

The name volkonskoite was first used in 1830 to describe a bright blue-green, chromium-bearing clay material from the Okhansk region, west of the Ural Mountains, U.S.S.R. Since that time, the name has been applied to numerous members of the smectite group of clay minerals, although the reported chromium content has ranged from 1% to about 30% Cr 2 O 3 . The name has also been applied to some chromian chlorites. Because volkonskoite has been used for materials that differ not only in their chromium content but also in their basic structure, the species status of the mineral has been unclear. To resolve this uncertainty, two specimens of volkonskoite from (1) Mount Efimiatsk, the type locality in the Soviet Union (USNM 16308) and (2) the Okhansk region in the Perm Basin, U.S.S.R. (USNM R4820), were examined by several mineralogical techniques. Neotype sample 16308 has the following structural formula: (Ca 0.11 Mg 0.11 Fe 2+ 0.03 K 0.02 )(Cr 1.18 Mg 0.78 Fe 3+ 0.29 Ca 0.02 )(Si 3.50 Al 0.51 )O 10 (OH) 2 ⋅3.64H 2 O. Sample R4820 has the following structural formula: (Ca 0.25 Mg 0.05 Fe 2+ 0.01 K 0.03 Mn 0.01 )(Cr 1.07 Mg 0.75 Fe 3+ 0.35 (Si 3.59 Al 0.43 )O 10 (OH) 2 ⋅4.22H 2 O. Mössbauer spectroscopy indicates that 91% and 98% of the iron is present as Fe 3+ in samples 16308 and R4820, respectively. X-ray powder diffraction patterns of both samples have broad lines corresponding to minerals of the smectite group. On the basis of these data, volkonskoite appears to be a dioctahedral member of the smectite group that contains chromium as the dominant cation in the octahedral layer. Smectites containing less than this amount of octahedral chromium should not be called volkonskoite, but should be named by chemical element adjectives, e.g., chromian montmorillonite, chromian nontronite.

Clays and Clay Minerals↗

USGS2024

Surface area of montmorillonite from the dynamic sorption of nitrogen and carbon dioxide

Surface area determinations were made on a montmorillonite with various cations emplaced on the exchangeable sites, utilizing nitrogen and carbon dioxide as adsorbates at 77 ° K and 195 ° K, respectively, in a dynamic system. From the fraction of a Mississippi montmorillonite less than about 1 μ in size, samples were prepared by replacing the original exchangeable cations with Li + , Na + , K + , Rb + , Cs + , Mg ++ , Ca ++ , Ba ++ , and NH 4 + , forming a series of homoionic montmorillonite species. Surface areas from 3-point B.E.T. plots (half-hour adsorption points), with nitrogen as the adsorbate, ranged from 61 m 2 /g for Li-montmorillonite to 138 m 2 /g for Cs-montmorillonite, thus reflecting a certain degree of nitrogen penetration between layers. Complete penetration should theoretically result in a surface area of over 300 m 2 /g for this clay with a nitrogen monolayer between each pair of platelets. The experimental data indicate that the extent of penetration is time-dependent and is also a function of the interlayer forces as governed by the size and charge of the replaceable cation. This finding negates the generally accepted concept that nitrogen at 77 ° K does not penetrate the layers and provides a measure only of the external surface of expandable clay minerals. A further measure of the variation of interlayer forces is provided by the adsorption of carbon dioxide at 195 ° K. Surface area values ranged from 99 m 2 /g for Li-montmorillonite to 315 m 2 /g for Csmontmorillonite. Although the carbon dioxide molecule is larger than the nitrogen molecule, its greater penetration apparently is a result of its being kinetically more energetic (with a larger diffusion coefficient) at its higher adsorption temperature. Similar differences have been found with both adsorbates in the study of microporous substances, such as coal, where activated diffusion is of considerable significance.

Clays and Clay Minerals↗

USGS2015

Weathering and transport of chromium and nickel from serpentinite in the Coast Range ophiolite to the Sacramento Valley, California, USA

A soil geochemical study in northern California was done to investigate the role that weathering and transport play in the regional distribution and mobility of geogenic Cr and Ni, which are both potentially toxic and carcinogenic. These elements are enriched in ultramafic rocks (primarily serpentinite) and the soils derived from them (1700–10,000 mg Cr per kg soil and 1300–3900 mg Ni per kg soil) in the Coast Range ophiolite. Chromium and Ni have been transported eastward from the Coast Range into the western Sacramento Valley and as a result, valley soil is enriched in Cr (80–1420 mg kg −1 ) and Ni (65–224 mg kg −1 ) compared to median values of U.S. soils of 50 and 15 mg kg −1 , respectively. Nickel in ultramafic source rocks and soils is present in serpentine minerals (lizardite, antigorite, and chrysotile) and is more easily weathered compared to Cr, which primarily resides in highly refractory chromite ([Mg,Fe 2+ ][Cr 3+ ,Al,Fe 3+ ] 2 O 4 ). Although the majority of Cr and Ni in soils are in refractory chromite and serpentine minerals, the etching and dissolution of these minerals, presence of Cr- and Ni-enriched clay minerals and development of nanocrystalline Fe (hydr)oxides is evidence that a significant fractions of these elements have been transferred to potentially more labile phases.

California↗

USGS2004

Vertical gradients in water chemistry and age in the southern High Plains Aquifer, Texas, 2002

The southern High Plains aquifer is the primary source of water used for domestic, industrial, and irrigation purposes in parts of New Mexico and Texas. Despite the aquifer's importance to the overall economy of the southern High Plains, fundamental ground-water characteristics, such as vertical gradients in water chemistry and age, remain poorly defined. As part of the U.S. Geological Survey's National Water-Quality Assessment Program, water samples from nested, short-screen monitoring wells installed in the southern High Plains aquifer at two locations (Castro and Hale Counties, Texas) were analyzed for field parameters, major ions, nutrients, trace elements, dissolved organic carbon, pesticides, stable and radioactive isotopes, and dissolved gases to evaluate vertical gradients in water chemistry and age in the aquifer. Tritium measurements indicate that recent (post-1953) recharge was present near the water table and that deeper water was recharged before 1953. Concentrations of dissolved oxygen were largest (2.6 to 5.6 milligrams per liter) at the water table and decreased with depth below the water table. The smallest concentrations were less than 0.5 milligram per liter. The largest major-ion concentrations generally were detected at the water table because of the effects of overlying agricultural activities, as indicated by postbomb tritium concentrations and elevated nitrate and pesticide concentrations at the water table. Below the zone of agricultural influence, major-ion concentrations exhibited small increases with depth and distance along flow paths because of rock/water interactions and mixing with water from the underlying aquifer in rocks of Cretaceous age. The concentration increases primarily were accounted for by dissolved sodium, bicarbonate, chloride, and sulfate. Nitrite plus nitrate concentrations at the water table were 2.0 to 6.1 milligrams per liter as nitrogen, and concentrations substantially decreased with depth in the aquifer to a maximum concentration of 0.55 milligram per liter as nitrogen. Dissolved-gas and nitrogen-isotope data from the deep wells in Castro County indicate that denitrification occurred in the aquifer, removing 74 to more than 97 percent of the nitrate originally present in recharge. There was no evidence of denitrification in the deep part of the aquifer in Hale County. After correcting for denitrification effects, the background concentration of nitrate in water recharged before 1953 ranged from 0.4 to 3.2 milligrams per liter as nitrogen, with an average of 1.6 milligrams per liter as nitrogen. The d15N composition of background nitrate at the time of recharge was estimated to range from 9.6 to 12.3 per mil. Mass-balance models indicate that the decreases in dissolved oxygen and nitrate concentrations and small increases in major-ion concentrations along flow paths can be accounted for by small amounts of silicate-mineral and calcite dissolution; SiO2, goethite, and clay-mineral precipitation; organic-carbon and pyrite oxidation; denitrification; and cation exchange. Mass-balance models for some wells also required mixing with water from the underlying aquifer in rocks of Cretaceous age to achieve mole and isotope balances. Carbon mass transfers identified in the models were used to adjust radiocarbon ages of water samples recharged before 1953. Adjusted radiocarbon ages ranged from less than 1,000 to 9,000 carbon-14 years before present. Radiocarbon ages were more sensitive to uncertainties in the carbon-14 content of recharge than uncertainties in carbon mass transfers, leading to 1-sigma uncertainties of about ?2,000 years in the adjusted ages. Despite these relatively large uncertainties in adjusted radiocarbon ages, it appears that deep water in the aquifer was considerably older (at least 1,000 years) than water near the water table. There was essentially no change in ground-water age with depth in deeper parts of the aquifer, indicating that water in that

Texas↗

USGS1984

Heavy minerals in surficial sediments from lower Cook Inlet, Alaska

Amphiboles, orthopyroxenes, and clinopyroxenes dominate the heavy mineral suite of surficial sediments in lower Cook Inlet, Alaska. Sources for these sediments include the igneous arc terrane of the northeast Alaska Range, reworked intrabasinal sediments, and local drainages in lower Cook Inlet. The distribution of these deposits is a reflection of both the tidal currents and the prevailing southerly net movement from the head of Cook Inlet. The heavy mineral studies concur with similar findings from gravel analyses, clay mineral investigations, and quartz microtexture observations. ?? 1984 Springer-Verlag New York Inc.

Geo-Marine Letters↗

USGS1983

Sorption of radium-226 from oil-production brine by sediments and soils

The sorption of226Ra from oil-production brine by soils and sediments was investigated. Sorption was rapid, and the percentage sorbed increased with brine dilution. Greatest removals of226Ra from sediments in the laboratory occurred with alkaline DTPA, HCl, and BaCl2, with lesser removals using CaCl2 and NaCl solutions. Digestion of sediments with NaOCl indicates that most of the native and sorbed226Ra is associated with the mineral rather than organic fraction of the sediments. Correlation analysis based on 14 soils indicates that the retention of226Ra may involve precipitation reactions associated with sulfate-bearing minerals, as well as ion-exchange reactions with the clay mineral fractions of surficial earth materials. ?? 1982 Springer-Verlag New York Inc.

Environmental Geology↗

USGS2001

Effects of clay dispersion on aquifer storage and recovery in coastal aquifers

Cyclic injection, storage, and withdrawal of freshwater in brackish aquifers is a form of aquifer storage and recovery (ASR) that can beneficially supplement water supplies in coastal areas. A 1970s field experiment in Norfolk, Virginia, showed that clay dispersion in the unconsolidated sedimentary aquifer occurred because of cation exchange on clay minerals as freshwater displaced brackish formation water. Migration of interstitial clay particles clogged pores, reduced permeability, and decreased recovery efficiency, but a calcium preflush was found to reduce clay dispersion and lead to a higher recovery efficiency. Column experiments were performed in this study to quantify the relations between permeability changes and clay mineralogy, clay content, and initial water salinity. The results of these experiments indicate that dispersion of montmorillonite clay is a primary contributor to formation damage. The reduction in permeability by clay dispersion may be expressed as a linear function of chloride content. Incorporating these simple functions into a radial, cross-sectional, variable-density, ground-water flow and transport model yielded a satisfactory simulation of the Norfolk field test - and represented an improvement over the model that ignored changes in permeability. This type of model offers a useful planning and design tool for ASR operations in coastal clastic aquifer systems.

Transport in Porous Media↗

USGS2009

Weathering of the New Albany Shale, Kentucky: II. Redistribution of minor and trace elements

During weathering, elements enriched in black shale are dispersed in the environment by aqueous and mechanical transport. Here a unique evaluation of the differential release, transport, and fate of Fe and 15 trace elements during progressive weathering of the Devonian New Albany Shale in Kentucky is presented. Results of chemical analyses along a weathering profile (unweathered through progressively weathered shale to soil) describe the chemically distinct pathways of the trace elements and the rate that elements are transferred into the broader, local environment. Trace elements enriched in the unweathered shale are in massive or framboidal pyrite, minor sphalerite, CuS and NiS phases, organic matter and clay minerals. These phases are subject to varying degrees and rates of alteration along the profile. Cadmium, Co, Mn, Ni, and Zn are removed from weathered shale during sulfide-mineral oxidation and transported primarily in aqueous solution. The aqueous fluxes for these trace elements range from 0.1 g/ha/a (Cd) to 44 g/ha/a (Mn). When hydrologic and climatic conditions are favorable, solutions seep to surface exposures, evaporate, and form Fe-sulfate efflorescent salts rich in these elements. Elements that remain dissolved in the low pH (<4) streams and groundwater draining New Albany Shale watersheds become fixed by reactions that increase pH. Neutralization of the weathering solution in local streams results in elements being adsorbed and precipitated onto sediment surfaces, resulting in trace element anomalies. Other elements are strongly adsorbed or structurally bound to solid phases during weathering. Copper and U initially are concentrated in weathering solutions, but become fixed to modern plant litter in soil formed on New Albany Shale. Molybdenum, Pb, Sb, and Se are released from sulfide minerals and organic matter by oxidation and accumulate in Fe-oxyhydroxide clay coatings that concentrate in surface soil during illuviation. Chromium, Ti, and V are strongly correlated with clay abundance and considered to be in the structure of illitic clay. Illite undergoes minimal alteration during weathering and is concentrated during illuvial processes. Arsenic concentration increases across the weathering profile and is associated with the succession of secondary Fe(III) minerals that form with progressive weathering. Detrital fluxes of particle-bound trace elements range from 0.1 g/ha/a (Sb) to 8 g/ha/a (Mo). Although many of the elements are concentrated in the stream sediments, changes in pH and redox conditions along the sediment transport path could facilitate their release for aqueous transport.

Applied Geochemistry↗

USGS2010

A high-pyrite semianthracite of Late Permian age in the Songzao Coalfield, southwestern China: Mineralogical and geochemical relations with underlying mafic tuffs

The No. 12 Coal (Late Permian) in the Songzao Coalfield, Chongqing, southwestern China, is characteristically high in pyrite and some trace elements. It is uniquely deposited directly above mafic tuff beds. Samples of coal and tuffs have been studied for their mineralogy and geochemistry using inductively coupled plasma-mass spectrometry, X-ray fluorescence, plasma low-temperature ashing plus powder X-ray diffraction, and scanning electron microscopy equipped with energy-dispersive X-ray analysis.The results show that the minerals of the No. 12 Coal are mainly composed of pyrite, clay minerals (kaolinite, chamosite, and illite), ankerite, calcite, and trace amounts of quartz and boehmite. Kaolinite and boehmite were mainly derived from sediment source region of mafic tuffs. Chamosite was formed by the reaction of kaolinite with Fe-Mg-rich fluids during early diagenesis. The high pyrite (Sp,d=8.83%) in the coal was related to marine transgression over peat deposits and abundant Fe derived from the underlying mafic tuff bed. Ankerite and calcite were precipitated from epigenetic fluids.Chemical compositions of incompatible elements indicate that the tuffs were derived from enriched mantle and the source magmas had an alkali-basalt character. Compared to other coals from the Songzao Coalfield and common Chinese coals, the No. 12 Coal has a lower SiO2/Al2O3 (1.13) but a higher Al2O3/Na2O (80.1) value and is significantly enriched in trace elements including Sc (13.5??g/g), V (121??g/g), Cr (33.6??g/g), Co (27.2??g/g), Ni (83.5??g/g), Cu (48.5??g/g), Ga (17.3??g/g), Y (68.3??g/g), Zr (444??g/g), Nb (23.8??g/g), and REE (392??g/g on average). Above mineralogical compositions, as well as similar ratios of selected elements (e.g., SiO2/Al2O3 and Al2O3/Na2O) and similar distribution patterns of incompatible elements (e.g., the mantle-normalized diagram for incompatible elements and chondrite-normalized diagram for rare earth elements) of coal and tuff, indicated that enriched trace elements above were largely derived from mafic tuffs, in addition to a minor amount from the Kandian Oldland. ?? 2010 Elsevier B.V.

International Journal of Coal Geology↗

USGS2016

Iron oxide minerals in dust-source sediments from the Bodélé Depression, Chad: Implications for radiative properties and Fe bioavailability of dust plumes from the Sahara

Atmospheric mineral dust can influence climate and biogeochemical cycles. An important component of mineral dust is ferric oxide minerals (hematite and goethite) which have been shown to influence strongly the optical properties of dust plumes and thus affect the radiative forcing of global dust. Here we report on the iron mineralogy of dust-source samples from the Bodélé Depression (Chad, north-central Africa), which is estimated to be Earth’s most prolific dust producer and may be a key contributor to the global radiative budget of the atmosphere as well as to long-range nutrient transport to the Amazon Basin. By using a combination of magnetic property measurements, Mössbauer spectroscopy, reflectance spectroscopy, chemical analysis, and scanning electron microscopy, we document the abundance and relative amounts of goethite, hematite, and magnetite in dust-source samples from the Bodélé Depression. The partition between hematite and goethite is important to know to improve models for the radiative effects of ferric oxide minerals in mineral dust aerosols. The combination of methods shows (1) the dominance of goethite over hematite in the source sediments, (2) the abundance and occurrences of their nanosize components, and (3) the ubiquity of magnetite, albeit in small amounts. Dominant goethite and subordinate hematite together compose about 2% of yellow-reddish dust-source sediments from the Bodélé Depression and contribute strongly to diminution of reflectance in bulk samples. These observations imply that dust plumes from the Bodélé Depression that are derived from goethite-dominated sediments strongly absorb solar radiation. The presence of ubiquitous magnetite (0.002–0.57 wt%) is also noteworthy for its potentially higher solubility relative to ferric oxide and for its small sizes, including PM < 0.1 μm. For all examined samples, the average iron apportionment is estimated at about 33% in ferric oxide minerals, 1.4% in magnetite, and 65% in ferric silicates. Structural iron in clay minerals may account for much of the iron in the ferric silicates. We estimate that the mean ferric oxides flux exported from the Bodélé Depression is 0.9 Tg/yr with greater than 50% exported as ferric oxide nanoparticles (<0.1 μm). The high surface-to-volume ratios of ferric oxide nanoparticles once entrained into dust plumes may facilitate increased atmospheric chemical and physical processing and affect iron solubility and bioavailability to marine and terrestrial ecosystems.

Aeolian Research↗

USGS2015

Factors controlling Li concentration and isotopic composition in formation waters and host rocks of Marcellus Shale, Appalachian Basin

In this study, water and whole rock samples from hydraulically fractured wells in the Marcellus Shale (Middle Devonian), and water from conventional wells producing from Upper Devonian sandstones were analyzed for lithium concentrations and isotope ratios (δ 7 Li). The distribution of lithium concentrations in different mineral groups was determined using sequential extraction. Structurally bound Li, predominantly in clays, accounted for 75-91 wt. % of total Li, whereas exchangeable sites and carbonate cement contain negligible Li (< 3%). Up to 20% of the Li is present in the oxidizable fraction (organic matter and sulfides). The δ 7 Li values for whole rock shale in Greene Co., Pennsylvania, and Tioga Co., New York, ranged from -2.3 to + 4.3&permil;, similar to values reported for other shales in the literature. The δ 7 Li values in shale rocks with stratigraphic depth record progressive weathering of the source region; the most weathered and clay-rich strata with isotopically light Li are found closest to the top of the stratigraphic section. Diagenetic illite-smectite transition could also have partially affected the bulk Li content and isotope ratios of the Marcellus Shale. In Greene Co., southwest Pennsylvania, the Upper Devonian sandstone formation waters have δ 7 Li values of + 14.6 ± 1.2 (2SD, n = 25), and are distinct from Marcellus Shale formation waters which have δ 7 Li of + 10.0 ± 0.8 (2SD, n = 12). These two formation waters also maintain distinctive 87 Sr/ 86 Sr ratios suggesting hydrologic separation between these units. Applying temperature-dependent illitilization model to Marcellus Shale, we found that Li concentration in clay minerals increased with Li concentration in pore fluid during diagenetic illite-smectite transition. Samples from north central PA show a much smaller range in both δ 7 Li and 87 Sr/ 86 Sr than in southwest Pennsylvania. Spatial variations in Li and δ 7 Li values show that Marcellus formation waters are not homogeneous across the Appalachian Basin. Marcellus formation waters in the northeastern Pennsylvania portion of the basin show a much smaller range in both δ 7 Li and 87 Sr/ 86 Sr, suggesting long term, cross-formational fluid migration in this region. Assessing the impact of potential mixing of fresh water with deep formation water requires establishment of a geochemical and isotopic baseline in the shallow, fresh water aquifers, and site specific characterization of formation water, followed by long-term monitoring, particularly in regions of future shale gas development.

New York, Pennsylvania↗

USGS1955

Geochemistry and mineralogy of a uraniferous lignite [South Dakota]

Detailed studies have been carried out on a uraniferous lignite from the Mendenhall strip mine, Harding County, S. Dak. By means of heavy-liquid separations, a mineral-free concentrate of the lignite was obtained that contained 13.8 percent ash and 0.31 percent uranium in the ash. The minerals (gypsum 69 percent, jarosite 10 percent, quartz 2 percent, kaolinite and clay minerals 19 percent, and calcite trace) contain only 7 percent of the uranium in the original coal, indicating an association of the uranium with the organic components of the lignite.Batch extractions show that 88.5 percent of the uranium can be extracted from the lignite by two consecutive treatments with boiling 1 N hydrochloric acid. Continuous extraction with hot 6 N hydrochloric acid removes 98.6 percent of the uranium.Columns of coal were treated with water, 1 N hydrochloric acid, 6 N hydrochloric acid, and a solution of lanthanum nitrate. The experiment with lanthanum nitrate indicated that only 1.2 percent of the uranium in the coal is held by ion exchange. The elutriation experiments showed that the uranium is held in the coal as an organo-uranium compound or complex that is soluble at a pH of less than 2.18.A geochemical mechanism by which the uranium may have been introduced into and retained by the lignite is discussed.

South Dakota↗

USGS2017

Vanadium

Vanadium is used primarily in the production of steel alloys; as a catalyst for the chemical industry; in the making of ceramics, glasses, and pigments; and in vanadium redox-flow batteries (VRBs) for large-scale storage of electricity. World vanadium resources in 2012 were estimated to be 63 million metric tons, which include about 14 million metric tons of reserves. The majority of the vanadium produced in 2012 was from China, Russia, and South Africa. Vanadium is extracted from several different types of mineral deposits and from fossil fuels. These deposits include vanadiferous titanomagnetite (VTM) deposits, sandstone-hosted vanadium (with or without uranium) deposits (SSV deposits), and vanadium-rich black shales. VTM deposits are the principal source of vanadium and consist of magmatic accumulations of ilmenite and magnetite containing 0.2 to 1 weight percent vanadium pentoxide (V 2 O 5 ). SSV deposits are another important source; these deposits have average ore grades that range from 0.1 to greater than 1 weight percent V 2 O 5 . The United States has been and is currently the main producer of vanadium from SSV deposits, particularly those on the Colorado Plateau. Vanadium-rich black shales occur in marine successions that were deposited in epeiric (inland) seas and on continental margins. Concentrations in these shales regularly exceed 0.18 weight percent V 2 O 5 and can be as high as 1.7 weight percent V 2 O 5 . Small amounts of vanadium have been produced from the Alum Shale in Sweden and from ferrophosphorus slag generated during the reduction of phosphate to elemental phosphorus in ore from shales of the Phosphoria Formation in Idaho and Wyoming. Because vanadium enrichment occurs in beds that are typically only a few meters thick, most of the vanadiferous black shales are not currently economic, although they may become an important resource in the future. Significant amounts of vanadium are recovered as byproducts of petroleum refining, and processing of coal, tar sands, and oil shales may be important future sources. Vanadium occurs in one of four oxidation states in nature: +2, +3, +4, and +5. The V 3+ ion has an octahedral radius that is almost identical to that of (Fe 3+ ) and (Al 3+ ) and, therefore, it substitutes in ferromagnesian minerals. During weathering, much of the vanadium may partition into newly formed clay minerals, and it either remains in the +3 valence state or oxidizes to the +4 valence state, both of which are relatively insoluble. If erosion is insignificant but chemical leaching is intense, the residual material may be enriched in vanadium, as are some bauxites and laterites. During the weathering of igneous, residual, or sedimentary rocks, some vanadium oxidizes to the +5 valence state, especially in the intensive oxidizing conditions that are characteristic of arid climates. The average contents of vanadium in the environment are as follows: soils [10 to 500 parts per million (ppm)]; streams and rivers [0.2 to 2.9 parts per billion (ppb)]; and coastal seawater (0.3 to 2.8 ppb). Concentrations of vanadium in soils (548 to 7,160 ppm) collected near vanadium mines in China, the Czech Republic, and South Africa are many times greater than natural concentrations in soils. Additionally, if deposits contain sulfide minerals such as chalcocite, pyrite, and sphalerite, high levels of acidity may be present if sulfide dissolution is not balanced by the presence of acid-neutralizing carbonate minerals. Some of the vanadium-bearing deposit types, particularly some SSV and black-shale deposits, contain appreciable amounts of carbonate minerals, which lowers the acid-generation potential. Vanadium is a micronutrient with a postulated requirement for humans of less than 10 micrograms per day, which can be met through dietary intake. Primary and secondary drinking water regulations for vanadium are not currently in place in the United States. Vanadium toxicity is thought to result from an intake of more than 10 to 20 milligrams per day. Vanadium is essential for some biological processes and organisms. For example, some nitrogen-fixing bacteria require vanadium for producing enzymes necessary to convert nitrogen from the atmosphere into ammonia, which is a more biologically accessible form of nitrogen.

Professional Paper↗

USGS1954

Progress report on the Happy Jack mine, Which Canyon area, San Juan county, Utah

The Happy Jack mine is in the White Canyon area, San Juan county, Utah. Production is from high-grade uranium deposits in the Shinarump conglomerate of the Triassic age. In this area the Shinarump beds range from about 16 to 40 feet in thickness and the lower part of these beds fills an east-trending channel this is note than 750 feet wide and 10 feet deep. The Shinarump conglomerate consists of beds of coarse- to fine-grained quartzose sandstone, conglomerate, siltstone, and claystone. Carbonized wood is abundant in these beds, and in the field it was classified as mineral charcoal and coal. Intra-Shinarump channels, cross-stratification, current lineation, and slumping and compaction structures have been recognized in the mine. Steeply dipping fractures have dominant trends in four directions -- N 65°W, N 60°E, N 85°E, and due north. Uranium occurs as bedded deposits, as replacement bodies in accumulations of "trash", and as replacements of larger fragments of wood. An "ore shoot" is formed where the three types of uranium deposits occur together; these ore shoots appear to be elongate masses with sharp boundaries. Uranium minerals include uraninite, sooty pitchblende(?), and the sulfate--betazippeite, johannite, and uranopilite. Associated with the uraninite are the sulfide minerals covellite, bornite, chalcopyritw, and pyrite. Galena and sphalerite have been found in close association with uranium minerals. The gaunge minerals include: limonite and hematite present in most of the sandstone beds throughout the deposit, jarosite that impregnates much of the sandstone in the outer parts of the mine workings, gypsum that fills many of the fractures, and barite that impregnates the sandstone in at least one part of the mine. Secondary copper minerals, mainly copper sulfates, occur throughout the mine, but most abundant near the adits in the outermost 30 feet of the workings. The minerals comprising the bulk of the country rock include quartz, feldspar, and clay minerals. The amount of uranium minerals deposited in a sandstone bed is believed to have been determined by the position of the bed in the channel, the permeability of the sandstone in the bed, and the amount of carbonized wood and plant remains within the bed. The beds considered most favorable for uranium deposition contain an abundance of claystone and siltstone both as matrix filling and as fragments and pebbles. Suggested exploration guides from uranium ore bodies include the following: (1) interbedded siltstone lenses, (2) claystone and siltstone cement and pabbles, (3) concentrations of "trash", (4) covelllite and bornite, (5) chalcopyrite, and (6) carbonized wood.

Utah↗