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Geochemical and isotopic study of soils and waters from an Italian contaminated site: Agro Aversano (Campania)

Lead isotope applications have been widely used in recent years in environmental studies conducted on different kinds of sampled media. In the present paper, Pb isotope ratios have been used to determine the sources of metal pollution in soils and waters in the Agro Aversano area. During three different sampling phases, a total of 113 surface soils (5-20. cm), 20 samples from 2 soil profiles (0-1. m), 11 stream waters and 4 groundwaters were collected. Major element concentrations in sampled media have been analyzed by the ICP-MS technique. Surface soils (20 samples), all soil profiles and all waters have been also analyzed for Pb isotope compositions by thermal ionization (TIMS). The geochemical data were assessed using statistic methods and cartographically elaborated in order to have a clear picture of the level of disturbance of the area. Pb isotopic data were studied to discriminate between anthropogenic and geologic sources. Our results show that As (5.6-25.6. mg/kg), Cu (9-677. mg/kg), Pb (22-193. mg/kg), Tl (0.53-3.62. mg/kg), V (26-142. mg/kg) and Zn (34-215. mg//kg) contents in analyzed soils, exceed the intervention limits fixed by the Italian Environmental Law for residential areas in some of the sampled sites, while intervention limit for industrial areas is exceeded only for Cu concentrations. Lead isotopic data, show that there is a high similarity between the ratios measured in the leached soil samples and those deriving from anthropic activities. This similarity with anthropogenic Pb is also evident in the ratios measured in both groundwater and stream water samples. ?? 2010 Elsevier B.V.

Journal of Geochemical Exploration

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

The distribution of selected elements and minerals in soil of the conterminous United States

In 2007, the U.S. Geological Survey initiated a low-density (1 site per 1600 km 2 , 4857 sites) geochemical and mineralogical survey of soil of the conterminous United States as part of the North American Soil Geochemical Landscapes Project. Three soil samples were collected, if possible, from each site; (1) a sample from a depth of 0 to 5 cm, (2) a composite of the soil A-horizon, and (3) a deeper sample from the soil C-horizon or, if the top of the C-horizon was at a depth greater than 100 cm, from a depth of approximately 80–100 cm. The < 2 mm fraction of each sample was analysed for a suite of 45 major and trace elements following near-total multi-acid digestion. The major mineralogical components in samples from the soil A- and C-horizons were determined by a quantitative X-ray diffraction method using Rietveld refinement. Sampling ended in 2010 and chemical and mineralogical analyses were completed in May 2013. Maps of the conterminous United States showing predicted element and mineral concentrations were interpolated from actual soil data for each soil sample type by an inverse distance weighted (IDW) technique using ArcGIS software. Regional- and national-scale map patterns for selected elements and minerals apparent in interpolated maps are described here in the context of soil-forming factors and possible human inputs. These patterns can be related to (1) soil parent materials, for example, in the distribution of quartz, (2) climate impacts, for example, in the distribution of feldspar and kaolinite, (3) soil age, for example, in the distribution of carbonate in young glacial deposits, and (4) possible anthropogenic loading of phosphorus (P) and lead (Pb) to surface soil. This new geochemical and mineralogical data set for the conterminous United States represents a major step forward from prior national-scale soil geochemistry data and provides a robust soil data framework for the United States now and into the future.

Journal of Geochemical Exploration

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

Pb-Sr isotopic and geochemical constraints on sources and processes of lead contamination in well waters and soil from former fruit orchards, Pennsylvania, USA: A legacy of anthropogenic activities

Isotopic discrimination can be an effective tool in establishing a direct link between sources of Pb contamination and the presence of anomalously high concentrations of Pb in waters, soils, and organisms. Residential wells supplying water containing up to 1600 ppb Pb to houses built on the former Mohr orchards commercial site, near Allentown, PA, were evaluated to discern anthropogenic from geogenic sources. Pb (n = 144) and Sr (n = 40) isotopic data and REE (n = 29) data were determined for waters from residential wells, test wells (drilled for this study), and surface waters from pond and creeks. Local soils, sediments, bedrock, Zn-Pb mineralization and coal were also analyzed (n = 94), together with locally used Pb-As pesticide (n = 5). Waters from residential and test wells show overlapping values of 206 Pb/ 207 Pb, 208 Pb/ 207 Pb and 87 Sr/ 86 Sr. Larger negative Ce anomalies (Ce/Ce*) distinguish residential wells from test wells. Results show that residential and test well waters, sediments from residential water filters in water tanks, and surface waters display broad linear trends in Pb isotope plots. Pb isotope data for soils, bedrock, and pesticides have contrasting ranges and overlapping trends. Contributions of Pb from soils to residential well waters are limited and implicated primarily in wells having shallow water-bearing zones and carrying high sediment contents. Pb isotope data for residential wells, test wells, and surface waters show substantial overlap with Pb data reflecting anthropogenic actions (e.g., burning fossil fuels, industrial and urban processing activities). Limited contributions of Pb from bedrock, soils, and pesticides are evident. High Pb concentrations in the residential waters are likely related to sediment build up in residential water tanks. Redox reactions, triggered by influx of groundwater via wells into the residential water systems and leading to subtle changes in pH, are implicated in precipitation of Fe oxyhydroxides, oxidative scavenging of Ce(IV), and desorption and release of Pb into the residential water systems. The Pb isotope features in the residences and the region are best interpreted as reflecting a legacy of industrial Pb present in underlying aquifers that currently supply the drinking water wells.

Pennsylvania

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

Geochemical and Pb isotopic characterization of soil, groundwater, human hair, and corn samples from the Domizio Flegreo and Agro Aversano area (Campania region, Italy)

A geochemical survey was carried out to investigate metal contamination in the Domizio Littoral and Agro Aversano area (Southern Italy) by means of soil, groundwater, human hair and corn samples. Pb isotope ratios were also determined to identify the sources of metals. Specifically, the investigation focused on topsoils ( n = 1064), groundwater ( n = 26), 25 human hair ( n = 24) and corn samples ( n = 13). Topsoils have been sampled and analysed in a previous study for 53 elements (including potentially harmful ones), and determined by ICP-MS after dissolving with aqua regia. Groundwater was analysed for 72 elements by ICP-MS and by ICP-ES. Samples of human hair were prepared and analysed for 16 elements by ICP-MS. Dried corn collected at several farms were also analysed for 53 elements by ICP-MS. The isotopic ratios of 206 Pb/ 207 Pb and 208 Pb/ 207 Pb in selected topsoil ( n = 24), groundwater ( n = 9), human hair ( n = 9) and corn ( n = 4) samples were analysed from both eluates and residues to investigate possible anthropogenic contamination and geogenic contributions. All data were processed and mapped by ArcGis software to produce interpolated maps and contamination factor maps of potentially harmful elements, in accordance with Italian Environmental Law (Legislative Decree 152/06). Results show that soil sampling sites are characterized by As, Cd, Co, Cr, Cu, Hg, Pb, Se, and Zn contents exceeding the action limits established for residential land use (RAL) and, in some cases, also the action limits for industrial land use (IAL) as established by Legislative Decree 152/06. A map of contamination factors and a map showing the degrees of contamination indicate that the areas in the municipalities of Acerra, Casoria and Giugliano have been affected by considerable anthropogenic-related pollution. To interpret the isotopic data and roughly estimate proportion of Pb from an anthropogenic source we broadly defined possible natural and anthropogenic Pb end-member fields based on literature data. For example, we summarized data for Vesuvius and Campi Flegrei volcanic rocks, gasoline, and aerosol deposits. Lead isotope data show mixing between geogenic and anthropogenic sources. Topsoil, groundwater, human hair and corn samples show a greater contribution from geogenic sources like the Yellow Tuff (from Campi Flegrei) and volcanic rocks from Mt. Vesuvius. Aerosols, fly ash and gasoline (anthropogenic sources) have also been contributors. In detail, 46% of the topsoil residues, 96% of topsoil leachates, 88% of groundwater, 90% of human hair, and 25% of corn samples indicate that > 50% percent of the lead in this area can be ascribed to anthropogenic activity.

Campania region

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

Selected trace-elements in alluvium and rocks, western Mojave Desert, southern California

Concentrations of twenty-seven elements, including naturally-occurring water-quality contaminants arsenic, chromium, and uranium, were measured in 217 samples of alluvium and rock from the western Mojave Desert, southern California, using portable (pXRF) and laboratory (LXRF) X-ray fluorescence. Comparison of measurements with NIST-traceable standards was good, although pXRF overestimated iron compared to LXRF. Results suggest pXRF survey data are sufficiently accurate to assess regional geochemical differences in geologic-source terrains. Principal component analysis showed rubidium and potassium were associated with alluvium eroded from felsic terrain, while iron, copper, chromium, and to a lesser extent titanium, manganese, and nickel were associated with alluvium eroded from mafic terrain. Zinc, vanadium, and arsenic were associated with alluvium eroded from hydrothermal terrain. Elemental assemblages associated with different source terrains were traced spatially to identify the source and composition of alluvium composing aquifers pumped for water supply. Changes in geologic source terrain to the Mojave River, associated with movement along the San Andreas Fault over the past one to five million years, reduced the mafic fraction and increased the felsic fraction of alluvium deposited to the regionally important floodplain aquifer along the Mojave River—lowering chromium concentrations in alluvium through geologic time. Comparison of pXRF and sequential extraction data from 40 samples showed arsenic and uranium were more abundant on the surfaces of mineral grains, while chromium and vanadium remained mostly within unweathered mineral grains—suggesting arsenic and uranium may be more readily mobilized into groundwater with changes in pH, redox, or ionic strength than chromium or vanadium.

California

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

Ore mineralization in the Mofete and San Vito geothermal fields, Campi Flegrei volcanic complex, Naples, Italy

The Mofete and San Vito geothermal fields, located west of Naples, Italy, are part of the Campi Flegrei volcanic complex. In the 1970s, exploratory wells were drilled to a depth of ~3000 m in an attempt to locate high-enthalpy fluids for potential power production. Drill core samples from Mofete wells (MF1, MF2, and MF5) and from San Vito wells (SV1 and SV3) contain authigenic ore mineralization. Pyrite, pyrrhotite, and galena are abundant. Less common are chalcopyrite, sphalerite, arsenopyrite, and scheelite; rare are millerite, violarite, native bismuth, tellurobismuthite, cassiterite, molybdenite, and acanthite. Mineral chemistry was determined by electron microprobe wavelength dispersive spectroscopy aided by a scanning electron microscope equipped with energy-dispersive spectroscopy. The mineral assemblage suggests a low sulfidation environment and the absence of pyrrhotite in the MF1 well and upper part of the SV1 well indicates variable sulfur activity. Both molybdenite and scheelite were identified in samples SV1–2860 and SV3–2353 and scheelite in the SV3 well is zoned with variable Mo 6+ content; low Mo 6+ zones show blue cathodoluminescence, whereas, zones with high Mo 6+ content are yellow to brown. Zoned scheelite and the occurrence of both Mo-bearing minerals attest to the variability of ƒO 2 and ƒS 2 in the geothermal fluid.

Naples

Top-down targeted network analysis of critical mineral commodities applied to international geochemistry database

The global demand for critical mineral commodities is rapidly increasing, making domestic production an important factor in supporting the economy and national security. Large scale, publicly available geochemical databases allow for the application of data informatics methods to interrogate critical mineral commodities data for correlations in deposit formation and distribution, particularly for identifying enrichment of multiple critical mineral commodities at the same deposit. In this study, we applied network analysis to the Critical Minerals Mapping Initiative (CMMI) ore geochemistry (Critical Minerals in Ores, CMiO) database to identify the high concentration (defined as 10× bulk crustal abundance) co-occurrence of different critical mineral commodities across a mineral system hierarchy from deposit environments to individual deposits. Identifying patterns or unique outliers in enrichment in network communities will allow for the location of secondary critical mineral commodity resources from under-utilized deposits. We find trends in the enrichment of critical mineral commodities in network-communities between the elements praseodymium (Pr), neodymium (Nd), terbium (Tb), and dysprosium (Dy) across multiple CMiO database deposit environments and groups down to specific deposit types and sites. A separate trend in network community deposition is observed as well between iridium (Ir) and platinum (Pt) in deposit environments, groups, types, and sites. Network analysis focused on critical minerals in magmatic-hydrothermal deposits identified multiple deposit sites from different deposit types within the CMiO database with concentrations of Dy, Nd, Tb, Pr, Ir, and Pt that are at least ten times greater than the crustal average. This approach can be applied to any target element(s) or deposit(s) of interest, allowing broad investigation of co-enriched critical mineral commodities.

Journal of Geochemical Exploration

Some statistical relationships between stream sediment and soil geochemistry in northwestern Wisconsin - can stream sediment compositions be used to predict compositions of soils in glaciated terranes?

Mean stream sediment chemical compositions from northwestern Wisconsin in the north central United States, based on more than 800 samples, differ significantly from mean A-horizon and C-horizon soil compositions, based on about 380 samples of each horizon. Differences by a factor greater than 1.5 exist for some elements (Ca, Mn, Mg, P, Ti, Ni, Pb, Se, Zn). A very large database of stream sediment geochemistry exists for the region (more than 2200 samples) and for the U.S. (roughly 400,000 samples), whereas data on the chemistry of soils is much sparser both regionally and nationally. Therefore, we have attempted to quantify trends in compositional differences between stream sediments and nearby soils to test whether the abundant stream sediment data can be used to predict soil compositions. A simple computational technique of adjusting the stream sediment compositions according to the ratio of means of soils and stream sediments was conducted. A variety of techniques of correction and interpolation of data were tested and indicate that repetitive testing of results allows an optimum correction to be achieved. Predicted soil compositions compared to analytically determined soil compositions show a range of results from relatively good correspondence for some elements to rather poor correspondence for others. In general, predictions are best at midranges of compositions. The technique does not predict well more extreme or anomalous values. Thus, this technique appears to be useful for estimating background soil compositions and delineating regional compositional trends in soils in situations where large amounts of stream sediment analyses and smaller amounts of soil analyses are available. The technique also provides probabilistic qualifications on the expected error between predicted and actual soil compositions so that individual users can judge if the technique provides data of sufficient accuracy for specific needs. ?? 2003 Elsevier B.V. All rights reserved.

Journal of Geochemical Exploration

Geochemical patterns in soils of the karst region, Croatia

Soil samples were collected at 420 locations in a 5-km grid pattern in the Istria and Gorski Kotar areas of Croatia, and on the Croatian islands of Cres, Rab and Krk, in order to relate geochemical variation in the soils to underlying differences in geology, bedrock lithology, soil type, environment and natural versus anthropogenic influences. Specific objectives included assessment of possible agricultural and industrial sources of contamination, especially from airborne effluent emitted by a local power plant. The study also tested the adequacy of a fixed-depth soil sampling procedure developed for meager karstic soils. Although 40 geochemical variables were analyzed, only 15 elements and 5 radionuclides are common to all the sample locations. These elements can be divided into three groups: (1) those of mostly anthropogenic origin — Pb, V, Cu and Cr; (2) those of mixed origin — radionuclides and Zn; and (3) those of mostly geogene origin — Ba, Sr, Ti, Al, Na, Ca, Mg, Fe, Mn, Ni and Co. Variation in Pb shows a strong correlation with the pattern of road traffic in Istria. The distributions of Ca, Na and Mg in the flysch basins of southern Istria and Slovenia are clearly distinguishable from the distributions of these elements in the surrounding carbonate terrains, a consequence of differences in bedrock permeability, type of drainage and pH. The spatial pattern of 137 Cs from the Chernobyl nuclear power plant accident reflects almost exclusively the precipitation in Istria during the days immediately after the explosion.

Journal of Geochemical Exploration

Occurrence and transport of total mercury and methyl mercury in the Sacramento River Basin, California

Mercury poses a water-quality problem for California's Sacramento River, a large river with a mean annual discharge of over 650 m3/s. This river discharges into the San Francisco Bay, and numerous fish species of the bay and river contain mercury levels high enough to affect human health if consumed. Two possible sources of mercury are the mercury mines in the Coast Ranges and the gold mines in the Sierra Nevada. Mercury was once mined in the Coast Ranges, west of the Sacramento River, and used to process gold in the Sierra Nevada, east of the river. The mineralogy of the Coast Ranges mercury deposits is mainly cinnabar (HgS), but elemental mercury was used to process gold in the Sierra Nevada. Residual mercury from mineral processing in the Sierra Nevada is mainly in elemental form or in association with oxide particles or organic matter and is biologically available. Recent bed-sediment sampling, at sites below large reservoirs, showed elevated levels of total mercury (median concentration 0.28 ??g/g) in every large river (the Feather, Yuba, Bear, and American rivers) draining the Sierra Nevada gold region. Monthly sampling for mercury in unfiltered water shows relatively low concentrations during the nonrainy season in samples collected throughout the Sacramento River Basin, but significantly higher concentrations following storm-water runoff. Measured concentrations, following storm-water runoff, frequently exceeded the state of California standards for the protection of aquatic life. Results from the first year of a 2-year program of sampling for methyl mercury in unfiltered water showed similar median concentrations (0.1 ng/l) at all sampling locations, but with apparent high seasonal concentrations measured during autumn and winter. Methyl mercury concentrations were not significantly higher in rice field runoff water, even though rice production involves the creation of seasonal wetlands: higher rates of methylation are known to occur in stagnant wetland environments that have high dissolved carbon.Mercury poses a water-quality problem for California's Sacramento River, a large river with a mean annual discharge of over 650 m3/s. This river discharges into the San Francisco Bay, and numerous fish species of the bay and river contain mercury levels high enough to affect human health if consumed. Two possible sources of mercury are the mercury mines in the Coast Ranges and the gold mines in the Sierra Nevada. Mercury was once mined in the Coast Ranges, west of the Sacramento River, and used to process gold in the Sierra Nevada east of the river. The mineralogy of the Coast Ranges mercury deposits is mainly cinnabar (HgS), but elemental mercury was used to process gold in the Sierra Nevada. Residual mercury from mineral processing in the Sierra Nevada is mainly in elemental form or in association with oxide particles or organic matter and is biologically available. Recent bed-sediment sampling, at sites below large reservoirs, showed elevated levels of total mercury (median concentration 0.28 ??g/g) in every large river (the Feather, Yuba, Bear, and American rivers) draining the Sierra Nevada gold region. Monthly sampling for mercury in unfiltered water shows relatively low concentrations during the nonrainy season in samples collected throughout the Sacramento River Basin, but significantly higher concentrations following storm-water runoff. Measured concentrations, following storm-water runoff, frequently exceeded the state of California standards for the protection of aquatic life. Results from the first year of a 2-year program of sampling for methyl mercury in unfiltered water showed similar median concentrations (0.1 ng/l) at all sampling locations, but with apparent high seasonal concentrations measured during autumn and winter. Methyl mercury concentrations were not significantly higher in rice field runoff water, even though rice production involves the creation of seasonal wetlands: higher rates of methylation a

Journal of Geochemical Exploration

In-situ alteration of minerals by acidic ground water resulting from mining activities: Preliminary evaluation of method

The chemical composition of the Cu-mining-related acidic ground water (pH ∼ 3.5 to near neutral) in Pinal Creek Basin, Arizona has been monitored since 1980. In-situ experiments are planned using alluvial sediments placed in the ground-water flow path to measure changes in mineral and chemical composition and changes in dissolution rates of subsurface alluvial sediments. The test results should help refine developed models of predicted chemical changes in ground-water composition and models of streamflow. For the preliminary test, sediment from the depth of the well screen of a newly drilled well was installed in three wells, the source well (pH 4.96) and two up-gradient wells (pHs 4.27 and 4.00). The sediment was placed in woven macrofilters, fastened in series to polyvinyl chloride (PVC) pipes, and hung at the screened level of each well. After interacting with the slowly moving ground water for 48 days, the test sediments were removed for analysis. There was no evidence that any of the materials used were biologically or chemically degraded or that the porosity of the filters was diminished by ferric hydroxide precipitation. These materials included 21-μm-pore (21PEMF) and 67-μm-pore polyester and the 174-μm-pore fluorocarbon Spectra/mesh macrofilters containing the in-situ sediment, the polypropylene (PP) macrofilter support structures, and the Nylon (NY) monofilament line used to attach the samples to the PVC pipe. Based on chemical and mineral composition and on particle-size distribution of the sediment before and after ground-water exposure, the 21PEMF macrofilter was chosen as the most suitable macrofilter for the long-term in-situ experiment. Tests also showed that the PP support structures and the NY monofilament line were sufficiently durable for this experiment.

Arizona