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USGS2011

A Holocene record of endogenic iron and manganese precipitation and vegetation history in a lake-fen complex in northwestern Minnesota

Little Shingobee Lake and Fen are part of the extensive network of lakes and wetlands in the Shingobee River headwaters of northwestern Minnesota, designed to study the interactions between surface and ground waters. Prior to about 11.2 cal. ka, most of these lakes and wetlands were interconnected to form glacial Lake Willobee, which apparently formed when a debris flow dammed the Shingobee River. Between 11.2 and 8.5 cal. ka, the level of Lake Willobee fell as a result of breaching of the dam, transforming the deep lake into the existing lakes and wetlands. Analyses of a 9-m core from Little Shingobee Lake (LSL-B), and lacustrine sediments under 3.3 m of peat in a 17-m core from Little Shingobee Fen (LSF-10), show that the dominant components are allogenic clastic material, and endogenic CaCO 3 and organic matter. In both cores almost all of the iron (Fe) and manganese (Mn) are incorporated in endogenic minerals, presumed to be X-ray amorphous oxyhydroxide minerals, that occur in significant quantities throughout the cores; almost no Fe and Mn are contributed from detrital aluminosilicate minerals. This suggests that, for most of the Holocene, the allogenic watershed contributions to lake chemistry were minor compared to the dissolved mineral load. In addition, prior to 3.5 cal. ka, pollen zone boundaries coincide with large changes in lake-sediment mineralogy, indicating that both landscape and climate processes were linked to early- and mid-Holocene lake chemistry. The pollen time series, with sequential domination by spruce, pine, sagebrush-oak, birch-oak and, finally, white pine is typical of the region and reflects the changing location of the prairie-forest transition zone over time. These changes in vegetation had some profound effects on the geochemistry of the lake waters.

Minnesota↗

USGS2007

Rare-earth elements in the Permian Phosphoria formation: Paleo proxies of ocean geochemistry

The geochemistry of deposition of the Meade Peak Member of the Phosphoria Formation (MPM) in southeast Idaho, USA, a world-class sedimentary phosphate deposit of Permian age that extends over 300,000 km 2 , is ascertained from its rare earth element (REE) composition. Ratios of REE:Al 2 O 3 suggest two sources—seawater and terrigenous debris. The seawater-derived marine fraction identifies bottom water in the Phosphoria Sea as O 2 -depleted, denitrifying (suboxic) most of the time, and seldom sulfate-reducing (anoxic). This interpretation is supported by earlier research that showed progressively greater ratios in the marine sediment fraction of Cr:Ni>V:Ni⪢Mo:Ni, relative to their ratios in seawater; for which marine Cr, V, and Mo can have a dominantly O 2 –depleted bottom-water source and Ni a photic-zone, largely algal, source. The water chemistry was maintained by a balance between bacterial oxidation of organic matter settling through the water column, determined largely by primary productivity in the photic zone, and the flux of oxidants into the bottom water via advection of seawater from the open ocean. Samples strongly enriched in carbonate fluorapatite, the dominant REE host mineral, have variable Er/Sm, Tm/Sm, and Yb/Sm ratios. Their distribution may represent greater advection of seawater between the Phosphoria Sea and open ocean during deposition of two ore zones than a center waste and greater upwelling of nutrient-enriched water into the photic zone. However, the mean rate of deposition of marine Ni, a trace nutrient of algae, and PO 4 3− , a limiting nutrient, indicate that primary productivity was probably high throughout the depositional history. An alternative interpretation of the variable enrichments of Er, Tm, and Yb, relative to Sm, is that they may reflect temporally variable carbonate alkalinity of open-ocean seawater in Permian time. A more strongly negative Ce anomaly for all phosphatic units than the Ce anomaly of modern pelletal phosphate is further indicative of an elevated O 2 concentration in the Permo-Carboniferous open ocean, as proposed by others, in contrast to the depletion of O 2 in the bottom water of the Phosphoria Sea itself. The oceanographic conditions under which the deposit accumulated were likely similar to conditions under which many sedimentary phosphate deposits have accumulated and to conditions under which many black shales that are commonly phosphate poor have accumulated. A shortcoming of several earlier studies of these deposits has resulted from a failure to examine the marine fraction of elements separate from the terrigenous fraction.

Idaho↗

USGS1985

Germanium geochemistry and mineralogy

Germanium is enriched in the following geologic environments: 1. (1) iron meteorites and terrestrial iron-nickel; 2. (2) sulfide ore deposits, particularly those hosted by sedimentary rocks; 3. (3) iron oxide deposits; 4. (4) oxidized zones of Ge-bearing sulfide deposits; 5. (5) pegmatites, greisens, and skarns; and 6. (6) coal and lignitized wood. In silicate melts, Ge is highly siderophile in the presence of native iron-nickel; otherwise, it is highly lithophile. Among silicate minerals, Ge is concentrated in those having less polymerized silicate tetrahedra such as olivine and topaz. In deposits formed from hydrothermal solutions, Ge tends to be enriched mostly in either sulfides or in fluorine-bearing phases; it is thus concentrated both in some hydrothermal sulfide deposits and in pegmatites, greisens, and skarns. In sulfide deposits that formed from solutions having low to moderate sulfur activity, Ge is concentrated in sphalerite in amounts up to 3000 ppm. Sulfide deposits that formed from solutions having higher sulfur activity allowed Ge to either form its own sulfides, particularly with Cu, or to substitute for As, Sn, or other metals in sulfosalts. The Ge in hydrothermal fluids probably derives from enrichment during the fractional crystallization of igneous fluids, or is due to the incorporation of Ge from the country rocks, particularly from those containing organic material. Germanium bonds to lignin-derivative organic compounds that are found in peat and lignite, accounting for its common concentration in coals and related organic material. Germanium is precipitated from water together with iron hydroxide, accounting for its concentration in some sedimentary and supergene iron oxide deposits. It also is able to substitute for Fe in magnetite in a variety of geologic environments. In the oxidized zone of Ge-bearing sulfide deposits, Ge is concentrated in oxides, hydroxides, and hydroxy-sulfates, sometimes forming its own minerals. It is particularly enriched in some iron- and manganese-bearing oxides and hydroxides, including goethite (up to 5300 ppm) and hematite (up to 7000 ppm).

Geochimica et Cosmochimica Acta↗

USGS2011

Hillslope chemical weathering across Paraná, Brazil: a data mining-GIS hybrid approach

Self-organizing map (SOM) and geographic information system (GIS) models were used to investigate the nonlinear relationships associated with geochemical weathering processes at local (~100 km 2 ) and regional (~50,000 km 2 ) scales. The data set consisted of 1) 22 B-horizon soil variables: P, C, pH, Al, total acidity, Ca, Mg, K, total cation exchange capacity, sum of exchangeable bases, base saturation, Cu, Zn, Fe, B, S, Mn, gammaspectrometry (total count, potassium, thorium, and uranium) and magnetic susceptibility measures; and 2) six topographic variables: elevation, slope, aspect, hydrological accumulated flux, horizontal curvature and vertical curvature. It is characterized at 304 locations from a quasi-regular grid spaced about 24 km across the state of Paraná. This data base was split into two subsets: one for analysis and modeling (274 samples) and the other for validation (30 samples) purposes. The self-organizing map and clustering methods were used to identify and classify the relations among solid-phase chemical element concentrations and GIS derived topographic models. The correlation between elevation and k-means clusters related the relative position inside hydrologic macro basins, which was interpreted as an expression of the weathering process reaching a steady-state condition at the regional scale. Locally, the chemical element concentrations were related to the vertical curvature representing concave–convex hillslope features, where concave hillslopes with convergent flux tends to be a reducing environment and convex hillslopes with divergent flux, oxidizing environments. Stochastic cross validation demonstrated that the SOM produced unbiased classifications and quantified the relative amount of uncertainty in predictions. This work strengthens the hypothesis that, at B-horizon steady-state conditions, the terrain morphometry were linked with the soil geochemical weathering in a two-way dependent process: the topographic relief was a factor on environmental geochemistry while chemical weathering was for terrain feature delineation.

Parana↗

USGS2005

Gas geochemistry of a shallow submarine hydrothermal vent associated with the El Requesón fault zone, Bahía Concepción, Baja California Sur, México

We investigated hydrothermal gas venting associated with a coastal fault zone along the western margin of Bahía Concepción, B.C.S., México. Copious discharge of geothermal liquid (≈ 90 °C) and gas is occurring in the intertidal and shallow subtidal zones (to a depth of 13 m) through soft sediments and fractures in rocks along a &sim;750 m linear trend generally sub-parallel to an onshore fault near Punta Santa Barbara. Hydrothermal activity shows negative correlation with tidal height; temperatures in the area of hydrothermal activity were up to 11.3 °C higher at low tide than at high tide (measured tidal range ≈ 120 cm). Gas samples were collected using SCUBA and analyzed for chemical composition and stable isotope values. The main components of the gas are N 2 (≈ 53%; 534 mmol/mol), CO 2 (≈ 43%; 435 mmol/mol), and CH 4 (≈ 2.2%; 22 mmol/mol). The δ 13 C values of the CH 4 (mean = − 34.3&permil;), and the ratios of CH 4 to C 2 H 6 (mean = 89), indicate that the gas is thermogenic in origin. The carbon stable isotopes and the δ 15 N of the N 2 in the gas (mean = 1.7&permil;) suggest it may be partially derived from the thermal alteration of algal material in immature sedimentary organic matter. The He isotope ratios ( 3 He / 4 He = 1.32 R A ) indicate a significant mantle component (16.3%) in the gas. Here, we suggest the name El Requesón fault zone for the faults that likely formed as a result of extension in the region during the late Miocene, and are currently serving as conduits for the observed hydrothermal activity.

Chemical Geology↗

USGS2015

Enhanced microbial coalbed methane generation: A review of research, commercial activity, and remaining challenges

Coalbed methane (CBM) makes up a significant portion of the world’s natural gas resources. The discovery that approximately 20% of natural gas is microbial in origin has led to interest in microbially enhanced CBM (MECoM), which involves stimulating microorganisms to produce additional CBM from existing production wells. This paper reviews current laboratory and field research on understanding processes and reservoir conditions which are essential for microbial CBM generation, the progress of efforts to stimulate microbial methane generation in coal beds, and key remaining knowledge gaps. Research has been primarily focused on identifying microbial communities present in areas of CBM generation and attempting to determine their function, in-situ reservoir conditions that are most favorable for microbial CBM generation, and geochemical indicators of metabolic pathways of methanogenesis (i.e., acetoclastic or hydrogenotrophic methanogenesis). Meanwhile, researchers at universities, government agencies, and companies have focused on four primary MECoM strategies: 1) microbial stimulation (i.e., addition of nutrients to stimulate native microbes); 2) microbial augmentation (i.e., addition of microbes not native to or abundant in the reservoir of interest); 3) physically increasing microbial access to coal and distribution of amendments; and 4) chemically increasing the bioavailability of coal organics. Most companies interested in MECoM have pursued microbial stimulation: Luca Technologies, Inc., successfully completed a pilot scale field test of their stimulation strategy, while two others, Ciris Energy and Next Fuel, Inc., have undertaken smaller scale field tests. Several key knowledge gaps remain that need to be addressed before MECoM strategies can be implemented commercially. Little is known about the bacterial community responsible for coal biodegradation and how these microorganisms may be stimulated to enhance microbial methanogenesis. In addition, research is needed to understand what fraction of coal is available for biodegradation, and methods need to be developed to determine the extent of in-situ coal biodegradation by MECoM processes for monitoring changes to coal quality. Questions also remain about how well field-scale pilot tests will scale to commercial production, how often amendments will need to be added to maintain new methane generation, and how well MECoM strategies transfer between coal basins with different formation water geochemistries and coal ranks. Addressing these knowledge gaps will be key in determining the feasibility and commercial viability of MECoM technology.

International Journal of Coal Geology↗

USGS1997

Environmental geochemistry and sediment quality in Lake Pontchartrain: database development and review

This paper reports on preliminary results of a project to develop a comprehensive data base of chemical and environmental information on sediments from Lake Pontchartrain, Louisiana, and surrounding water bodies. The goal is to evaluate all data for reliability and comparability, and to make it widely accessible and useful to all users. Methods for processing heterogeneous, historical data follow previous methods employed in the Boston Harbor and Massachusetts Bay area. Data from 11 different data sets, encompassing about 900 total samples, have been entered to date. Questionable or anomalous data were noted in a minority of cases. Problems tend to follow distinct patterns and are relatively easy to identify. Hence, comparability of data has not proven to be the major obstacle to synthesis efforts that was anticipated in earlier years (NRC, 1989). Quality-controlled data sets show that the bulk of sediment samples in the more central parts of Lake Pontchartrain have values within normal background for heavy metals like Cu, Pb, and Zn. The same or lower concentrations were found in the vicinity of the Bonnet Carre Spillway, representing influx from the Mississippi River. Mean concentrations for Cu, Pb, and Zn were 17, 21, and 74 µg/g (total dissolution analyses), respectively. However, values as high as 267 µg/g Pb and comparable increases for other metal and organic contaminants are found in sediments within 2 km of the coastal strip of New Orleans. Additional sampling in such areas and in other inland coastal waterways is needed, since such levels are above the threshold for potential toxic effects on benthic organisms, according to effects-based screening criteria. The most contaminated sites, Bayou Trepagnier and Bayou Bonfouca, involve industrial areas where waste discharge has now been controlled or remediated, but where sediments may retain large concentrations of contaminants, e.g. tenths of a percent of Pb, Cr, and Zn or more for Bayou Trepagnier.

Louisiana↗

USGS2012

Sulfur, carbon, hydrogen, and oxygen isotope geochemistry of the Idaho cobalt belt

Cobalt-copper ± gold deposits of the Idaho cobalt belt, including the deposits of the Blackbird district, have been analyzed for their sulfur, carbon, hydrogen, and oxygen isotope compositions to improve the understanding of ore formation. Previous genetic hypotheses have ranged widely, linking the ores to the sedimentary or diagenetic history of the host Mesoproterozoic sedimentary rocks, to Mesoproterozoic or Cretaceous magmatism, or to metamorphic shearing. The δ 34 S values are nearly uniform throughout the Blackbird dis- trict, with a mean value for cobaltite (CoAsS, the main cobalt mineral) of 8.0 ± 0.4‰ ( n = 19). The data suggest that (1) sulfur was derived at least partly from sedimentary sources, (2) redox reactions involving sulfur were probably unimportant for ore deposition, and (3) the sulfur was probably transported to sites of ore for- mation as H 2 S. Hydrogen and oxygen isotope compositions of the ore-forming fluid, which are calculated from analyses of biotite-rich wall rocks and tourmaline, do not uniquely identify the source of the fluid; plausible sources include formation waters, metamorphic waters, and mixtures of magmatic and isotopically heavy meteoric waters. The calculated compositions are a poor match for the modified seawaters that form vol- canogenic massive sulfide (VMS) deposits. Carbon and oxygen isotope compositions of siderite, a mineral that is widespread, although sparse, at Blackbird, suggest formation from mixtures of sedimentary organic carbon and magmatic-metamorphic carbon. The isotopic compositions of calcite in alkaline dike rocks of uncertain age are consistent with a magmatic origin. Several lines of evidence suggest that siderite postdated the emplacement of cobalt and copper, so its significance for the ore-forming event is uncertain. From the stable isotope perspective, the mineral deposits of the Idaho cobalt belt contrast with typical VMS and sedimentary exhalative deposits. They show characteristics of deposit types that form in deeper environments and could be related to metamorphic processes or magmatic processes, although the isotopic evidence for magmatic components is relatively weak.

Idaho↗

USGS2004

Regional analysis of spiculite faunas in the permian phosphoria basin: Implications for paleoceanography

The sponge spiculites of the Permian Phosphoria basin, Antler high, and eastern Havallah basin were the southernmost expression of one of the largest spiculite belts in the Earth's history. This spiculite belt extended from Nevada to the Barents Sea. In Idaho and Nevada, the spicule populations of this belt are dominated by demosponge spicules and are distinctive for their abundant rhax microscleres, large monaxons, and lithistid desmas. They form an Eastern Belt of spiculites that interfingers with spicule assemblages derived from choristid demosponges and hexactinellids that lived along the eastern margin of the deeper Havallah basin. The Havallah basin assemblages are similar to those in Permian arc terranes to the west, and together the sponge populations in this domain constitute a dis- tinct Central Belt. Radiolarians are virtually absent in the siliceous microfossil populations of the Eastern Belt, abundant in the populations of the Central Belt, and dominant in the populations of a Western Belt confined to Mesozoic accretionary complexes in the Pacific Coast States. The scattered sponge spicules in the Western Belt radiolarites were derived from hexactinellids. During the Permian, the relative abundance and apparent diversity of siliceous sponges expanded over a wide range of depths in the basins from Nevada and Idaho to the open ocean. Radiolarian preservation and apparent diversity increased in the deeper Cordilleran basins as well. In the Arctic regions, significant sponge spiculites were deposited in epicratonic basins. At the same time that siliceous sponge populations expanded along the northwestern margin of Pangea, warm-water carbonate producers disappeared. Suppression of carbonate-producing organisms along the margin was critical to the accu- mulation and preservation of both the demosponge spiculites in the Eastern Belt and the spicule-rich argillites of the Central Belt. Vigorous thermohaline circulation was the major control on the paleobiogeography of the late Early, Middle, and early Late Permian along northwest Pangea. It was driven by cold, nutrient- and oxygen-rich northern waters and it produced a coastal current that swept down the margin of the supercontinent. The upwelling associated with deposition of world-class phosphorites in the Phosphoria basin was a part of this larger oceanographic system.

Handbook of Exploration and Environmental Geochemi↗

USGS2018

Hydrogeochemical controls on brook trout spawning habitats in a coastal stream

Brook trout ( Salvelinus fontinalis ) spawn in fall and overwintering egg development can benefit from stable, relatively warm temperatures in groundwater-seepage zones. However, eggs are also sensitive to dissolved oxygen concentration, which may be reduced in discharging groundwater (i.e., seepage). We investigated a 2 km reach of the coastal Quashnet River in Cape Cod, Massachusetts, USA, to relate preferred fish spawning habitats to geology, geomorphology, and discharging groundwater geochemistry. Thermal reconnaissance methods were used to locate zones of rapid groundwater discharge, which were predominantly found along the central channel of a wider stream valley section. Pore-water chemistry and temporal vertical groundwater flux were measured at a subset of these zones during field campaigns over several seasons. Seepage zones in open-valley sub-reaches generally showed suboxic conditions and higher dissolved solutes compared to the underlying glacial outwash aquifer. These discharge zones were cross-referenced with preferred brook trout redds and evaluated during 10 years of observation, all of which were associated with discrete alcove features in steep cutbanks, where stream meander bends intersect the glacial valley walls. Seepage in these repeat spawning zones was generally stronger and more variable than in open-valley sites, with higher dissolved oxygen and reduced solute concentrations. The combined evidence indicates that regional groundwater discharge along the broader valley bottom is predominantly suboxic due to the influence of near-stream organic deposits; trout show no obvious preference for these zones when spawning. However, the meander bends that cut into sandy deposits near the valley walls generate strong oxic seepage zones that are utilized routinely for redd construction and the overwintering of trout eggs. Stable water isotopic data support the conclusion that repeat spawning zones are located directly on preferential discharges of more localized groundwater. In similar coastal systems with extensive valley peat deposits, the specific use of groundwater-discharge points by brook trout may be limited to morphologies such as cutbanks, where groundwater flow paths do not encounter substantial buried organic material and remain oxygen-rich.

Hydrology and Earth System Sciences↗

USGS2006

Petrography and geochemistry of the Middle Devonian coal from Luquan, Yunnan Province, China

Coals from Luquan, Yunnan Province, China, have high contents of cutinite and microsporinite, with an average of 55 and 33.5 vol%, respectively, (on a mineral-free basis). The coals are classified as cutinitic liptobiolith, sporinite-rich durain, cutinite-rich durain, and sporinitic liptobiolith. These four liptinite-rich coals are often interlayered within the coal bed section and vary transversely within the coal bed. The vitrinite content varies from as low as 1.6-20.5% (mineral-free basis), and it is dominated by collodetrinite, collotelinite, and corpogelinite. The maceral composition may be attributed to the type of the peat-forming plant communities. Moreover, the Luquan coals are characterized by high contents of volatile matter, hydrogen, and oxygen, and the high values of the atomic hydrogen to carbon ratio as a result of the maceral composition. As compared with the common Chinese coals and the upper continental crust, the Luquan coals are enriched in Li, B, Cu, Ga, Se, Rb, Mo, Ba, Pb, Bi, and U, with averages of 99.9, 250, 111, 24.4, 4.55, 130, 58.8, 1276, 162, 3.85, and 34.1 ??g/g, respectively. The SEM-EDX results show that V, Cr, Ga, and Rb occur mainly in clay minerals, and Cu and Pb are associated with clay minerals and pyrite, and Mo and U are mainly in clay minerals and organic matter. Barite and clay minerals are the main carrier of barium. The high B and U contents are probably resulted from deep seawater influence during coal formation. ?? 2005 Elsevier Ltd. All rights reserved.

Fuel↗

USGS2007

Formation of mixed Al-Fe colloidal sorbent and dissolved-colloidal partitioning of Cu and Zn in the Cement Creek - Animas River Confluence, Silverton, Colorado

Transport and chemical transformations of dissolved and colloidal Al, Fe, Cu and Zn were studied by detailed sampling in the mixing zone downstream from the confluence of Cement Creek (pH 4.1) with the Animas River (pH 7.6). Complete mixing resulted in circumneutral pH in the downstream reach of the 1300 m study area. All four metals were transported through this mixing zone without significant losses to the streambed, and they exhibited transformations from dissolved to colloidal forms to varying degrees during the mixing process. Nearly all of the Al formed colloidal hydrous Al oxides (HAO) as pH increased (4.8–6.5), whereas colloidal hydrous Fe oxides (HFO) were supplied by Cement Creek as well as formed in the mixing zone primarily at higher pH (>6.5). The short travel time through the mixing zone (approx. 40 min) and pH limited the formation of HFO from dissolved Fe 2+ supplied by Cement Creek. Although the proportions of HAO and HFO varied as the streams mixed, the colloidal sorbent typically was enriched in HAO relative to HFO by a factor of 1.5–2.1 (by mole) in the pH range where dissolved-to-colloidal partitioning of Cu and Zn was observed. Model simulations of sorption by HFO (alone) greatly underestimated the dissolved-to-colloidal partitioning of Zn. Previous studies have shown that HAO–HFO mixtures can sorb greater amounts of Zn than HFO alone, but the high Zn-to-sorbent ratio in this mixing zone could also account for greater partitioning. In contrast to Zn, comparisons with model simulations did not show that Cu sorption was greater than that for HFO alone, and also indicated that sorption was possibly less than what would be expected for a non-interactive mixture of these two sorbents. These field results for Cu, however, might be influenced by (organic) complexation or other factors in this natural system. Laboratory mixing experiments using natural source waters (upstream of the confluence) showed that the presence of HFO in the mixed sorbent resulted in greater Cu partitioning than for HAO alone, and that the effect was greater with increasing (mole fraction) HFO. This was consistent with field results that showed greater Cu sorption when additional HFO was formed in the downstream reach of the mixing zone. Further research is needed to identify the significance of surface-related mechanisms specific to HAO–HFO mixtures that could affect the partitioning of Cu in natural systems.

Colorado↗

USGS1992

Extraction of whole versus ground source rocks: Fundamental petroleum geochemical implications including oil-source rock correlation

In petroleum geochemistry, extractable hydrocarbons (HCs) in source rocks have typically been studied by grinding the rock to a fine powder (≤100 mesh) and then extracting the HCs from the rock with a solvent. This procedure carries the implicit assumption that the HCs are homogeneously distributed throughout the rock. However, sequential Soxhlet extractions of whole (unpowdered) source rocks have shown that progressive extracts from the same rock can be quite different and may not even correlate with each other. A crude oil-like material clearly has been fractionated from indigenous bitumen in these rocks, has moved to cracks and parting laminae in the rocks, is ready for expulsion from the rocks, and is thus most accessible to the first extracting solvents. This process, which we believe is largely due to HC gases and carbon dioxide generated over all maturation ranks in source rocks, carries petroleum geochemical implications of a fundamental nature for oil-source rock correlations and gives insight into primary migration mechanisms, origin of oil deposits, and use of maturity and organic-facies indices.

Geochimica et Cosmochimica Acta↗

USGS2006

Trace element geochemistry and surface water chemistry of the Bon Air coal, Franklin County, Cumberland Plateau, southeast Tennessee

Mean contents of trace elements and ash in channel, bench-column, and dump samples of the abandoned Bon Air coal (Lower Pennsylvanian) in Franklin County, Tennessee are similar to Appalachian COALQUAL mean values, but are slightly lower for As, Fe, Hg, Mn, Na, Th, and U, and slightly higher for ash, Be, Cd, Co, Cr, REEs, Sr, and V, at the 95% confidence level. Compared to channel samples, dump sample means are slightly lower in chalcophile elements (As, Cu, Fe, Ni, Pb, S, Sb, and V) and slightly higher in clay or heavy-mineral elements (Al, K, Mn, REEs, Th, Ti, U, and Y), but at the 95% confidence level, only As and Fe are different. Consistent abundances of clay or heavy-mineral elements in low-Br, high-S, high-ash benches that are relatively enriched in quartz and mire-to-levee species like Paralycopodites suggest trace elements are largely fluvial in origin. Factor analysis loadings and correlation coefficients between elements suggest that clays host most Al, Cr, K, Ti, and Th, significant Mn and V, and some Sc, U, Ba, and Ni. Heavy accessory minerals likely house most REEs and Y, lesser Sc, U, and Th, and minor Cr, Ni, and Ti. Pyrite appears to host As, some V and Ni, and perhaps some Cu, but Cu probably exists largely as chalcopyrite. Data suggest that organic debris houses most Be and some Ni and U, and that Pb and Sb occur as Pb-Sb sulfosalt(s) within organic matrix. Most Hg, and some Mn and Y, appear to be hosted by calcite, suggesting potential Hg remobilization from original pyrite, and Hg sorption by calcite, which may be important processes in abandoned coals. Most Co, Zn, Mo, and Cd, significant V and Ni, and some Mn probably occur in non-pyritic sulfides; Ba, Sr, and P are largely in crandallite-group phosphates. Selenium does not show organic or "clausthalite" affinities, but Se occurrence is otherwise unclear. Barium, Mn, Ni, Sc, U, and V, with strongly divided statistical affinities, likely occur subequally in multiple modes. For study area surface waters, highest levels of most trace elements occur in mine-adit or mine-dump drainage. Effluent flow rates strongly affect both acidity and trace element levels. Adit drainages where flow is only a trickle have the most acidic waters (pH 3.78-4.80) and highest trace element levels (up to two orders of magnitude higher than in non-mine site waters). Nonetheless, nearly all surface waters have low absolute concentrations of trace elements of environmental concern, and all waters sampled meet U.S. EPA primary drinking water standards and aquatic life criteria for all elements analyzed. Secondary drinking water standards are also met for all parameters except Al, pH, Fe, and Mn, but even in extreme cases (mine waters with pH as low as 3.78 and up to 1243 ppb Al, 6280 ppb Fe, and 721 ppb Mn, and non-mine dam-outflow waters with up to 18,400 ppb Fe and 1540 ppb Mn) downslope attenuation is apparently rapid, as down-drainage plateau-base streams show background levels for all these parameters. ?? 2005 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

USGS2005

Geochemistry and the understanding of ground-water systems

Geochemistry has contributed significantly to the understanding of ground-water systems over the last 50 years. Historic advances include development of the hydrochemical facies concept, application of equilibrium theory, investigation of redox processes, and radiocarbon dating. Other hydrochemical concepts, tools, and techniques have helped elucidate mechanisms of flow and transport in ground-water systems, and have helped unlock an archive of paleoenvironmental information. Hydrochemical and isotopic information can be used to interpret the origin and mode of ground-water recharge, refine estimates of time scales of recharge and ground-water flow, decipher reactive processes, provide paleohydrological information, and calibrate ground-water flow models. Progress needs to be made in obtaining representative samples. Improvements are needed in the interpretation of the information obtained, and in the construction and interpretation of numerical models utilizing hydrochemical data. The best approach will ensure an optimized iterative process between field data collection and analysis, interpretation, and the application of forward, inverse, and statistical modeling tools. Advances are anticipated from microbiological investigations, the characterization of natural organics, isotopic fingerprinting, applications of dissolved gas measurements, and the fields of reaction kinetics and coupled processes. A thermodynamic perspective is offered that could facilitate the comparison and understanding of the multiple physical, chemical, and biological processes affecting ground-water systems.

Hydrogeology Journal↗

USGS1996

Sulfur isotope geochemistry of ore and gangue minerals from the Silesian-Cracow Mississippi Valley-type ore district, Poland

Studies of the sulfur isotopic composition of ore and gangue minerals from the Silesian-Cracow Zn-Pb district were conducted to gain insights into processes that controlled the location and distribution of the ore deposits. Results of this study show that minerals from the Silesian-Cracow ore district have the largest range of sulfur isotope compositions in sulfides observed from any Mississippi Valley-type ore district in the world. The ??34S values for sulfide minerals range from +38 to -32 per mil for the entire paragenetic sequence but individual stages exhibit smaller ranges. There is a well developed correlation between the sulfur isotope composition and paragenetic stage of ore deposition. The first important ore stage contains mostly positive ??34S values, around 5 per mil. The second stage of ore formation are lower, with a median value of around -5 to -15 per mil, and with some values as low as -32 per mil. Late stage barite contains isotopically heavy sulfur around +32 per mil. The range in sulfur isotope compositions can be explained by contributions of sulfur from a variety of source rocks together with sulfur isotope fractionations produced by the reaction paths for sulfate reduction. Much of the variation in sulfur isotope compositions can be explained by bacterial reduction of sedimentary sulfate and disequilibrium reactions by intermediate-valency sulfur species, especially in the late-stage pyrite and sphalerite. Organic reduction of sulfate and thermal release of sulfur from coals in the Upper Silesian Coal Basin may have been important contributors to sulfur in the ore minerals. The sulfur isotopic data, ore mineral textures, and fluid inclusion data, are consistent with the hypothesis that fluid mixing was the dominant ore forming mechanism. The rather distinct lowering of ?? 34S values in sulfides from stage 2 to stage 3 is believed to reflect some fundamental change in the source of reduced sulfur and/or hydrology of the ore-forming environment. A change in the hydrology of the ore forming environment could be accomplished by extensional faulting that was coeval with ore formation. Late stage barite contains high values of ??34S which may reflect the final collapse of the hydrothermal system.

Prace - Panstwowego Instytutu Geologicznego↗

USGS2023

Groundwater availability, geochemistry, and flow pathways to public-supply wells in the Atlantic Coastal Plain and bedrock aquifers, Aiken County and part of Lexington County, South Carolina, 2015–2019

Between 2015 and 2019, the U.S. Geological Survey (USGS) studied concerns related to projected increases in demand for groundwater, in collaboration with municipal water providers and county managers within the study area, Aiken County and part of Lexington County, South Carolina. A three-dimensional (3D), numerical groundwater-flow model of the Atlantic Coastal Plain (ACP) aquifers, confining units, and the underlying bedrock aquifer in the study area was constructed using the USGS software program MODFLOW–NWT in conjunction with a groundwater-recharge model using the Soil-Water-Balance (SWB) model. Water budgets for dry (2012) and wet (2015) year conditions, future (2017–2065) groundwater-demand scenarios based on general circulation models (GCMs) of future climates, and future agricultural irrigation demands were simulated. Overall, the GCMs projected increased recharge rates. Simulation of projected increased demand on groundwater by agriculture irrigation indicated little drawdown in the study area. Groundwater-quality samples were collected from representative public-supply wells (PSWs) and analyzed in the field and laboratory. In general, the groundwater in the ACP aquifers is acidic, dilute, and oxic. Conversely, groundwater in the bedrock aquifer was of neutral pH, mineralized, and anoxic. Total-radium concentrations across all PSWs ranged from 0.55 to 6.69 picocuries per liter (pCi/L). Groundwater from some PSWs contained detectable but low concentrations of commonly and historically used volatile organic compounds, such as chloroform, methyl tert -butyl ether (MTBE), cis -1,2-dichloroethylene ( cis -1,2-DCE), 1,1-dichloroethane (1,1-DCA), and 1,1-dichloroethylene (1,1-DCE). The stable isotopes of groundwater sampled from all wells indicate the possibility that groundwater from the bedrock aquifer may discharge into the ACP. Finally, groundwater age-dating results and MODPATH simulations indicate recharge between the 1950s and 1980s for PSWs in the ACP and recharge between the 1940s and 1950s for PSWs in bedrock. Maximum groundwater-flow pathways ranged from 270 to 7,470 feet, with the longest simulated-flow pathway for wells pumped at higher rates.

South Carolina↗

USGS2003

Isotope geochemistry and chronology of offshore ground water beneath Indian River Bay, Delaware

Results of geophysical surveys in Indian River Bay, Delaware, indicate a complex pattern of salinity variation in subestuarine ground water. Fresh ground-water plumes up to about 20 meters thick extending hundreds of meters offshore are interspersed with saline ground water, with varying degrees of mixing along the salinity boundaries. It is possible that these features represent pathways for nutrient transport and interaction with estuarine surface water, but the geophysical data do not indicate rates of movement or nutrient sources and reactions. In the current study, samples of subestuarine ground water from temporary wells with short screens placed 3 to 22 meters below the sediment-water interface were analyzed chemically and isotopically to determine the origins, ages, transport pathways, and nutrient contents of the fresh and saline components. Apparent ground-water ages determined from chlorofluorocarbons (CFCs), sulfur hexafluoride (SF6), tritium (3H), and helium isotopes (3He and 4He) commonly were discordant, but nevertheless indicate that both fresh and saline ground waters ranged from a few years to at least 50 years in age. Tritium-helium (3H-3He) ages, tentatively judged to be most reliable, indicate that stratified offshore freshwater plumes originating in distant recharge areas on land were bounded by relatively young saline water that was recharged locally from the overlying estuary. Undenitrified and partially denitrified nitrate of agricultural or mixed origin was transported laterally beneath the estuary in oxic and suboxic fresh ground water. Ammonium produced by anaerobic degradation of organic matter in estuarine sediments was transported downward in suboxic saline ground water around the freshwater plumes. Many of the chemical and isotopic characteristics of the subestuarine ground waters are consistent with conservative mixing of the fresh (terrestrial) and saline (estuarine) endmember water types. These data indicate that freshwater plumes detected by geophysical surveys beneath Indian River Bay represent lateral continuations of the active surficial nitrate-contaminated freshwater flow systems originating on land, but they do not indicate directly the magnitude of fresh ground-water discharge or nutrient exchange with the estuary. There is evidence that some of the terrestrial ground-water nitrate is reduced before discharging directly beneath the estuary. Local estuarine sediment-derived ammonium in saline pore water may be a substantial benthic source of nitrogen in offshore areas of the estuary.

Delaware↗