SEARCH · Search USGS

Results for “Chemical Geology”

Search indexed USGS publications on groundwater, aquifers, geologic maps, mineral resources and earthquakes. Explore source records by subject and place.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 91 records · Page 5Linked to original sources

USGS1981

Determination of selenium at trace levels in geologic materials by energy-dispersive X-ray fluorescence spectrometry

Low levels of selenium (0.1-500 ppm) in both organic and inorganic geologic materials can be semiquantitatively measured by isolating Se as a thin film for presentation to an energy-dispersive X-ray fluorescence spectrometer. Suitably pulverized samples are first digested by fusing with a mixture of Na2CO3 and Na2O2. The fusion cake is dissolved in distilled water, buffered with NH4Cl, and filtered to remove Si and the R2O3 group. A carrier solution of Na2TeO4, plus solid KI, hydrazine sulfate and Na2SO3, is added to the filtrate. The solution is then vacuum-filtered through a 0.45-??m pore-size filter disc. The filter, with the thin film of precipitate, is supported between two sheets of Mylar?? film for analysis. Good agreement is shown between data reported in this study and literature values reported by epithermal neutron-activation analysis and spectrofluorimetry. The method can be made quantitative by utilizing a secondary precipitation to assure complete recovery of the Se. The X-ray method offers fast turn-around time and a reasonably high production rate. ?? 1981.

Chemical Geology↗

USGS2017

New biotite and muscovite isotopic reference materials, USGS57 and USGS58, for δ2H measurements–A replacement for NBS 30

The advent of continuous-flow isotope-ratio mass spectrometry (CF-IRMS) coupled with a high temperature conversion (HTC) system enabled faster, more cost effective, and more precise δ 2 H analysis of hydrogen-bearing solids. Accurate hydrogen isotopic analysis by on-line or off-line techniques requires appropriate isotopic reference materials (RMs). A strategy of two-point calibrations spanning δ 2 H range of the unknowns using two RMs is recommended. Unfortunately, the supply of the previously widely used isotopic RM, NBS 30 biotite, is exhausted. In addition, recent measurements have shown that the determination of δ 2 H values of NBS 30 biotite on the VSMOW-SLAP isotope-delta scale by on-line HTC systems with CF-IRMS may be unreliable because hydrogen in this biotite may not be converted quantitatively to molecular hydrogen. The δ 2 H VSMOW-SLAP values of NBS 30 biotite analyzed by on-line HTC systems can be as much as 21 mUr (or ‰) too positive compared to the accepted value of − 65.7 mUr, determined by only a few conventional off-line measurements. To ensure accurate and traceable on-line hydrogen isotope-ratio determinations in mineral samples, we here propose two isotopically homogeneous, hydrous mineral RMs with well-characterized isotope-ratio values, which are urgently needed. The U.S. Geological Survey (USGS) has prepared two such RMs, USGS57 biotite and USGS58 muscovite. The δ 2 H values were determined by both glassy carbon-based on-line conversion and chromium-based on-line conversion, and results were confirmed by off-line conversion. The quantitative conversion of hydrogen from the two RMs using the on-line HTC method was carefully evaluated in this study. The isotopic compositions of these new RMs with 1-σ uncertainties and mass fractions of hydrogen are: USGS57 (biotite) δ 2 H VSMOW-SLAP = − 91.5 ± 2.4 mUr ( n = 24) Mass fraction hydrogen = 0.416 ± 0.002% ( n = 4) Mass fraction water = 3.74 ± 0.02% ( n = 4) USGS58 (muscovite) δ 2 H VSMOW-SLAP = − 28.4 ± 1.6 mUr ( n = 24) Mass fraction hydrogen = 0.448 ± 0.002% ( n = 4) Mass fraction water = 4.03 ± 0.02% ( n = 4). These δ 2 H VSMOW-SLAP values encompass typical ranges for solid unknowns of crustal and mantle origin and are available to users for recommended two-point calibration.

Chemical Geology↗

USGS2017

Rare-earth elements

The rare-earth elements (REEs) are 15 elements that range in atomic number from 57 (lanthanum) to 71 (lutetium); they are commonly referred to as the “lanthanides.” Yttrium (atomic number 39) is also commonly regarded as an REE because it shares chemical and physical similarities and has affinities with the lanthanides. Although REEs are not rare in terms of average crustal abundance, the concentrated deposits of REEs are limited in number. Because of their unusual physical and chemical properties, the REEs have diverse defense, energy, industrial, and military technology applications. The glass industry is the leading consumer of REE raw materials, which are used for glass polishing and as additives that provide color and special optical properties to the glass. Lanthanum-based catalysts are used in petroleum refining, and cerium-based catalysts are used in automotive catalytic converters. The use of REEs in magnets is a rapidly increasing application. Neodymium-iron-boron magnets, which are the strongest known type of magnets, are used when space and weight are restrictions. Nickel-metal hydride batteries use anodes made of a lanthanum-based alloys. China, which has led the world production of REEs for decades, accounted for more than 90 percent of global production and supply, on average, during the past decade. Citing a need to retain its limited REE resources to meet domestic requirements as well as concerns about the environmental effects of mining, China began placing restrictions on the supply of REEs in 2010 through the imposition of quotas, licenses, and taxes. As a result, the global rare-earth industry has increased its stockpiling of REEs; explored for deposits outside of China; and promoted new efforts to conserve, recycle, and substitute for REEs. New mine production began at Mount Weld in Western Australia, and numerous other exploration and development projects noted in this chapter are ongoing throughout the world. The REE-bearing minerals are diverse and often complex in composition. At least 245 individual REE-bearing minerals are recognized; they are mainly carbonates, fluorocarbonates, and hydroxylcarbonates (n = 42); oxides (n = 59); silicates (n = 85); and phosphates (n = 26). Many of the world’s significant REE deposits occur in carbonatites, which are carbonate igneous rocks. The REEs also have a strong genetic association with alkaline magmatism. The systematic geologic and chemical processes that explain these observations are not well understood. Economic or potentially economic REE deposits have been found in (a) carbonatites, (b) peralkaline igneous systems, (c) magmatic magnetite-hematite bodies, (d) iron oxide-copper-gold (IOCG) deposits, (e) xenotime-monazite accumulations in mafic gneiss, (f) ion-absorption clay deposits, and (g) monazite-xenotime-bearing placer deposits. Carbonatites have been the world’s main source for the light REEs since the 1960s. Ion-adsorption clay deposits in southern China are the world’s primary source of the heavy REEs. Monazite-bearing placer deposits were important sources of REEs before the mid-1960s and may be again in the future. In recent years, REEs have been produced from large carbonatite bodies mined at the Mountain Pass deposit in California and, in China, at the Bayan Obo deposit in Nei Mongol Autonomous Region, the Maoniuping deposit in Sichuan Province, the Daluxiang deposit in Sichuan Province, and the Weishan deposit in Anhui Province. Alkaline igneous complexes have recently been targeted for exploration because of their enrichments in the heavy REEs. Information relevant to the environmental aspects of REE mining is limited. Little is known about the aquatic toxicity of REEs. The United States lacks drinking water standards for REEs. The concentrations of REEs in environmental media are influenced by their low abundances in crustal rocks and their limited solubility in most groundwaters and surface waters. The scarcity of sulfide minerals, including pyrite, minimizes or eliminates concerns about acid-mine drainage for carbonatite-hosted deposits and alkaline-intrusion-related REE deposits. For now, insights into environmental responses of REE mine wastes must rely on predictive models.

Professional Paper↗

USGS2009

Essentials of iron, chromium, and calcium isotope analysis of natural materials by thermal ionization mass spectrometry

The use of isotopes to understand the behavior of metals in geological, hydrological, and biological systems has rapidly expanded in recent years. One of the mass spectrometric techniques used to analyze metal isotopes is thermal ionization mass spectrometry, or TIMS. While TIMS has been a useful analytical technique for the measurement of isotopic composition for decades and TIMS instruments are widely distributed, there are significant difficulties associated with using TIMS to analyze isotopes of the lighter alkaline earth elements and transition metals. Overcoming these difficulties to produce relatively long-lived and stable ion beams from microgram-sized samples is a non-trivial task. We focus here on TIMS analysis of three geologically and environmentally important elements (Fe, Cr, and Ca) and present an in-depth look at several key aspects that we feel have the greatest potential to trouble new users. Our discussion includes accessible descriptions of different analytical approaches and issues, including filament loading procedures, collector cup configurations, peak shapes and interferences, and the use of isotopic double spikes and related error estimation. Building on previous work, we present quantitative simulations, applied specifically in this study to Fe and Ca, that explore the effects of (1) time-variable evaporation of isotopically homogeneous spots from a filament and (2) interferences on the isotope ratios derived from a double spike subtraction routine. We discuss how and to what extent interferences at spike masses, as well as at other measured masses, affect the double spike-subtracted isotope ratio of interest (44Ca/40Ca in the case presented, though a similar analysis can be used to evaluate 56Fe/54Fe and 53Cr/52Cr). The conclusions of these simulations are neither intuitive nor immediately obvious, making this examination useful for those who are developing new methodologies. While all simulations are carried out in the context of a specific isotope system, it should be noted that the same methods can be used to evaluate any isotope system of interest. ?? 2008 Elsevier B.V.

Chemical Geology↗

USGS1989

Comparison of several analytical methods for the determination of tin in geochemical samples as a function of tin speciation

Accurate and precise determinations of tin in geological materials are needed for fundamental studies of tin geochemistry, and for tin prospecting purposes. Achieving the required accuracy is difficult because of the different matrices in which Sn can occur (i.e. sulfides, silicates and cassiterite), and because of the variability of literature values for Sn concentrations in geochemical reference materials. We have evaluated three methods for the analysis of samples for Sn concentration: graphite furnace atomic absorption spectrometry (HGA-AAS) following iodide extraction, inductively coupled plasma atomic emission spectrometry (ICP-OES), and energy-dispersive X-ray fluorescence (EDXRF) spectrometry. Two of these methods (HGA-AAS and ICP-OES) required sample decomposition either by acid digestion or fusion, while the third (EDXRF) was performed directly on the powdered sample. Analytical details of all three methods, their potential errors, and the steps necessary to correct these errors were investigated. Results showed that similar accuracy was achieved from all methods for unmineralized samples, which contain no known Sn-bearing phase. For mineralized samples, which contain Sn-bearing minerals, either cassiterite or stannous sulfides, only EDXRF and fusion ICP-OES methods provided acceptable accuracy. This summary of our study provides information which helps to assure correct interpretation of data bases for underlying geochemical processes, regardless of method of data collection and its inherent limitations. ?? 1989.

Chemical Geology↗

USGS1988

Composition and stable-isotope geochemistry of natural gases from Kansas, Midcontinent, U.S.A.

More than 28??1012 ft.3 (79??1010 m3) of natural gas and 5.3??109 bbl (8.4??108 m3) of oil have been produced in Kansas, U.S.A., from Paleozoic carbonate and sandstone reservoirs on structural uplifts and shallow embayments along the northern margin of the Anadarko basin. A heavily-explored, geologically well-characterized state, Kansas is an excellent place to study hydrocarbon migration and to test geochemical models for the origin of natural gases. Immature to marginally-mature rocks of eastern Kansas (Cherokee and Forest City basins) produce mixed microbial and thermogenic gases. Gases in this region have wetness = 0.03-51%, methane ??13C = -65 to -43??? and methane ??D = -260 to -150???. Gases from central and western Kansas (Nemaha uplift to Hugoton embayment) are entirely thermogenic and have wetness =4-51%, methane ??13C = -48 to -39??? and methane ??D = -195 to -140???. Ethane and propane ??13C-values throughout Kansas vary from -38 to -28??? and from -35 to -24???, respectively. Mature thermogenic gas (generated from source rocks in southwestern Kansas and the Anadarko basin with 1.0% ??? Ro ??? 1.4%) is recognized throughout the state. Lateral migration into shallow reservoirs on the Central Kansas and northern Nemaha uplifts and in the Cherokee basin probably occurred along basal Pennsylvanian conglomerates and weathered Lower Paleozoic carbonates at the regional sub-Pennsylvanian unconformity. Early thermogenic gas (generated by local source rocks with Ro ??? 0.7%) is recognized in isolated fields in the Salina and Forest City basins, in Ordovician reservoirs beneath the sub-Pennsylvanian unconformity in the Cherokee basin, and in reservoirs generally above the unconformity in the Cherokee and Sedgwick basins, the eastern Central Kansas uplift and the Hugoton embayment. ?? 1988.

Chemical Geology↗

USGS2005

Ferric iron-bearing sediments as a mineral trap for CO2 sequestration: Iron reduction using sulfur-bearing waste gas

We present a novel method for geologic sequestration of anthropogenic CO2 in ferrous carbonate, using ferric iron present in widespread redbeds and other sediments. Iron can be reduced by SO2 that is commonly a component of flue gas produced by combustion of fossil fuel, or by adding SO2 or H2S derived from other industrial processes to the injected waste gas stream. Equilibrium and kinetically controlled geochemical simulations at 120 bar and 50 and 100 ??C with SO2 or H2S show that iron can be transformed almost entirely to siderite thereby trapping CO2, and simultaneously, that sulfur can be converted predominantly to dissolved sulfate. If there is an insufficient amount of sulfur-bearing gas relative to CO2 as for typical flue gas, then some of the iron is not reduced, and some of the CO2 is not sequestered. If there is an excess of sulfur-bearing gas, then complete iron reduction is ensured, and some of the iron precipitates as pyrite or other solid iron sulfide, depending on their relative precipitation kinetics. Gas mixtures with insufficient sulfur relative to CO2 can be used in sediments containing Ca, Mg, or other divalent metals capable of precipitating carbonate minerals. For quartz arenite with an initial porosity of 21% and containing 0.25 wt.% Fe2O3, approximately 0.7 g of CO2 is sequestered per kg of rock, and the porosity decrease is less than 0.03%. Sequestration of CO2 using ferric iron has the advantage of disposing of SO2 that may already be present in the combustion gas. ?? 2005 Published by Elsevier B.V.

Chemical Geology↗

USGS2010

Influence of sulfur-bearing polyatomic species on high precision measurements of Cu isotopic composition

An increased interest in high precision Cu isotope ratio measurements using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has developed recently for various natural geologic systems and environmental applications, these typically contain high concentrations of sulfur, particularly in the form of sulfate (SO 4 2- ) and sulfide (S). For example, Cu, Fe, and Zn concentrations in acid mine drainage (AMD) can range from 100??g/L to greater than 50mg/L with sulfur species concentrations reaching greater than 1000mg/L. Routine separation of Cu, Fe and Zn from AMD, Cu-sulfide minerals and other geological matrices usually incorporates single anion exchange resin column chromatography for metal separation. During chromatographic separation, variable breakthrough of SO 4 2- during anion exchange resin column chromatography into the Cu fractions was observed as a function of the initial sulfur to Cu ratio, column properties, and the sample matrix. SO 4 2- present in the Cu fraction can form a polyatomic 32 S- 14 N- 16 O- 1 H species causing a direct mass interference with 63 Cu and producing artificially light ?? 65 Cu values. Here we report the extent of the mass interference caused by SO 4 2- breakthrough when measuring ?? 65 Cu on natural samples and NIST SRM 976 Cu isotope spiked with SO 4 2- after both single anion column chromatography and double anion column chromatography. A set of five 100??g/L Cu SRM 976 samples spiked with 500mg/L SO 4 2- resulted in an average ?? 65 Cu of -3.50?????5.42??? following single anion column separation with variable SO 4 2- breakthrough but an average concentration of 770??g/L. Following double anion column separation, the average SO 4 2- concentration of 13??g/L resulted in better precision and accuracy for the measured ?? 65 Cu value of 0.01?????0.02??? relative to the expected 0??? for SRM 976. We conclude that attention to SO 4 2- breakthrough on sulfur-rich samples is necessary for accurate and precise measurements of ?? 65 Cu and may require the use of a double ion exchange column procedure. ?? 2010.

Chemical Geology↗

USGS1993

Accessory minerals and subduction zone metasomatism: a geochemical comparison of two mélanges (Washington and California, U.S.A.)

The ability of a subducted slab or subducted sediment to contribute many incompatible trace elements to arc source regions may depend on the stabilities of accessory minerals within these rocks, which can only be studied indirectly. In contrast, the role of accessory minerals in lower- T and - P metasomatic processes within paleo-subduction zones can be studied directly in subduction-zone metamorphic terranes. The Gee Point-Iron Mountain locality of the Shuksan Metamorphic Suite, North Cascades, Washington State, is a high- T mélange of metamafic blocks in a matrix of meta-ultramafic rocks. This mélange is similar in geologic setting and petrology to the upper part of an unnamed amphibolite unit of the Catalina Schist, Santa Catalina Island, southern California. Both are interpreted as shear zones between mantle and slab rocks that formed during the early stages of subduction. Some garnet amphibolite blocks from the Gee Point-Iron Mountain locality display trace-element enrichments similar to those in counterparts from the Catalina Schist. Some Catalina blocks are highly enriched in Th, rare-earth elements (REE), the high-field-strength elements Ti, Nb, Ta, Zr and Hf (HFSE), U and Sr compared to mid-ocean ridge basalt (MORB), and to other garnet amphibolite blocks in the same unit. Textural and geochemical data indicate that accessory minerals of metamorphic origin control the enrichment of Th, REE and HFSE in blocks from both areas. The Mg-rich rinds around blocks and the meta-ultramafic matrix from both mélanges are highly enriched in a large number of trace elements compared to harzburgites, dunites and serpentinites. Evidence for recrystallization or formation of accessory minerals in the former rocks suggests that these minerals control some of the trace-element enrichments. Data from the Gee Point and Catalina mélanges suggest that the accessory minerals titanite, rutile, apatite, zircon and REE-rich epidote play a significant role in the enrichment of trace elements in both mafic and ultramafic rocks during subduction-related fluid-rock interaction. Mobilization of incompatible elements, and deposition of such elements in the accessory minerals of mafic and ultramafic rocks may be fairly common in fluid-rich metamorphic environments in subduction zones.

Chemical Geology↗

USGS2014

Hydrogeochemistry of prairie pothole region wetlands: Role of long-term critical zone processes

This study addresses the geologic and hydrogeochemical processes operating at a range of scales within the prairie pothole region (PPR). The PPR is a 750,000 km 2 portion of north central North America that hosts millions of small wetlands known to be critical habitat for waterfowl and other wildlife. At a local scale, we characterized the geochemical evolution of the 92-ha Cottonwood Lake study area (CWLSA), located in North Dakota, USA. Critical zone processes are the long-term determinant of wetland water and groundwater geochemistry via the interaction of oxygenated groundwater with pyrite in the underlying glacial till. Pyrite oxidation produced a brown, iron oxide-bearing surface layer locally over 13 m thick and an estimated minimum of 1.3 × 10 10 g sulfate (SO 4 2 − ) at CWLSA. We show that the majority of this SO 4 2− now resides in solid-phase gypsum (CaSO 4 •2H 2 O) and gypsum-saturated groundwater. Results from the CWLSA were scaled up to a 9700 km 2 area surrounding CWLSA using ~ 1800 drill logs and literature data on wetland water chemistry for 178 wetlands within this larger area. The oxidized brown zone depth and wetland water compositional trends are very similar to the CWLSA. Additionally, surface water data from 176 southern Canadian pothole wetlands that conform to the same wetland water geochemical trends as those recorded in the CWLSA further corroborate that SO 4 2 − accumulation driven by pyrite oxidation is a nearly ubiquitous process in the prairie pothole region and distinguishes PPR wetlands from other wetlands worldwide that have a similar overall hydrology.

Manitoba, North Dakota, Saskatchewan↗

USGS2026

The Sedimentary Geochemistry and Paleoenvironments Project Phase 2 data release: An open data resource for the study of Earth's environmental history

Geochemical data from sedimentary rocks are the primary source of information regarding Earth's surface evolution through time, including its air and water envelopes and interactions with life and deep Earth processes. The Sedimentary Geochemistry and Paleoenvironments Project (SGP) is a scientific consortium centered around open data and community-driven development of cyberinfrastructure tools and resources for sedimentary geochemistry and Earth history. Here we describe the SGP Phase 2 data release, which focused on incorporating Paleoproterozoic and Mesoproterozoic (2500–1000 million years ago) data and better accommodating carbonate data. This data release was built through the involvement of >200 researchers worldwide in academia, government, and industry, and provides the largest available public data resource for our user community in the academic fields of geochemistry, sedimentology, tectonics, paleontology, Earth history, and paleoclimate, as well as the petroleum and minerals industries. The dataset now encompasses 126,006 samples and 4,132,371 geochemical analyses. In addition to direct entry by SGP Team Members, we have ingested and incorporated datasets from the Geoscience Australia OZCHEM database, the Alberta Geological Survey, and the Deep-Time Marine Sedimentary Element Database (DM-SED) compilation. This paper details sampling in the Phase 2 dataset with respect to age, geography, lithology, and other geological characteristics, documents access via our search website and API, discusses possible issues and/or biases in the dataset that could impact analyses, describes plans for governance and stewardship of data from Indigenous lands, and serves as the citable reference paper for the data release.

Chemical Geology↗

USGS2006

Nd, Pb, Sr, and O isotopic characterization of Saudi Arabian Shield terranes

New Nd, Sr and O isotopic data for granitoid rocks of the Saudi Arabian Shield are presented together with published Nd, Pb, Sr and O isotopic data and all available geologic and geochronologic information to re-evaluate the terranes defined for the Saudi Arabian part of the Arabian-Nubian Shield. Three groups of terranes are identified: 1) the western arc terranes, 2) the eastern arc terranes, and 3) the Khida terrane. The Khida terrane is the only terrane composed of pre-Neoproterozoic continental crust. The western arc terranes are of oceanic arc affinity, and have the least radiogenic Pb and Sr and most radiogenic Nd isotopic compositions and some of the lowest ??18O values of any rocks of the Saudi Arabian Shield. Although some previous studies have characterized the eastern arc terranes as of continental affinity, this study shows that they too are composed of Neoproterozoic oceanic arcs, although their sources have slightly elevated 208Pb/204Pb, Nd, Sri, and ??18O values compared to the western arc terranes. These data suggest that either the isotopic composition of the mantle source for the western arc terranes is more depleted than that of the eastern arc terranes or the eastern arc terranes have been mixed with a small amount of cratonic source material, or both. We further elaborate on the Hulayfah-Ad Dafinah fault zone as a major boundary within the Saudi Arabian portion of the East African Orogen. With further study, its northern extension may be shown to pass through what has been defined as the Hail terrane, and its southern extension appears to lie under cover east of the Tathlith-Malahah terrane and extend into Yemen. It may represent the collision zone between East and West Gondwana, and at the very least it is an important suture between groups of arc terranes of contrasting isotopic composition caught between two converging continents.

Chemical Geology↗

USGS1989

Oxygen isotope exchange kinetics of mineral pairs in closed and open systems: Applications to problems of hydrothermal alteration of igneous rocks and Precambrian iron formations

The systematics of stable-isotope exchange between minerals and fluids are examined in the context of modal mineralogical variations and mass-balance considerations, both in closed and in open systems. On mineral-pair ??18O plots, samples from terranes that have exchanged with large amounts of fluid typically map out steep positively-sloped non-equilibrium arrays. Analytical models are derived to explain these effects; these models allow for different exchange rates between the various minerals and the external fluids, as well as different fluid fluxes. The steep arrays are adequately modelled by calculated isochron lines that involve the whole family of possible exchange trajectories. These isochrons have initially-steep near-vertical positive slopes that rotate toward a 45?? equilibrium slope as the exchange process proceeds to completion. The actual data-point array is thus analogous to the hand of an "isotopic clock" that measures the duration of the hydrothermal episode. The dimensionless ratio of the volumetric fluid flux to the kinetic rate parameter ( u k) determines the shape of each individual exchange trajectory. In a fluid-buffered system ( u k ??? 1), the solutions to the equations: (1) are independent of the mole fractions of the solid phases; (2) correspond to Taylor's open-system water/rock equation; and (3) yield straight-line isochrons that have slopes that approach 1 f, where f is the fraction reacted of the more sluggishly exchanging mineral. The isochrons for this simple exchange model are closely congruent with the isochrons calculated for all of the more complex models, thereby simplifying the application of theory to actual hydrothermal systems in nature. In all of the models an order of magnitude of time (in units of kt) separates steep non-equilibrium arrays (e.g., slope ??? 10) from arrays approaching an equilibrium slope of unity on a ??-?? diagram. Because we know the approximate lifetimes of many hydrothermal systems from geologic and heat-balance constraints, we can utilize the 18O 16O data on natural mineral assemblages to calculate the kinetic rate constants (k's) and the effective diffusion constants (D's) for mineral-H2O exchange: these calculated values (kqtz ??? 10-14, kfeld ??? 10-13-10-12) agree with experimental determinations of such constants. In nature, once the driving force or energy source for the external infiltrating fluid phase is removed, the disequilibrium mineral-pair arrays will either: (1) remain "frozen" in their existing state, if the temperatures are low enough, or (2) re-equilibrate along specific closed-system exchange vectors determined solely by the temperature path and the mineral modal proportions. Thus, modal mineralogical information is a particularly important parameter in both the open- and closed-system scenarios, and should in general always be reported in stable-isotopic studies of mineral assemblages. These concepts are applied to an analysis of 18O 16O systematics of gabbros (Plagioclase-clinopyroxene and plagioclase-amphibole pairs), granitic plutons (quartz-feldspar pairs), and Precambrian siliceous iron formations (quartz-magnetite pairs). In all these examples, striking regularities are observed on ??-?? and ??-?? plots, but we point out that ??-?? plots have many advantages over their equivalent ??-?? diagrams, as the latter are more susceptible to misinterpretation. Using the equations developed in this study, these regularities can be interpreted to give semiquantitative information on the exchange histories of these rocks subsequent to their formation. In particular, we present a new interpretation indicating that Precambrian cherty iron formations have in general undergone a complex fluid exchange history in which the iron oxide (magnetite precursor?) has exchanged much faster with low-temperature (< 400??C) fluids than has the relatively inert quartz. ?? 1989.

Chemical Geology↗

USGS2016

Arsenic and radionuclide occurrence and relation to geochemistry in groundwater of the Gulf Coast Aquifer System in Houston, Texas, 2007–11

The U.S. Geological Survey (USGS), in cooperation with the City of Houston, began a study in 2007 to determine concentrations, spatial extent, and associated geochemical conditions that might be conducive for mobility and transport of selected naturally occurring trace elements and radionuclides in the Gulf Coast aquifer system in Houston, Texas. Water samples were collected from 91 municipal supply wells completed in the Evangeline and Chicot aquifers of the Gulf Coast aquifer system in northeastern, northwestern, and southwestern Houston; hereinafter referred to as northeast, northwest and southwest Houston areas. Wells were sampled in three phases: (1) 28 municipal supply wells were sampled during 2007–8, (2) 60 municipal supply wells during 2010, and (3) 3 municipal supply wells during December 2011. During each phase of sampling, samples were analyzed for major ions, selected trace elements, and radionuclides. At a subset of wells, concentrations of arsenic species and other radionuclides (carbon-14, radium-226, radium-228, radon-222, and tritium) also were analyzed. Selected physicochemical properties were measured in the field at the time each sample was collected, and oxidation-reduction potential and unfiltered sulfides also were measured at selected wells. The source-water (the raw, ambient water withdrawn from municipal supply wells prior to water treatment) samples were collected for assessment of aquifer conditions in order to provide community water-system operators information that could be important when they make decisions about which treatment processes to apply before distributing finished drinking water. Geochemical conditions of groundwater of the Gulf Coast aquifer system are suitable in some instances for release of arsenic and radionuclides from aquifer materials. Recent changes to the U.S. Environmental Protection Agency (EPA) primary drinking-water regulations for arsenic and a selected number of natural radionuclides have highlighted the necessity for municipal supply system managers to be aware of the occurrence and distribution of these constituents in their source water. Concentrations of arsenic ranged from 0.58 to 23.5 micrograms per liter (μg/L), with relatively low median and 75th percentile concentrations (2.7 and 3.6 μg/L, respectively). The gross alpha-particle activity completed within 72 hours after sample collection ranged from R-1.1 (nondetect where the result was below the sample specific critical level) to 39.7 picocuries per liter (pCi/L), with a median of 10.3 pCi/L. After 30 days, the gross alpha-particle activities in the 91 samples ranged from R-0.94 to 25.5 pCi/L, with a median of 5.60 pCi/L. Concentrations of uranium ranged from less than 0.02 to 42.7 μg/L, with a median value of 1.69 μg/L and a 75th-percentile value of 6.48 μg/L. The maximum concentrations of radium-226 and combined radium (sum of radium-226 plus radium-228) were 4.34 pCi/L and 3.23 pCi/L, respectively. Aquifer major-ion geochemistry was characterized and shown to contain three chemical types of water as grouped by a simplified predominant cation and anion classification system: (1) calcium- bicarbonate type, (2) sodium-bicarbonate type, and (3) sodium-chloride type. Aquifer geochemistry also was characterized into four reduction-oxidation (redox) categories: (1) oxic, (2) suboxic, (3) mixed, and (4) anoxic. Within the anoxic category, groundwater was further characterized into four presumed predominant reduction processes: (1) iron or sulfate or both [Fe(III)/SO 4 ] reducing, (2) iron [Fe(III)] reducing, (3) iron and sulfate [Fe(III)-SO 4 ] reducing, or (4) methanogenic, as defined by composition of redox species. The oxic category was associated with calcium-bicarbonate-type water, and the methanogenic-anoxic process was associated exclusively with the sodium-bicarbonate-type water. The species of arsenic and the dominant radionuclide present were associated with specific redox categories. Arsenate was associated primarily with oxic water and did not exceed 3.5 µg/L, whereas arsenite was associated with iron-reducing, anoxic water samples and, at the highest concentrations, occurred in sulfate-reducing, anoxic; methanogenic-anoxic; or both water samples. Uranium was associated exclusively with the oxic water, whereas the highest concentrations of combined radium were associated with the iron-reducing, anoxic water. The gross alpha-particle activity was greatest in the oxic waters where the source of the radioactivity was the uranium. Associated geochemical conditions conducive for mobility of arsenic and radionuclides and their spatial and vertical extent in the Gulf Coast aquifer system in Houston are important aspects to the areal management of the municipal groundwater supplies in Houston. Ongoing research is seeking to define chemical or geological factors that are the optimal indicators for elevated concentrations of these naturally occurring constituents.

Texas↗

USGS1969

Saline water in southeastern New Mexico

Saline waters from formations of several geologic ages are being studied in a seven-county area in southeastern New Mexico and western Texas, where more than 30,000 oil and gas tests have been drilled in the past 40 years. This area of 7,500 sq. miles, which is stratigraphically complex, includes the northern and eastern margins of the Delaware Basin between the Guadalupe and Glass Mountains. Chloride-ion concentrations in water produced from rocks of various ages and depths have been mapped in Lea County, New Mexico, using machine map-plotting techniques and trend analyses. Anomalously low chloride concentrations (1,000–3,000 mg/l) were found along the western margin of the Central Basin platform in the San Andres and Capitan Limestone Formations of Permian age. These low chloride-ion concentrations may be due to preferential circulation of ground water through the more porous and permeable rocks. Data being used in the study were obtained principally from oil companies and from related service companies. The P.B.W.D.S. (Permian Basin Well Data System) scout-record magnetic-tape file was used as a framework in all computer operations. Shallow or non-oil-field water analyses acquired from state, municipal, or federal agencies were added to these data utilizing P.B.W.D.S.-compatible reference numbers and decimal latitude-longitude coordinates. Approximately 20,000 water analyses collected from over 65 sources were coded, recorded on punch cards and stored on magnetic tape for computer operations. Extensive manual and computer error checks for duplication and accuracy were made to eliminate data errors resulting from poorly located or identified samples; non-representative or contaminated samples; mistakes in coding, reproducing or key-punching; laboratory errors; and inconsistent reporting. The original 20,000 analyses considered were reduced to 6,000 representative analyses which are being used in the saline water studies.

New Mexico↗

USGS2010

Reactive transport modeling to study changes in water chemistry induced by CO 2 injection at the Frio-I Brine Pilot

To demonstrate the potential for geologic storage of CO 2 in saline aquifers, the Frio-I Brine Pilot was conducted, during which 1600 tons of CO 2 were injected into a high-permeability sandstone and the resulting subsurface plume of CO 2 was monitored using a variety of hydrogeological, geophysical, and geochemical techniques. Fluid samples were obtained before CO 2 injection for baseline geochemical characterization, during the CO 2 injection to track its breakthrough at a nearby observation well, and after injection to investigate changes in fluid composition and potential leakage into an overlying zone. Following CO 2 breakthrough at the observation well, brine samples showed sharp drops in pH, pronounced increases in HCO 3 - and aqueous Fe, and significant shifts in the isotopic compositions of H 2 O and dissolved inorganic carbon. Based on a calibrated 1-D radial flow model, reactive transport modeling was performed for the Frio-I Brine Pilot. A simple kinetic model of Fe release from the solid to aqueous phase was developed, which can reproduce the observed increases in aqueous Fe concentration. Brine samples collected after half a year had lower Fe concentrations due to carbonate precipitation, and this trend can be also captured by our modeling. The paper provides a method for estimating potential mobile Fe inventory, and its bounding concentration in the storage formation from limited observation data. Long-term simulations show that the CO 2 plume gradually spreads outward due to capillary forces, and the gas saturation gradually decreases due to its dissolution and precipitation of carbonates. The gas phase is predicted to disappear after 500 years. Elevated aqueous CO 2 concentrations remain for a longer time, but eventually decrease due to carbonate precipitation. For the Frio-I Brine Pilot, all injected CO 2 could ultimately be sequestered as carbonate minerals. ?? 2010 Elsevier B.V.

Chemical Geology↗

USGS1997

The history of a continent from U-Pb ages of zircons from Orinoco River sand and Sm-Nd isotopes in Orinoco basin river sediments

We report SHRIMP U-Pb ages of 49 zircons from a sand sample from the lower Orinoco River, Venezuela, and Nd model ages of the fine sediment load from the main river and tributaries. The U-Pb ages reflect individual magmatic or metamorphic events, the Sm-Nd model ages reflect average crustal-residence ages of the sediment sources. Together they allow delineation of the crust-formation history of the basement precursors of the sediments. The U-Pb ages range from 2.83 to 0.15 Ga, and most are concordant or nearly so. Discrete age groupings occur at ??? 2.8, ??? 2.1, and ??? 1.1 Ga. The oldest group contains only three samples but is isolated from its closest neighbors by a ??? 600 Ma age gap. Larger age groupings at ??? 2.1 and ??? 1.1 Ga make up about a third and a quarter of the total number of analyses, respectively. The remaining analyses scatter along concordia, and most are younger than 1.6 Ga. The ??? 2.8 and ??? 2.1 Ga ages correspond to periods of crust formation of the Imataca and Trans-Amazonian provinces of the Guyana Shield, respectively, and record intervals of short but intensive continental growth. These ages coincide with ??? 2.9 and ??? 2.1 Ga Nd model ages of sediments from tributaries draining the Archean and Proterozoic provinces of the Guyana Shield, respectively, indicating that the U-Pb ages record the geological history of the crystalline basement of the Orinoco basin. Zircons with ages corresponding to the major orogenies of the North Atlantic continents (the Superior at ??? 2.7 Ga and Hudsonian at 1.7-1.9 Ga) were not found in the Orinoco sample. The age distribution may indicate that South and North America were separated throughout their history. Nd model ages of sediments from the lower Orinoco River and Andean tributaries are ??? 1.9 Ga, broadly within the range displayed by major rivers and dusts. This age does not coincide with known thermal events in the region and reflects mixing of sources with different crust-formation ages. The igneous and metamorphic history of these sources, as recorded by the detrital zircons, is that of the Orinoco basin basement. This implies that, despite evidence of fast sedimentary recycling, global similarities in Nd crustal-residence ages, and the probability of cross-continent mixing through continental drift, the sedimentary material carried by individual rivers is mainly derived from the crystalline basement in the basin. The global semblance in Nd isotope ratios in major river sediments and atmospheric dusts results from the averaging effect of large-scale sampling of the continents, which are heterogeneous in age on smaller regional scales. A large portion of the continental crust in the Orinoco basin formed during the Trans-Amazonian orogeny at 2.0-2.1 Ga, and smaller portions formed both earlier, at ??? 2.8 Ga, and later, after 1.6 Ga. These observations, which are consistent with the relative sizes of crustal age provinces in the Orinoco basin, indicate that sediments from the lower Orinoco and Andean tributaries contain 25-35% of material added to the crust since Trans-Amazonian times. Nd model ages of these sediments underestimate the average crust-formation age of the basement of the Orinoco basin by only about 10%. If this relationship holds in other river basins, then Nd model ages of major rivers and wind blown particulates indicate that the mean age of the continental crust is ??? 1.9-2 Ga. ?? 1997 Elsevier Science B.V.

Chemical Geology↗

USGS1997

Stable isotope evidence for an atmospheric origin of desert nitrate deposits in northern Chile and southern California, U.S.A.

Natural surficial accumulations of nitrate-rich salts in the Atacama Desert, northern Chile, and in the Death Valley region of the Mojave Desert, southern California, are well known, but despite many geologic and geochemical studies, the origins of the nitrates have remained controversial. N and O isotopes in nitrate, and S isotopes in coexisting soluble sulfate, were measured to determine if some proposed N sources could be supported or rejected, and to determine if the isotopic signature of these natural deposits could be used to distinguish them from various types of anthropogenic nitrate contamination that might be found in desert groundwaters. High-grade calich-a-type nitrate deposits from both localities have δ 15 N values that range from −5 to +5‰, but are mostly near 0‰. Values of δ 15 N near 0‰ are consistent with either bulk atmospheric N deposition or microbial N fixation as major sources of the N in the deposits. δ 18 O values of those desert nitrates with δ 15 N near 0‰ range from about +31 to +50‰ (V-SMOW), significantly higher than that of atmospheric O 2 (+23.5‰). Such high values of δ 18 O are considered unlikely to result entirely from nitrification of reduced N, but rather resemble those of modern atmospheric nitrate in precipitation from some other localities. Assuming that limited modern atmospheric isotope data are applicable to the deposits, and allowing for nitrification of co-deposited ammonium, it is estimated that the fraction of the nitrate in the deposits that could be, accounted for isotopically by atmospheric N deposition may be at least 20% and possibly as much as 100%. δ 34 S values are less diagnostic but could also be consistent with atmospheric components in some of the soluble sulfates associated with the deposits. The stable isotope data support the hypothesis that some high-grade caliche-type nitrate-rich salt deposits in some of the Earth's hyperarid deserts represent long-term accumulations of atmospheric deposition (possibly in the order of 104 yr for the Death Valley region, 10 7 yr for the Atacama Desert) in the relative absence of soil leaching or biologic cycling. The combined N and O isotope signature of the nitrate in these deposits is significantly different from those of many other natural and anthropogenic sources of nitrate.

Chemical Geology↗