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An analytical method for hydrogeochemical surveys: Inductively coupled plasma-atomic emission spectrometry after using enrichment coprecipitation with cobalt and ammonium pyrrolidine dithiocarbamate

Trace metals that are commonly associated with mineralization were concentrated and separated from natural water by coprecipitation with ammonium pyrollidine dithiocarbamate (APDC) and cobalt and determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The method is useful in hydrogeochemical surveys because it permits preconcentration near the sample sites, and selected metals are preserved shortly after the samples are collected. The procedure is relatively simple: (1) a liter of water is filtered; (2) the pH is adjusted; (3) Co chloride and APDC are added to coprecipitate the trace metals; and (4) later, the precipitate is filtered, dissolved, and diluted to 10 ml for a 100-fold concentration enrichment of the separated metals. Sb(III), As(III), Cd, Cr, Cu, Fe, Pb, Mo, Ni, Ag, V, and Zn can then be determined simultaneously by ICP-AES. In an experiment designed to measure the coprecipitation efficiency, Sb(III), Cd and Ag were recovered at 70 to 75% of their original concentration. The remaining metals were recovered at 85 to 100% of their original concentrations, however. The range for the lower limits of determination for the metals after preconcentration is 0.1 to 3.0 μg/l.

Journal of Geochemical Exploration

Reconnaissance guidelines for gold exploration in Central Alaska

Distribution of more than 300 gold-bearing samples from the Livengood (Tolovana) and parts of the Fairbanks and Rampart mining districts in central Alaska, USA, indicate that the concentration of gold in placers is spatially related both to structural features and to Late Cretaceous and (or) Tertiary felsic plutons. The regional consistency of these spatial relationships is demonstrated by proximity analysis using a Geographic Information System (GIS), and suggests a genetic association between faults, felsic plutons, and gold occurrences. The local presence of gold within several of the plutons indicates that these are the source of some of the gold. In addition, some gold occurs proximal to faults where plutons are not present, suggesting that some of the gold was also derived from the country rock. We envision a model whereby weakly mineralized solutions, thermally driven by latent plutonic heat, were enriched by circulation through clastic units that may have had a naturally elevated gold background. The resultant enriched solutions were channeled and reconcentrated along or adjacent to large-scale fault systems. Future exploration to define individual target areas should be directed toward areas where Late Cretaceous and (or) Tertiary felsic plutons occur near major faults. ?? 1993.

Journal of Geochemical Exploration

Sagebrush as a sampling medium for gold exploration in the Great Basin - evaluation from a greenhouse study

Seedlings (Artemisia tridentata subsp, tridentata germinated from seed collected near Preble, Nevada were grown in soils containing Carlin-type disseminated gold ore. After 4 months growth leaves, twigs and stems were combined and analyzed by INAA. Plants grown in soils containing Carlin ore did not accumulate significantly more gold than those growing in control soil. On the other hand, sagebrush grown in soils containing Carlin ores accumulated significantly more arsenic and antimony compared to those grown in control soils. Results suggest that sagebrush would be a good prospecting medium for detecting concealed Carlin-type deposits in the Great Basin if arsenic and antimony are used as the pathfinder elements. Results also suggest that true gold anomalies in sagebrush will be more difficult to separate from aeolian contamination than those for arsenic and antimony in arid environments. -from Authors

Journal of Geochemical Exploration

Effects of iron on arsenic speciation and redox chemistry in acid mine water

Concern about arsenic is increasing throughout the world, including areas of the United States. Elevated levels of arsenic above current drinking-water regulations in ground and surface water can be the result of purely natural phenomena, but often are due to anthropogenic activities, such as mining and agriculture. The current study correlates arsenic speciation in acid mine drainage and mining-influenced water with the important water-chemistry properties Eh, pH, and iron(III) concentration. The results show that arsenic speciation is generally in equilibrium with iron chemistry in low pH AMD, which is often not the case in other natural-water matrices. High pH mine waters and groundwater do not always hold to the redox predictions as well as low pH AMD samples. The oxidation and precipitation of oxyhydroxides deplete iron from some systems, and also affect arsenite and arsenate concentrations through sorption processes. ?? 2004 Elsevier B.V. All rights reserved.

Journal of Geochemical Exploration

Methane-derived authigenic carbonates from the northern Gulf of Mexico - MD02 Cruise

Authigenic carbonates were sampled in piston cores collected from both the Tunica Mound and the Mississippi Canyon area on the continental slope of the northern Gulf of Mexico during a Marion Dufresne cruise in July 2002. The carbonates are present as hardgrounds, porous crusts, concretions or nodules and shell fragments with or without carbonate cements. Carbonates occurred at gas venting sites which are likely to overlie gas hydrates bearing sediments. Electron microprobe, X-ray diffraction (XRD) and thinsection investigations show that these carbonates are high-Mg calcite (6–21 mol% MgCO 3 ), with significant presence of framboidal pyrite. All carbonates are depleted in 13 C ( δ 13 C = − 61.9 to − 31.5‰ PDB) indicating that the carbon is derived mainly from anaerobic methane oxidation (AMO). Age estimates based on 14 C dating of shell fragments and on regional sedimentation rates indicate that these authigenic carbonates formed within the last 1000 yr in the Mississippi Canyon and within 5500 yr at the Tunica Mound. The oxygen isotopic composition of carbonates ranges from + 3.4 to + 5.9‰ PDB. Oxygen isotopic compositions and Mg 2+ contents of carbonates, and present in-situ temperatures of bottom seawater/sediments, show that some of these carbonates, especially from a core associated with underlying massive gas hydrates precipitated in or near equilibrium with bottom-water. On the other hand, those carbonates more enriched in 18 O are interpreted to have precipitated from 18 O-rich fluids which are thought to have been derived from the dissociation of gas hydrates. The dissociation of gas hydrates in the northern Gulf of Mexico within the last 5500 yr may be caused by nearby salt movement and related brines.

Journal of Geochemical Exploration

Composition and quality of coals in the Huaibei Coalfield, Anhui, China

The Huaibei Coalfield, Anhui Province, China, is one of the largest coalfields in China. The coals of Permian age are used mainly for power generation. Coal compositions and 47 trace elements of the No. 10 Coal of the Shanxi Formation, the No. 7, 5, and 4 Coals of the Lower Shihezi Formation, and the No. 3 Coal of the Upper Shihezi Formation from the Huaibei Coalfield were studied. The results indicate that the Huaibei coals have low ash, moisture, and sulfur contents, but high volatile matter and calorific value. The ash yield increases stratigraphically upwards, but the volatile matter and total sulfur contents show a slight decrease from the lower to upper seams. Magmatic intrusion into the No. 5 Coal resulted in high ash, volatile matter, and calorific value, but low moisture value in the coal. Among the studied 47 trace elements, Ba, Co, Cr, Cu, Hg, Mo, Ni, Pb, Sb, Th, U, V, and Zn are of environmental concerns. Four elements Hg, Mo, Zn, and Sb are clearly enriched in the coals as compared with the upper continental crust. ?? 2007 Elsevier B.V. All rights reserved.

Journal of Geochemical Exploration

Acid rock drainage and climate change

Rainfall events cause both increases and decreases in acid and metals concentrations and their loadings from mine wastes, and unmined mineralized areas, into receiving streams based on data from 3 mines sites in the United States and other sites outside the US. Gradual increases in concentrations occur during long dry spells and sudden large increases are observed during the rising limb of the discharge following dry spells (first flush). By the time the discharge peak has occurred, concentrations are usually decreased, often to levels below those of pre-storm conditions and then they slowly rise again during the next dry spell. These dynamic changes in concentrations and loadings are related to the dissolution of soluble salts and the flushing out of waters that were concentrated by evaporation. The underlying processes, pyrite oxidation and host rock dissolution, do not end until the pyrite is fully weathered, which can take hundreds to thousands of years. These observations can be generalized to predict future conditions caused by droughts related to El Ni??o and climate change associated with global warming. Already, the time period for dry summers is lengthening in the western US and rainstorms are further apart and more intense when they happen. Consequently, flushing of inactive or active mine sites and mineralized but unmined sites will cause larger sudden increases in concentrations that will be an ever increasing danger to aquatic life with climate change. Higher average concentrations will be observed during longer low-flow periods. Remediation efforts will have to increase the capacity of engineered designs to deal with more extreme conditions, not average conditions of previous years.

Journal of Geochemical Exploration

Lead isotopes in soils and groundwaters as tracers of the impact of human activities on the surface environment: The Domizio-Flegreo Littoral (Italy) case study

The isotopic signature of geogenic and anthropogenic materials, in combination with concentration data for pollutants, can help trace the origin and the extent of contamination in the environment. This approach is particularly effective if naturally occurring and anthropogenically introduced metals have different isotopic ratios. Lead isotope analysis on soils from 7 profiles (1 m depth) and on groundwaters from 8 wells have been used to determine the impact of human activities on the surface environment of Domizio-Flegreo Littoral. Result obtained show that in sub-rural areas the isotopic composition of the samples collected along the soil profiles of Domizio-Flegreo Littoral is likely mostly controlled by the nature of the parent geologic material (natural) while in more urbanized areas (Giugliano) Pb isotopic composition in superficial soils is mostly influenced by anthropic sources such as motor vehicles. Lead isotopic ratios in groundwaters also show that the use of pesticides and, probably, the influence of aerosols and the presence of illegal waste disposal can influence water quality.

The Domizio-Flegreo Littoral

Temporal and spatial distribution of alteration, mineralization and fluid inclusions in the transitional high-sulfidation epithermal-porphyry copper system at Red Mountain, Arizona

Red Mountain, Arizona, is a Laramide porphyry Cu system (PCD) that has experienced only a modest level of erosion compared to most other similar deposits in the southwestern United States. As a result, the upper portion of the magmatic–hydrothermal system, which represents the transition from shallower high-sulfidation epithermal mineralization to deeper porphyry Cu mineralization, is well preserved. Within the Red Mountain system, alteration, mineralization and fluid inclusion assemblages show a systematic distribution in both time and space. Early-potassic alteration (characterized by the minerals biotite and magnetite) is paragenetically earlier than late-potassic alteration (K-feldspar–anhydrite) and both are followed by later phyllic (sericite–pyrite) alteration. Advanced argillic alteration (pyrophyllite–alunite–other clay minerals) is thought to be coeval with or postdate phyllic alteration. Minerals characteristic of advanced argillic alteration are present in the near surface. Phyllic alteration extends to greater depths compared to advanced argillic alteration. Early-potassic and late-potassic alteration are only observed in the deepest part of the system. Considerable overlap of phyllic alteration with both early-potassic and late-potassic alteration zones is observed. The hypogene mineralization contains 0.4–1.2% Cu and is spatially and temporally related to the late-potassic alteration event. Molybdenum concentration is typically < 300 ppm but positive anomalies (between 600 and 1200 ppm) occur, and typically correlate with the zones of higher Cu grades. Silver and Au range up to 50 ppm and 1 ppm, respectively, and mostly occur in the deeper parts of the system. Individual assays of up to 18 ppm Au and 274 ppm Ag in the shallower part of the system are interpreted to be associated with areas of highly focused fluid flow (i.e., breccias and thick veins). A near-surface, discontinuous chalcocite blanket is represented by scattered Cu anomalies within the mixed oxide/sulfide zone and its discontinuous nature may reflect differential permeability along fractures and faults. In the deepest part of the system, an early generation of low-to-moderate density and salinity liquid + vapor inclusions with opaque daughter minerals is followed in time by halite-bearing inclusions that also contain opaque daughter minerals indicating that an early intermediate-density magmatic fluid evolved to a high-density, high-salinity mineralizing fluid. The increase in density and salinity of fluids with time observed in the deeper parts of the system may be the result of immiscibility (“boiling”) of the earlier magmatic fluids or may reflect the compositional evolution of fluids that exsolved from the magma. Trails of inclusions consisting of only vapor-rich inclusions are common in the shallow parts of the system, and are associated with advanced argillic alteration, suggesting that intense boiling (“flashing”) occurred at (or below) this level. Fluid inclusion assemblages consisting of coexisting vapor-rich and halite-bearing inclusions are observed in samples extending from the surface to the upper part of the late-potassic zone, indicating that fluid immiscibility occurred within this depth interval.

Arizona

Mercury in stream water at five Czech catchments across a Hg and S deposition gradient

The Czech Republic was heavily industrialized in the second half of the 20th century but the associated emissions of Hg and S from coal burning were significantly reduced since the 1990s. We studied dissolved (filtered) stream water mercury (Hg) and dissolved organic carbon (DOC) concentrations at five catchments with contrasting Hg and S deposition histories in the Bohemian part of the Czech Republic. The median filtered Hg concentrations of stream water samples collected in hydrological years 2012 and 2013 from the five sites varied by an order of magnitude from 1.3 to 18.0 ng L &minus; 1 . The Hg concentrations at individual catchments were strongly correlated with DOC concentrations r from 0.64 to 0.93 and with discharge r from 0.48 to 0.75. Annual export fluxes of filtered Hg from individual catchments ranged from 0.11 to 13.3 &mu;g m &minus; 2 yr &minus; 1 and were highest at sites with the highest DOC export fluxes. However, the amount of Hg exported per unit DOC varied widely; the mean Hg/DOC ratio in stream water at the individual sites ranged from 0.28 to 0.90 ng mg &minus; 1 . The highest stream Hg/DOC ratios occurred at sites Pluhův Bor and Jezeř&iacute; which both are in the heavily polluted Black Triangle area. Stream Hg/DOC was inversely related to mineral and total soil pool Hg/C across the five sites. We explain this pattern by greater soil Hg retention due to inhibition of soil organic matter decomposition at the sites with low stream Hg/DOC and/or by precipitation of a metacinnabar (HgS) phase. Thus mobilization of Hg into streams from forest soils likely depends on combined effects of organic matter decomposition dynamics and HgS-like phase precipitation, which were both affected by Hg and S deposition histories.

Journal of Geochemical Exploration

Ion-adsorption REEs in regolith of the Liberty Hill pluton, South Carolina, USA: An effect of hydrothermal alteration

Ion-adsorbed rare earth element (REE) deposits supply the majority of world heavy REE production and substantial light REE production, but relatively little is known of their occurrence outside Southeast Asia. We examined the distribution and forms of REEs on a North American pluton located in the highly weathered and slowly eroding South Carolina Piedmont. The Hercynian Liberty Hill pluton experiences a modern climate that includes ~ 1500 mm annual rainfall and a mean annual temperature of 17 °C. The pluton is medium- to coarse-grained biotite-amphibole granite with minor biotite granite facies. REE-bearing phases are diverse and include monazite, zircon, titanite, allanite, apatite and bastnäsite. Weathered profiles were sampled up to 7 m-deep across the ~ 400 km 2 pluton. In one profile, ion-adsorbed REEs plus yttrium (REE + Y) ranged up to 581 mg/kg and accounted for up to 77% of total REE + Y in saprolite. In other profiles, ion-adsorbed REE + Y ranged 12–194 mg/kg and only accounted for 3–37% of totals. The profile most enriched in ion-adsorbed REEs was located along the mapped boundary of two granite facies and contained trioctahedral smectite in the saprolite, evidence suggestive of hydrothermal alteration of biotite at that location. Post-emplacement deuteric alteration can generate easily weathered REE phases, particularly fluorocarbonates. In the case of Liberty Hill, hydrothermal alteration may have converted less soluble to more soluble REE minerals. Additionally, regolith P content was inversely correlated with the fraction ion-adsorbed REEs, and weathering related secondary REE-phosphates were found in some regolith profiles. Both patterns illustrate how low P content aids in the accumulation of ion-adsorbed REEs. The localized occurrence at Liberty Hill sheds light on conditions and processes that generate ion-adsorbed REEs.

South Carolina

Mapping of compositional properties of coal using isometric log-ratio transformation and sequential Gaussian simulation – A comparative study for spatial ultimate analyses data

Chemical properties of coal largely determine coal handling, processing, beneficiation methods, and design of coal-fired power plants. Furthermore, these properties impact coal strength, coal blending during mining, as well as coal's gas content, which is important for mining safety. In order for these processes and quantitative predictions to be successful, safer, and economically feasible, it is important to determine and map chemical properties of coals accurately in order to infer these properties prior to mining. Ultimate analysis quantifies principal chemical elements in coal. These elements are C, H, N, S, O, and, depending on the basis, ash, and/or moisture. The basis for the data is determined by the condition of the sample at the time of analysis, with an “as-received” basis being the closest to sampling conditions and thus to the in-situ conditions of the coal. The parts determined or calculated as the result of ultimate analyses are compositions, reported in weight percent, and pose the challenges of statistical analyses of compositional data. The treatment of parts using proper compositional methods may be even more important in mapping them, as most mapping methods carry uncertainty due to partial sampling as well. In this work, we map the ultimate analyses parts of the Springfield coal from an Indiana section of the Illinois basin, USA, using sequential Gaussian simulation of isometric log-ratio transformed compositions. We compare the results with those of direct simulations of compositional parts. We also compare the implications of these approaches in calculating other properties using correlations to identify the differences and consequences. Although the study here is for coal, the methods described in the paper are applicable to any situation involving compositional data and its mapping.

Indiana

The isometric log-ratio (ilr)-ion plot: A proposed alternative to the Piper diagram

The Piper diagram has been a staple for the analysis of water chemistry data since its introduction in 1944. It was conceived to be a method for water classification, determination of potential water mixing between end-members, and to aid in the identification of chemical reactions controlling a sample set. This study uses the information gleaned over the years since the release of the Piper diagram and proposes an alternative to it, capturing the strengths of the original diagram while adding new ideas to increase its robustness. The new method uses compositional data analysis to create 4 isometric log-ratio coordinates for the 6 major chemical species analyzed in the Piper diagram and transforms the data to a 4-field bi-plot, the ilr-ion plot. This ilr-ion plot conveys all of the information in the Piper diagram (water mixing, water types, and chemical reactions) while also visualizing additional data, the ability to examine Ca 2+ /Mg 2+ versus Cl-/SO 4 2− . The Piper and the ilr-ion plot were also compared using multiple synthetic and real datasets in order to illustrate the caveats and the advantages of using either diagram to analyze water chemistry data. Although there are challenges with using the ilr-ion plot (e.g., missing or zero values zeros in the dataset must be imputed by positive real numbers), it appears that the use of compositional data analysis coupled with the ilr-ion plot provides a more in-depth and complete analysis of water quality data compared to the original Piper diagram.

Journal of Geochemical Exploration

Tungsten skarn mineral resource assessment of the Great Basin region of western Nevada and eastern California

A new quantitative mineral resource assessment for tungsten, a critical mineral commodity with highly concentrated production and a moderate risk of global supply disruption, was conducted for the Great Basin region of western Nevada and eastern California. This assessment was part of a larger effort focusing on three regions in the United States and represents the first study of domestic tungsten resources and mineral potential in over twenty years. By integrating geology, bedrock and stream sediment geochemistry, geophysics, and remote sensing data with recently developed software tools and analyses, estimates of undiscovered tungsten skarn deposits in permissive tracts are combined with grade and tonnage distributions of known deposits to generate probabilistic estimates of undiscovered resources. Identified resources in the Great Basin region total 168 thousand metric tons (kt) of tungsten trioxide (WO 3 ), including 116 kt of past production and 52 kt remaining in place. Consistent with the historic significance of the Great Basin region as a past producer containing a large portion of U.S. identified resources, undiscovered resources are likely to occur adjacent to known deposits and prospects and at unexplored depths. Undiscovered deposits are estimated to contain median resources of 940 kt of WO 3 with a 90% probability of at least 420 kt and a 10% probability of at least 1.7 million metric tons (Mt), of which 240 kt to 1.1 Mt may be economic to extract. Based on a 20-year average price, median recoverable undiscovered resources are estimated at 570 kt WO 3 equivalent with a net present value of $3 billion U.S. dollars. The methods, data, results, and economic significance of the assessment contribute to a scientific understanding of a critical mineral resource with direct implications for policy and land management decisions.

California, Nevada

Regional occurrence of aqueous tungsten and relations with antimony, arsenic and molybdenum concentrations (Sardinia, Italy)

T ungsten (W) is rarely found in natural waters, yet it can be introduced into the food chain and cause potentially toxic effects. Uptake of W by plants and vegetables, or trace presence of W in drinking water are possible vectors for ingestion of W by humans. The latter is recognized as a possible cause of lymphatic leukemia. Increased uses of W might result in a degradation of water resources, with attendant adverse effects on biota and human health. Therefore, this study was aimed at investigating regional occurrence and speciation of W in aquatic systems in Sardinia, Italy, factors affecting W mobility and possible relations with other oxyanion-forming trace elements such as Sb, As and Mo. Although our results are specifically from Sardinia, the implications are broader and should prompt future studies in other areas with known high W concentrations. A total of 350 sample sites are reported here, including surface waters, groundwaters, mine drainages, thermal waters and local seawater. The waters were analyzed for major and trace components, including W, Sb, As and Mo. The waters showed a variety of major chemical compositions and W concentrations. High concentrations of W were found in some mine waters and drainages from slag heaps, with W, Sb and As up to 140, 5000 and 800 μg L −1 , respectively. The highest concentrations of W occurred under slightly alkaline pH and oxygenated conditions, and were likely due to the dissolution of scheelite [CaWO 4 ] hosted in materials with which the water came into contact. High W concentrations also were observed in thermal waters, under alkaline pH and reducing conditions, and sometimes coincided with relatively high concentrations either of As or Mo. Previous studies of W geochemistry have focused on WO 4 2− as the major dissolved form of W. For this study, we have augmented the thermodynamic database in PHREEQC to include possible formation of many other W-bearing complexes gleaned from the literature. The results of the speciation calculations with the newly added complexation reactions shows that the neutral species CaWO 4 ° and MgWO 4 ° are particularly dominant in most W-bearing waters and lead to undersaturation with respect to scheelite and other W-bearing minerals. Assessing W contamination in water systems and establishing W limits in drinking water may prevent potential adverse effects of W on human and ecosystem health.

Sardinia

Hyperspectral (VNIR-SWIR) analysis of roll front uranium host rocks and industrial minerals from Karnes and Live Oak Counties, Texas Coastal Plain

VNIR-SWIR (400–2500 nm) reflectance measurements were made on the surfaces of various cores, cuttings and sample splits of sedimentary rocks from the Tertiary Jackson Group, and Catahoula, Oakville and Goliad Formations. These rocks vary in composition and texture from mudstone and claystone to sandstone and are known host rocks for roll front uranium occurrences in Karnes and Live Oak Counties, Texas. Spectral reflectance profiles, 569 in total, were reduced to 125 representative spectral signatures, which were analyzed using the U.S. Geological Survey's (USGS) Material Identification and Characterization Algorithm (MICA). MICA uses an automated continuum-removal procedure together with a least-squares linear regression to determine the fit of observed sample spectral absorption features to those of reference mineral standards in a spectral library. The reference minerals include various clay, mica, carbonate, ferric and ferrous iron minerals and their mixtures. In addition, absorption feature band-depth analysis was done to identify rock surfaces exhibiting absorption features related to uranium and zeolite minerals, which were not included in the command files used to execute MICA. Rocks from each of the four geologic units produced broadly similar spectral signatures as a result of comparable mineral compositions, but there were some notable differences. For example, Ca- and Na-montmorillonite was matched most frequently to the spectral absorption features in 2-μm (∼2000–2500 nm) wavelengths, while goethite occurred often at 1-μm (∼400–1000 nm) wavelengths. The latter is related to limonitic iron-staining in and around oxidized zones of the uranium roll front as described in previous papers. Rocks of the Jackson Group differed from those of the Catahoula, Oakville and Goliad units in that the former exhibited spectral features we interpret as being due to the presence of lignite-bearing mudstone layers. Goliad rocks exhibit spectral features related to dolomite, gypsum, anhydrite, and an unidentified green clay mineral that is possibly glauconite . Jackson Group rocks also exhibit weak but well-resolved absorption features at 964 and 1157 nm related to either or both zeolite minerals clinoptilolite and heulandite. These zeolite minerals and a few spectra exhibiting hydrous silica absorption features are indicative of alteration of volcanic glass in tuffaceous mudstone and claystone layers. A few sample spectra exhibited strong absorption features at around 1135 nm related to the uranium mineral coffinite. Both the 1135 nm coffinite and 1157 nm zeolite absorption features overlap somewhat, potentially making them difficult to distinguish without additional hyperspectral field, laboratory or remote sensing data. The results of this study were compared to mixtures of minerals described for ore, gangue and alteration minerals in deposit models for sandstone-hosted uranium, sedimentary bentonite and sedimentary zeolite. Use of these spectra can help facilitate mapping of both waste materials from the legacy mining of the above commodities, as well as future exploration and resource assessment activities.

Texas

The addition of 144Nd atomic mass to routine ICP-MS analysis as a Quick Screening Tool for Approximating Rare Earth Elements (Q-STAR) in natural waters

Rare earth elements (REEs) are a class of critical minerals, all of which can have supply chain vulnerability that impacts economic security. These elements are widely measured in environmental matrices via inductively coupled plasma mass spectrometry (ICP-MS); however, successful quantification can require time-consuming, sample-specific optimization. While a sample-by-sample approach is appropriate for targeted quantification studies, this approach is not suitable for mineral exploration efforts where rapidly screening thousands of samples for the presence of REEs is desired. Here, we demonstrated the use of a Quick Screening Tool for Approximating REEs (Q-STAR) to detect REEs in surface water and groundwater matrices, collected as part of existing environmental studies. A mass-to-charge ratio of 144 ( m / z = 144) was added to an ICP-MS method to screen for REEs in filtered water samples submitted for metals analyses to the U.S. Geological Survey (USGS) National Water Quality Laboratory. We detected the presence of REEs above a reference threshold of 1200 counts per second in 18 % of pre-selected 6626 samples. Using this screened dataset, we mapped estimated dissolved REE concentrations across the United States in relation to ecoregions and underlying geology. Data are constrained to where sample collection took place but nevertheless show estimated aqueous dissolved REE concentrations on a geographic scale that has not yet been studied. To validate Q-STAR, REEs were measured in a USGS standard reference sample, a subset of 88 archived filtered water samples, and in fresh filtered surface water samples. Our targeted analyses demonstrated a strong linear relationship between Q-STAR predicted and measured values in all archived samples for Nd (r 2 = 0.94), and light REEs (LREEs) such as lanthanum (La) (r 2 = 0.93), praseodymium (Pr) (r 2 = 0.94) and samarium (Sm) (r 2 = 0.94). Using Q-STAR screen values, nine field sites were identified and surface water samples recollected to confirm the continued presence of Nd and LREEs. Q-STAR can be used to screen an unlimited number of water samples for the presence of REEs prior to time-intensive and costly quantitative analyses and to generate large REE datasets for further investigation.

Journal of Geochemical Exploration