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Using sediment chemical fractions and multivariate statistics on water to identify sources, mobility, and bioavailability of aluminum in the Florida River near Durango, Colorado

The Florida River in southwestern Colorado, USA, flows through the Southern Ute Reservation and is a cultural and water resource to Tribal and non-Tribal communities. High concentrations of total Al, up to 16 400 µg l –1 , have been detected in the Florida River. Elevated Al concentrations in water may affect aquatic organisms’ ability to regulate ions and inhibit respiratory functions. Water chemistry collected during three sampling events in 2022 from the Florida River and two of its tributaries are used here to better understand the spatial distribution, seasonality, and sources of Al concentrations in the Florida River. Streambed sediment and rock chemistry is also used to infer geologic sources of Al in the watershed. A five-stage sequential extraction was performed on streambed sediment and rock samples to help determine Al transport processes. We assessed relations between major and trace elements in water using a principal component analysis, finding that high Al concentrations in the Florida River (>3500 µg l –1 total Al) are caused by the erosion of Al-laden sediments. We used a stepwise multiple linear regression to investigate the relationship between land use and Al concentrations. Land use did not reliably predict Al concentration, though increased streamflow connected to reservoir releases – particularly in the Salt Creek tributary – were found to contribute Al to the Florida River during the irrigation season. In this study, we demonstrate that successful metal source appropriation may be achieved through limited field sampling when performed with sufficient water chemistry analysis, sequential chemical extraction of stream sediments, and statistical and land-use analysis.

Colorado

Characterization of arsenic species in microbial mats from an inactive gold mine

Filamentous cyanobacterial mats and Fe oxyhydroxide-rich bacterial mats collected near an inactive gold mine in California are enriched in arsenic (As) approximately 1000-fold relative to the waters in contact with them. The predominant organism in the cyanobacterial mat could not be identified using morphological characteristics, but the unique morphology of the sheath-forming β protobacterium Leptothrix ochracea was used to identify this species in Fe oxyhydroxide mat samples from several sites near the gold mine. Leptothrix sheaths commonly exceed 10 μm in length and have an average diameter of 1 μm . The Fe-oxyhydroxide mats are dominated by L. ochracea sheaths, but use of fluorescently tagged genetic stains reveals the presence of sheathless bacteria that presumably also promote the formation of Fe oxyhydroxide. X-ray absorption fine structure (XAFS) spectroscopy was used to identify As species in these microbial mats. Mat-associated As is predominantly As(V), even when As(III) is the primary dissolved species in contact with the mats. The species of As(V) associated with the cyanobacterial mat could not be conclusively identified; however, it is not associated with Fe oxyhydroxide or other minerals, based on comparison to XAFS spectra of As adsorbed to various substrates. In addition, the cyanobacterial mat XAFS spectrum is different from that of aqueous As(V), suggesting that As(V) in the mat lacks some or all of the coordinating water molecules present in aqueous solution. We hypothesize that As is associated with the exopolysaccharide (EPS) matrix secreted by the cyanobacteria. In Leptothrix -dominated Fe-oxyhydroxide bacterial mats, XAFS analysis clearly indicates that As(V) is associated with the Fe oxyhydroxide as an adsorbed and/or coprecipitated complex.

California

Spectral reflectance properties (0.4-2.5 μm) of secondary Fe-oxide, Fe-hydroxide, and Fe-sulphate-hydrate minerals associated with sulphide-bearing mine wastes

Diffuse reflectance spectra of 15 mineral species commonly associated with sulphide-bearing mine wastes show diagnostic absorption bands related to electronic processes involving ferric and/or ferrous iron, and to vibrational processes involving water and hydroxyl. Many of these absorption bands are relatively broad and overlapping; however, spectral analysis methods, including continuum removal and derivative analysis, permit most of the minerals to be distinguished. Key spectral differences between the minerals are illustrated in a series of plots showing major absorption band centres and other spectral feature positions. Because secondary iron minerals are sensitive indicators of pH, Eh, relative humidity, and other environmental conditions, spectral mapping of mineral distributions promises to have important application to mine waste remediation studies.

Geochemistry: Exploration, Environment, Analysis

Natural versus anthropogenic dispersion of metals to the environment in the Wulik River area, western Brooks Range, northern Alaska

Zinc-lead-silver mineral deposits in the Wulik River region, Alaska, contain an enormous accumulation of Zn. In addition to the giant deposits at Red Dog, at least nine other deposits are known. Natural weathering of these deposits has dispersed metals over a wide region over a long period of time (c. 10 000 years) through transport by stream and groundwater, stream sediments, formation of soils, and perhaps wind-blown atmospheric deposition from weathering of naturally enriched Pb-Zn surface deposits. Anthropogenic input also contributes metals to the environment. Mining of the Red Dog deposit, which began in 1989, produces fine-grained galena and sphalerite concentrates that are transported from the mine site by truck to a storage port facility. Wind-blown dispersion of concentrate dust along the road and around the port facility has been a source of local metal-rich surficial materials. Geochemical and mineralogical characteristics provide a means of distinguishing the natural versus anthropogenic metal sources. Soils over deposits have patterns of increasing metal contents with depth and proximity to the metal-bearing source, whereas ore concentrate dust is localized at the surface. The acidity produced by weathering of the sulphide deposits creates an environment in which elements such as Se and Mo are stable whereas Ca is not. Consequently, high Mo (up to 29 ppm) and Se (up to 17 ppm) and low Ca (<0.4%) concentrations characterize surficial materials near natural deposits. Acidic conditions also yield high Pb-Zn ratios (up to 70) because sphalerite is preferentially dissolved and Zn is mobilized during chemical weathering. In natural materials, secondary jarosite and anglesite are developed, and minor galena is etched and rounded due to a history of chemical and mechanical weathering. In contrast, dust-bearing samples have Pb/Zn ratios that are 0.4 or less, Ca contents are higher (0.2 to 3.6%), and Mo (<10 ppm) and Se (not detected) concentrations are low. Furthermore, galena and sphalerite grains are angular and secondary minerals are lacking. ?? 2007 AAG/Geological Society of London.

Geochemistry: Exploration, Environment, Analysis

Mineral sources and transport pathways for arsenic release in a coastal watershed, USA

Metasedimentary bedrock of coastal Maine contains a diverse suite of As-bearing minerals that act as significant sources of elements found in ground and surface waters in the region. Arsenic sources in the Penobscot Formation include, in order of decreasing As content by weight: l&ouml;llingite and realgar ( c. 70%), arsenopyrite, cobaltite, glaucodot, and gersdorffite (in the range of 34&ndash;45%), arsenian pyrite (<4%), and pyrrhotite (<0.15%). In the Penobscot Formation, the relative stability of primary As-bearing minerals follows a pattern where the most commonly observed highly altered minerals are pyrrhotite, realgar, niccolite, l&ouml;llingite > glaucodot, arsenopyrite-cobaltian > arsenopyrite, cobaltite, gersdorffite, fine-grained pyrite, Ni-pyrite > coarse-grained pyrite. Reactions illustrate that oxidation of Fe-As disulphide group and As-sulphide minerals is the primary release process for As. Liberation of As by carbonation of realgar and orpiment in contact with high-pH groundwaters may contribute locally to elevated contents of As in groundwater, especially where As is decoupled from Fe. Released metals are sequestered in secondary minerals by sorption or by incorporation in crystal structures. Secondary minerals acting as intermediate As reservoirs include claudetite ( c. 75%), orpiment (61%), scorodite ( c. 45%), secondary arsenopyrite ( c. 46%), goethite (<4490&thinsp;ppm), natrojarosite (<42&thinsp;ppm), rosenite, melanterite, ferrihydrite, and Mn-hydroxide coatings. Some soils also contain Fe-Co-Ni-arsenate, Ca-arsenate, and carbonate minerals. Reductive dissolution of Fe-oxide minerals may govern the ultimate release of iron and arsenic &ndash; especially As(V) &ndash; to groundwater; however, dissolution of claudetite (arsenic trioxide) may directly contribute As(III). Processes thought to explain the release of As from minerals in bedrock include oxidation of arsenian pyrite or arsenopyrite, or carbonation of As-sulphides, and most models based on these generally rely on discrete minerals or on a fairly limited series of minerals. In contrast, in the Penobscot Formation and other metasedimentary rocks of coastal Maine, oxidation of As-bearing Fe-cobalt-nickel-sulphide minerals, dissolution (by reduction) of As-bearing secondary As and Fe hydroxide and sulphate minerals, carbonation and/or oxidation of As-sulphide minerals, and desorption of As from Fe-hydroxide mineral surfaces are all thought to be involved. All of these processes contribute to the occurrence of As in groundwaters in coastal Maine, as a result of variability in composition and in stability of the As source minerals. Arsenic contents of soils and groundwater thus reflect the predominant influence and integration of a spectrum of primary mineral reservoirs (instead of single or unique mineral reservoirs). Cycling of As through metasedimentary bedrock aquifers may therefore depend on consecutive stages of carbonation, oxidation and reductive dissolution of primary and secondary As host minerals.

Maine

Anthropogenic and natural lead isotopes in Fe-hydroxides and Fe-sulphates in a watershed associated with arsenic-enriched groundwater, Maine, USA

A survey of the natural and anthropogenic sources of lead contributing to secondary minerals in sulphidic schists associated with arsenic-enriched groundwater in Coastal Maine shows that the most likely source is natural Pb, particularly from coexisting sulphide minerals. The secondary minerals also reflect notable contributions from anthropogenic Pb. The Pb isotopes establish pathways by which Pb, and by inference As, could have been transported from As-bearing minerals (arsenian pyrite, arsenopyrite, lollingite, orpiment, arsenic oxide and others), via sulphide oxidation or carbonation reactions into multiple generations of secondary minerals (goethite, hematite, jarosite, natrojarosite and others). Lead isotopic compositions of the sulphides and secondary minerals determined by thermal ionization mass spectrometry ( n =53) range widely. Lead and As contents of the sulphides and secondary minerals overlap, and are generally positively correlated. Pyrite, the dominant sulphide in sulphidic schists associated with As-enriched groundwater in Coastal Maine, has values of 206 Pb/ 204 Pb from 18.186 to 18.391, 207 Pb/ 204 Pb from 15.617 to 15.657, 208 Pb/ 204 Pb from 38.052 to 38.210, 206 Pb/ 207 Pb from c . 1.1625 to 1.1760 and 208 Pb/ 207 Pb from c . 2.4276 to 2.4394. Mixtures of Fe-hydroxide and oxide minerals (predominantly goethite and hematite) and secondary Fe-sulphate minerals (jarosite, natrojarosite, rozenite and melanterite) in the sulphidic schists have overlapping but generally higher values of 206 Pb/ 204 Pb from 18.495 to 19.747 (one sample at 21.495), 207 Pb/ 204 Pb from 15.595 to 15.722 (one sample at 15.839), 208 Pb/ 204 Pb from 38.186 to 39.162, 206 Pb/ 207 Pb from c. 1.1860 to 1.2575 (one sample at 1.3855) and 208 Pb/ 207 Pb from c . 2.4441 to 2.4865 than the sulphides. Sulphides from Zn-Pb metal mines are somewhat less radiogenic than sulphides from the schists. Other sulphides (mostly pyrite) associated with pegmatites and granitic rocks are heterogeneous and more radiogenic than the pyrite-rich sulphidic schists. Sulphides from other regional bedrock units also have heterogeneous isotope values. Lead isotopic compositions of the sulphides from the sulphidic schists and coexisting Fe-oxides and Fe-sulphates produced by weathering and alteration overlap, but the secondary minerals extend toward more radiogenic values that broadly indicate the addition of Pb from anthropogenic origin. As a component of Pb from extensively used arsenical pesticides may also be present in the secondary minerals, the range in Pb isotope values is consistent with multiple sources: natural Pb from the schists and anthropogenic Pb (industrial and possibly from agricultural activities). Contributions from past mining activities or from other bedrock sources are not implicated.

Maine

Low-density geochemical mapping and the robustness of geochemical patterns

Geochemical mapping of entire continents and, ultimately, the world is still a challenge for applied geochemists. At sample densities traditionally used for geochemical exploration (1 site per 1-25 km2), geochemical mapping of whole continents is logistically extremely demanding and tremendously expensive. The first low-density geochemical surveys (1 site per 200 km2) were carried out during the late 1960s in Africa. Later surveys conducted in various parts of the world had sample densities ranging from 1 site per 300 km2 to 1 site per 18 000 km2. Although these surveys were deemed successful by the investigators in defining variations in background element content on a regional scale, the scientific community was sceptical that low-density geochemical mapping was possible and would provide useful information. The main area of criticism centred around the concern that at such low sample densities the resulting maps would not be robust, i.e. if the same area were resampled and remapped, different geochemical patterns would emerge. Different examples from the USA, Europe, China and Africa demonstrate that low-density geochemical mapping will result in stable and robust geochemical patterns at the continental scale. Such maps are urgently needed for a wide variety of applications. ?? 2008 AAG/ Geological Society of London.

Geochemistry: Exploration, Environment, Analysis

Metal contamination and post-remediation recovery in the Boulder River watershed, Jefferson County, Montana

The legacy of acid mine drainage and toxic trace metals left in streams by historical mining is being addressed by many important yet costly remediation efforts. Monitoring of environmental conditions frequently is not performed but is essential to evaluate remediation effectiveness, determine whether clean-up goals have been met, and assess which remediation strategies are most effective. Extensive pre- and post-remediation data for water and sediment quality for the Boulder River watershed in southwestern Montana provide an unusual opportunity to demonstrate the importance of monitoring. The most extensive restoration in the watershed occurred at the Comet mine on High Ore Creek and resulted in the most dramatic improvement in aquatic habitat. Removal of contaminated sediment and tailings, and stream-channel reconstruction reduced Cd and Zn concentrations in water such that fish are now present, and reduced metal concentrations in streambed sediment by a factor of c. 10, the largest improvement in the district. Waste removals at the Buckeye/Enterprise and Bullion mine sites produced limited or no improvement in water and sediment quality, and acidic drainage from mine adits continues to degrade stream aquatic habitat. Recontouring of hillslopes that had funnelled runoff into the workings of the Crystal mine substantially reduced metal concentrations in Uncle Sam Gulch, but did not eliminate all of the acidic adit drainage. Lead isotopic evidence suggests that the Crystal mine rather than the Comet mine is now the largest source of metals in streambed sediment of the Boulder River. The completed removal actions prevent additional contaminants from entering the stream, but it may take many years for erosional processes to diminish the effects of contaminated sediment already in streams. Although significant strides have been made, additional efforts to seal draining adits or treat the adit effluent at the Bullion and Crystal mines would need to be completed to achieve the desired restoration.

Montana

Multiple applications of the U.S. EPA 1312 leach procedure to mine waste from the Animas watershed, SW Colorado

Eleven acid-sulphate and quartz-sericite-pyrite altered mine waste samples from the Animas River watershed in SW Colorado were subjected to a series of 5 to 6 successive leaches using the US EPA 1312 leach protocol to evaluate the transport of metals and loss of acidity from mine wastes as a function of time. Multi-acid digestion ICP-AES analyses, X-ray diffraction (XRD) mineral identification, total sulphur, and net acid potential (NAP) determinations were performed on the initial starting materials. Multiple leaching steps generally showed a ‘flushing' effect, whereby elements loosely bound, presumably as water-soluble salts, were removed. Aluminum, Cd, Fe, Mg, Mn, Sr, Zn, and S showed decreasing concentration trends, whereas Cu concentrations showed initially decreasing trends, followed by increasing trends in later steps. Concentrations of Zn in the first leach step were independent of whole-sample Zn content. Lead and Ba concentrations consistently increased with each step, indicating that anglesite (PbSO 4 ) and barite (BaSO 4 ), respectively, were dissolving in successive leach steps. Comparison of Fe content with NAP resulted in a modest correlation. However, using the S analyses and XRD identification of sulphide minerals to apportion S amongst enargite, barite, anglesite/galena, and sphalerite, and assigning the remaining S to pyrite, provided a useful correlation between estimated pyrite content and NAP. Whole-sample mass loss correlated well with NAP, but individual elements' behaviors varied between positive correlation (e.g. Al, Fe, Mg), no apparent correlation (Ca, Cd, Pb, Zn), and negative correlation (Cu). Comparison of the summed titrated acidities of the leachates with the whole-sample NAP values yielded an estimate of the fraction of NAP consumed, and led to an estimate of the time it would take to consume the sample acidity by weathering. We estimate, on the basis of these experiments, the acidity in the upper 30 cm would be consumed in 200–1000 years. In addition, calculations suggest that the acidity would be depleted before the complete store of the metals Cu-Cd-Zn in these mine wastes would be released to the environment.

Colorado

Porphyry Cu indicator minerals in till as an exploration tool: Example from the giant Pebble porphyry Cu-Au-Mo deposit, Alaska, USA

Porphyry Cu indicator minerals are mineral species in clastic sediments that indicate the presence of mineralization and hydrothermal alteration associated with porphyry Cu and associated skarn deposits. Porphyry Cu indicator minerals recovered from shallow till samples near the giant Pebble Cu-Au-Mo porphyry deposit in SW Alaska, USA, include apatite, andradite garnet, Mn-epidote, visible gold, jarosite, pyrite, and cinnabar. Sulphide minerals other than pyrite are absent from till, most likely due to the oxidation of the till. The distribution of till samples with abundant apatite and cinnabar suggest sources other than the Pebble deposit. With three exceptions, all till samples up-ice of the Pebble deposit contain <10 grains/10kg of garnet (0.25-0.5 mm). Samples in the immediate vicinity of the Pebble deposit contain 10-20 grains, whereas samples with the most grains (>40grains/10kg) are in close proximity to smaller porphyry and skarn occurrences in the region. The distribution of Mn-epidote closely mimics the distribution of garnet in the till samples and further supports the interpretation that these minerals most likely reflect skarns associated with the porphyry deposits. All but two till samples, including those up-ice from the deposit, contain some gold grains. However, tills immediately west and down-ice of Pebble contain more abundant gold grains, and the overall number of grains decreases in the down-ice direction. Furthermore, all samples in the immediate vicinity of Pebble contain more than 65% pristine and modified grains compared to mostly re-shaped grains in distal samples. The pristine gold in till reflects short transport distances and/or liberation of gold during in-situ weathering of transported chalcopyrite grains. Jarosite is also abundant (1-2 500 grains/10kg) in samples adjacent to and up to 7 km down-ice from the deposit. Most jarosite grains are rounded and preliminary Ar/Ar dates suggest the jarosite formed prior to glaciation and it implies that a supergene cap existed over Pebble West. Assuming this interpretation is accurate, it suggests a shallow level of erosion of the Pebble deposit by glacial processes. Overall the results of this study indicate that porphyry Cu indicator minerals in till samples may be useful in the exploration for porphyry deposits in SW Alaska.

Alaska

Anthropogenic vs. natural pollution: An environmental study of an industrial site under remediation (Naples, Italy)

Heavy metal concentrations and Pb isotopic composition were determined in the soils, slags, scums and landfill materials from a shut down industrial (brownfield) site. This was the second largest integrated steelworks in Italy, and is now under remediation by a Government project. It is located in the outskirts of Napoli on the Bagnoli-Fuorigrotta plain (BFP), which is part of the Campi Flegrei (CF) volcanic caldera, where many spas and geothermal springs occur. The purpose of this work is to distinguish the natural (geogenic) component, originated by hydrothermal activity, from anthropogenic contamination owing to industrial activity. 'In-situ sediments' (soils), slags, scums and landfill materials from 20 drill-cores were selected from a network of 197 drills carried out on a 100 ?? 100 m grid, covering the entire brownfield site. In general, heavy metal enrichments in the upper 3 m of the cores strongly suggest mixing between natural (geogenic) and anthropogenic components. Pb isotopic data are suggestive of three potential end members, and confirm the existence of a strong natural component in addition to contamination from anthropogenic activities. The slags, scums and landfill materials have been proved, through mineralogy and leachate experiments, to be geochemically stable; this shows that metal pollutants are not bio-available and, hence, do not pose a risk to future developments on this site. The natural contribution of hydrothermal fluids to soil pollution, in addition to the non-bio-availability of metal pollutants from industrial materials, indicate that heavy metal remediation of soils in this area would be of little use. Continuous discharge from mineralized hydrothermal solutions would cancel out any remediation effort.

Geochemistry: Exploration, Environment, Analysis

Mercury methylation at mercury mines in the Humboldt River Basin, Nevada, USA

Total Hg and methylmercury concentrations were measured in mine-waste calcines (retorted ore), sediment, and water samples collected in and around abandoned mercury mines in western Nevada to evaluate Hg methylation at the mines and in the Humboldt River Basin. Mine-waste calcines contain total Hg concentrations as high as 14 000 ??g g-1. Stream-sediment samples collected within 1 km of the mercury mines contain total Hg concentrations as high as 170 ??g g-1, whereas stream sediments collected at a distance >5 km from the mines, and those collected from the Humboldt River and regional baseline sites, contain total Hg concentrations <0.5 ??g g-1. Similarly, methylmercury concentrations in mine-waste calcines are locally as high as 96 ng g-1, but methylmercury contents in stream sediments collected downstream from the mines and from the Humboldt River are lower, ranging from <0.05 to 0.95 ng g-1. Stream-water samples collected downstream from two mines studied contain total Hg concentrations ranging from 6 to 2000 ng 1-1, whereas total Hg in Humboldt River water was generally lower, ranging from 2.1 to 9.0 ng 1-1. Methylmercury concentrations in the Humboldt River water were the lowest in this study (<0.02-0.27 ng 1-1). Although total Hg and methylmercury concentrations are locally high in mine-waste calcines, there is significant dilution of Hg and there is also lower Hg methylation down gradient from the mines, especially in the sediments and water collected from the Humboldt River, which is >8 km from the nearest mercury mines. Our data indicate little transference of Hg and methylmercury from the sediment to the water column due to the lack of mine runoff in this desert climate.

Geochemistry: Exploration, Environment, Analysis

Mercury contamination from historic mining in water and sediment, Guadalupe River and San Francisco Bay, California

The New Almaden mercury mines in California (USA), which collectively represent the largest historic producers of mercury in North America, are a persistent source of mercury contamination to the San Francisco Bay estuary. An estimate based on total mercury concentration (HgTOT) and provisional stream flow data measured at a gauging station in the Guadalupe River during base flow conditions yields a base flow flux of 30 g of mercury for the month of October 2000. In contrast to this base flow estimate, one 2-day rain event in October 2000 resulted in a flux of 22 g of mercury past this site. An estimate of mercury transport from the entire Guadalupe River watershed based on a sediment transport model and our measured suspended particulate HgTOT (0.5-4 ??g g-1) results in a total of 4-30 kg year-1 transported to the southern reach of the estuary. Sediments in the southern reach have lower HgTOT (most ??? 0.4 ??g g-1 dry wt) and monomethyl-mercury (MMHg, c. 1 ng g-1 dry wt) concentrations than those in the Guadalupe River (HgTOT, 0.41-33 ??g g-1 dry wt; MMHg, 1-10 ng g-1 dry wt). Because the most elevated methylmercury concentrations (8-12 ng g-1 dry wt) were found in sediments deposited immediately upstream of hydraulic structures (e.g. diversion dams and weirs) within the river, it is proposed that such physical structures may represent important zones of MMHg production and fluxes to San Francisco Bay.

Geochemistry: Exploration, Environment, Analysis

Water-quality trends for a stream draining the Southern Anthracite Field, Pennsylvania

Stream flow, chemical and biological data for the northern part of Swatara Creek, which drains a 112 km 2 area in the Southern Anthracite Field of eastern Pennsylvania, indicate progressive improvement in water quality since 1959, after which most mines in the watershed had been flooded. Drainage from the flooded mines contributes substantially to base flow in Swatara Creek. Beginning in 1995, a variety of treatment systems and surface reclamation were implemented at some of the abandoned mines. At Ravine, Pa., immediately downstream of the mined area, median SO 4 concentration declined from about 150 mg l −1 in 1959 to 75 mg l −1 in 1999 while pH increased from acidic to near-neutral values (medians: c. pH 4 before 1975; c. pH 6 after 1975). Fish populations rebounded from non-existent during 1959–1990 to 21 species identified in 1999. Nevertheless, recent monitoring indicates (1) episodic acidification and elevated concentrations and transport of Fe, Al, Mn, and trace metals during storm flow; (2) elevated concentrations of Fe, Mn, Co, Cu, Pb, Ni, and Zn in streambed sediments relative to unmined areas and to toxicity guidelines for aquatic invertebrates and fish; and (3) elevated concentrations of metals in fish tissue, notably Zn. The metals are ubiquitous in the fine fraction (<0.063 mm) of bed sediment in mining-affected tributaries and the main stem of Swatara Creek. As a result of scour and transport of streambed deposits, concentrations of suspended solids and total metals in the water column are correlated, and those for storm flow typically exceed base flow. Nevertheless, the metals concentrations are poorly correlated with stream flow because concentrations of suspended solids and total metals typically peak prior to peak stream stage. In contrast, SO 4 , specific conductance and pH are inversely correlated with stream flow as a result of dilution of poorly buffered stream water with weakly acidic storm runoff derived mainly from low-pH rainfall. Declines in pH to values approaching 5.0 during storm flow events or declines in redox potential during burial of sediment could result in the remobilization of metals associated with suspended solids and streambed deposits.

Pennsylvania

Soil geochemical survey of abandoned mining sites in the Eastern-Central Peloritani Mountains, Sicily, Italy

This investigation focused on topsoils ( n = 122) and vertical profiles ( n = 6) distributed over an area of 250 km 2 in the eastern-central Peloritani Mountains, northeastern Sicily. Georeferenced concentration of 53 elements (including potentially harmful ones), determined by ICP-MS after an aqua regia leach, were used to produce geochemical maps by means of a GIS-aided spatial interpolation process. Results show that there are two distinct areas: the larger, located between the Fiumendinisi, Budali and Ali villages, and the other between C. Postlioni and Femmina Morta, which contain anomalous As (up to 727 mg/kg), Sb (up to 60 mg/kg), Ag (up to 1 mg/kg) and Au (up to 0.1 mg/kg) concentrations. Most of the investigated areas have high contamination levels for As, Zn, Sb, and Pb that exceed the threshold values (As = 20 mg/kg, Zn = 150 mg/kg, Sb = 10 mg/kg and Pb = 100 mg/kg) established for soils by the Italian Environmental Law ( Decreto Legislativo 2006 , number 152). The isotopic ratios of 206 Pb/ 207 Pb and 208 Pb/ 207 Pb have been measured in selected soils on both leaches [using 1M HNO 3 –1.75M HCl (50:50)] and residues thereof. Soil leach reflects possible anthropogenic contamination, whereas soil residues indicate geogenic contributions. Results suggest that most of contamination in the soils is related to the presence of sulphide and sulphosalt rock-forming minerals in the surveyed area. The soil fraction contains a Pb value >1600 mg/kg and has ratios of 1.1695 for 206 Pb/ 207 Pb and 2.4606 for 208 Pb/ 207 Pb. Only one soil leach isotopic composition could reflect possible anthropogenic contamination. The correlation among As, Zn, Pb contents v. Pb isotopic signatures of 206 Pb/ 207 Pb indicates that surface and deep soils collected from profiles are dominated by geogenic compositions.

Peloritani Mountains, Sicily

Arsenic and mercury contamination related to historical goldmining in the Sierra Nevada, California

Arsenic (As) is a naturally occurring constituent in low-sulphide gold-quartz vein deposits, the dominant deposit type for lode mines in the Sierra Nevada Foothills (SNFH) gold (Au) province of California. Concentrations of naturally occurring mercury (Hg) in the SNFH Au province are low, but extensive use and loss of elemental Hg during amalgamation processing of ore from lode and placer Au deposits led to widespread contamination of Hg in the Sierra Nevada foothills and downstream areas, such as the Sacramento–San Joaquin Delta and San Francisco Bay. This review paper provides an overview of As and Hg contamination related to historical Au mining in the Sierra Nevada of California. It summarizes the geology, mineralogy, and geochemistry of the Au deposits, and provides information on specific areas where detailed studies have been done in association with past, ongoing, and planned remediation activities related to the environmental As and Hg contamination. Arsenic is a naturally occurring constituent in low-sulphide Au-quartz vein deposits, the dominant deposit type for lode mines in the Sierra Nevada Foothills (SNFH) Au province ( Ashley 2002 ). Because of elevated concentrations of As in accessory iron-sulphide minerals including arsenopyrite (FeAsS) and arsenian pyrite (Fe(S,As) 2 ), As is commonly a contaminant of concern in lode Au mine waste, including waste rock and mill tailings. The principal pathways of human As exposure from mine waste include ingestion of soil or drinking water, and inhalation of dust in contaminated areas ( Mitchell 2014 ). Concentrations of naturally occurring Hg in the SNFH Au province are low, but extensive use and loss of elemental Hg during amalgamation processing of ore from lode and placer Au deposits ( Churchill 2000 ) led to widespread contamination of Hg in the Sierra Nevada foothills and downstream areas, such as the Sacramento–San Joaquin Delta and San Francisco Bay ( Alpers et al. 2005 a ). Conversion of Hg to monomethylmercury (MeHg) by sulphate-reducing and iron-reducing microbes facilitates its bioaccumulation ( Wiener et al. 2003 ). The human Hg exposure pathway of main concern is ingestion of MeHg from sport (non-commercial) fish, especially higher trophic levels such as bass species ( Davis et al. 2008 ). Wildlife exposure to MeHg is also a concern because of chronic and reproductive effects, for example in fish-eating and invertebrate-foraging birds (e.g. Wiener et al. 2003 ; Eagles-Smith et al. 2009 ; Ackerman et al. 2016 ).

California

Stream sediment geochemistry in mineral exploration: A review of fine-fraction, clay-fraction, bulk leach gold, heavy mineral concentrate and indicator mineral chemistry

Stream sediment surveys support early-stage reconnaissance mineral exploration and regional assessment programmes, enhanced by recent improvements in analytical method detection limits, continuously improving mineral chemistry, and new approaches to the interpretation of geochemical data. Sediment surveys may be used to predict catchment basin lithology, mineralization type based on pathfinder geochemistry, and geological features based on indicator mineral chemistry. Sediment surveys that target a finer-fraction sediment sample led to the discovery of the La Colosa gold deposit, Colombia. The Batu Hijau porphyry Cu–Au deposit in Indonesia was discovered based on an anomalous clay-sized fraction sample 12 km downstream. In an arid region with poorly developed drainages and minor topographic relief, the Ag-base-metal Navidad District in Argentina was discovered with clay-fraction sediment geochemistry. Heavy mineral concentrate (HMC) sediment surveys that include mineral chemistry determinations have led to global diamond discoveries. HMC surveys contributed to discovery of the Ring of Fire Ni–Cu–PGE and chromite district, Ontario, Canada. Discoveries and geochemical mapping can assist advancement of the application of stream sediment geochemistry in those global areas for which lithologies and deposits are exposed. Stream sediment surveys continue to be one of the most cost-effective geochemical methods for covering large areas for mineral exploration.

Geochemistry: Exploration, Environment, Analysis

Anthropogenic influence on groundwater geochemistry in Horn Creek Watershed near the Orphan Mine in Grand Canyon National Park, Arizona, USA

Breccia pipe deposits of the Grand Canyon region contain ore grade copper and uranium. Horn Creek is located near the Orphan Mine mineralized breccia pipe deposit and groundwater emerging from the bedrock in the headwaters of Horn Creek has the highest uranium concentrations in the region. Uranium decreases an order of magnitude between the groundwater at the top of the watershed and the groundwater emerging from the alluvial material lower in the watershed. Horn Creek water has low sulfur and uranium isotopic ratios which may suggest interaction with sulfide and uranium minerals found in mineralized breccia pipe deposits. Per- and polyfluoroalkyl substances (PFBA and PFBS) were found in low concentrations in groundwater from the bedrock and may be related to mining process materials or other anthropogenic activities. PHREEQC modeling suggests that water that is elevated in uranium emerging from the bedrock in the upper watershed may mix with other groundwater and atmospheric precipitation infiltrated into the alluvial material in the lower watershed. Tritium is elevated in Horn Creek groundwaters suggesting a component of modern water, some of which may have interacted with Orphan Mine workings. Additional studies could build on this understanding of chemistry changes in waters of Horn Creek to provide more direct evidence of contribution of water moving through the Orphan Mine.

Arizona