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USGS2003

Trends in chemical concentration in sediment cores from three lakes in New Jersey and one lake on Long Island, New York

Sediment cores were extracted from three lakes in northeastern New Jersey and one lake on western Long Island, New York, as part of the U.S. Geological Survey National Water-Quality Assessment Program. Sediment layers were dated by use of cesium-137 (137Cs), copper, lead, or dichlorodiphenyl-trichloroethane (DDT) profiles. Sediment layers were analyzed for seven selected trace elements, including arsenic, cadmium, chromium, lead, mercury, nickel, and zinc, and five hydrophobic organochlorine compounds, including chlordane, dieldrin, total DDT, total polychlorinated biphenyls (PCBs), and total polycyclic aromatic hydrocarbons (PAHs). All seven trace elements were detected throughout the cores from all four lakes. Concentrations of all elements, except arsenic, were elevated in the three cores from lakes within urbanized watersheds (Packanack Lake, Orange Reservoir, and Newbridge Pond) relative to the concentrations in the lake core collected below the largely forested, reference watershed (Clyde Potts Reservoir). Results of trend analyses indicate that concentrations of all trace elements, with the exception of arsenic and lead, were relatively constant throughout the core from the minimally urbanized Clyde Potts Reservoir. In urban lakes, significant upward trends in concentrations from deeper to shallower sediments were observed either to peak concentrations or throughout the core for all elements, with the exception of chromium at all lakes and arsenic and nickel at Orange Reservoir. This finding indicates that changes in population and land use in the urbanized watersheds over the period of sedimentary record have contributed to upward trends in trace-element concentrations. Although downward trends in concentrations were observed for some trace elements in the years after their concentrations peaked, concentrations of all trace elements in urban lake cores were higher in the most recently deposited sediments than at the base of each respective core. Lead concentrations over time were highly correlated with the population in the vicinity of the lake until the concentration peak in sediment deposited in the mid-1970’s. Concentrations of lead in lake sediment appear to be closely related to the use of leaded gasoline because lead concentrations generally decreased after the use of leaded gasoline was phased-out in the mid-1970’s. Zinc concentrations were highly correlated with population over the entire length of the core. In general, zinc concentrations increased in the three urbanized watersheds, probably in response to increasing population and vehicular use. This trend was not evident at Clyde Potts Reservoir, however, where vehicular traffic in the watershed is minimal. Detectable concentrations of chlordane, total DDT, and total PCBs were present in cores from all lakes; however, dieldrin was detected only in the Newbridge Pond and Packanack Lake cores. Concentrations generally were higher in cores from the urbanized Newbridge Pond and Orange Reservoir watersheds than in those from the minimally urbanized Clyde Potts Reservoir watershed. With the exception of chlordane in the Clyde Potts and Orange Reservoir cores, concentrations of the four organochlorine compounds had significant downward trends from peak concentrations to recently deposited sediment or non-significant trends throughout the core. On the basis of these findings and as a result of regulatory actions prohibiting the production and use of these compounds, downward trends in sedimentary concentrations are expected to continue; however, the persistence of these compounds indicates that a substantial amount of time may be required to purge them from the watersheds. Concentrations of PAHs in sediment generally increased with population growth and urbanization, probably as a result of increased fossil-fuel combustion (gasoline and home-heating fuels and other uses (roads and parking lots paved with asphalt) associated with increased urban development and vehicular traffic. This finding is supported by low concentrations of PAHs in Packanack Lake sediments in the 1930’s, before the watershed was urbanized and when automobiles were comparatively rare. As vehicular use and urbanization increase in these watersheds, the general increase of PAH concentrations in lake sediments can be expected to continue. Data from this study indicate that changes in population, land use, and chemical use in the urbanized watersheds over the period of sedimentary record have contributed to upward trends in concentrations of trace elements and hydrophobic organic compounds. Although downward trends were observed for some constituents in the years after their concentrations peaked, concentrations of most constituents in urban lake cores were higher in the most recently deposited sediments than at the base of each respective core and in the reference lake cores. Similar trends in concentrations of these constituents have been observed in sediment cores from other urban lakes across the United States.

New Jersey, New York↗

USGS2022

Potential for critical mineral deposits in Maine, USA

An analysis of the potential for deposits of critical minerals and elements in Maine presented here includes data and discussions for antimony, beryllium, cesium, chromium, cobalt, graphite, lithium, manganese, niobium, platinum group elements, rhenium, rare earth elements, tin, tantalum, tellurium, titanium, uranium, vanadium, tungsten, and zirconium. Deposits are divided into two groups based on geological settings and common ore-deposit terminology. One group consists of known deposits (sediment-hosted manganese, volcanogenic massive sulphide, porphyry copper-molybdenum, mafic- and ultramafic-hosted nickel-copper [-cobalt-platinum group elements], pegmatitic lithium-cesium-tantalum) that are in most cases relatively large, well-documented, and have been explored extensively in the past. The second, and much larger group of different minerals and elements, comprises small deposits, prospects, and occurrences that are minimally explored or unexplored. The qualitative assessment used in this study relies on three key criteria: (1) the presence of known deposits, prospects, or mineral occurrences; (2) favourable geologic settings for having certain deposit types based on current ore deposit models; and (3) geochemical anomalies in rocks or stream sediments, including panned concentrates. Among 20 different deposit types considered herein, a high resource potential is assigned only to three: (1) sediment-hosted manganese, (2) mafic- and ultramafic-hosted nickel-copper(-cobalt-platinum group elements), and (3) pegmatitic lithium-cesium-tantalum. Moderate potential is assigned to 11 other deposit types, including: (1) porphyry copper-molybdenum (-rhenium, selenium, tellurium, bismuth, platinum group elements); (2) chromium in ophiolites; (3) platinum group elements in ophiolitic ultramafic rocks; (4) granite-hosted uranium-thorium; (5) tin in granitic plutons and veins; (6) niobium, tantalum, and rare earth elements in alkaline intrusions; (7) tungsten and bismuth in polymetallic veins; (8) vanadium in black shales; (9) antimony in orogenic veins and replacements; (10) tellurium in epithermal deposits; and (11) uranium in peat.

Maine↗

USGS2019

Geochemical and petrological diversity of mafic magmas from Mount St. Helens

Quaternary eruptive products in the Cascade arc include a variety of different basalt types. At Mount St. Helens (MSH), the most active volcano in the Cascades throughout the last 35 ka, three different mafic endmembers erupted at the end of the Castle Creek period (1900–1700 years B.P.): (1) high-field strength element (HFSE)-rich basalt enriched in K, Ti, P, and incompatible trace elements; (2) low-K olivine tholeiite (LKOT) with lower amounts of incompatible trace elements; and (3) calc-alkaline (arc-type) basaltic andesite with a typical subduction signature, i.e., enrichment in fluid-mobile large ion lithophile elements (LILE) relative to immobile high-field strength elements (HFSE). Each type has compositions projecting backwards to more primitive endmembers in the Cascades. Single units encompassing basaltic-to-basaltic andesitic compositions with intermediate trace-element abundances form two almost continuous trends towards basaltic andesite. These trends are interpreted to result from assimilation of pre-existing, more evolved, calc-alkaline material (and in one case mixing of different mafic magma types) during migration of the magmas through the crust. Most of the erupted basalts are porphyritic (10–30%) with an assemblage dominated by olivine and plagioclase and show disequilibrium textures preventing detailed reconstruction of mantle melting processes. Although typical hydrous arc basalt produced by flux melting in the mantle is absent in the eruptive products of MSH, arc-type basaltic andesite suggests its presence at depth. LKOT magmas are interpreted as decompression melts from the upper mantle, whereas HFSE-rich basalts are likely derived from the water-poor periphery of the main flux melting regime, potentially tapping a trace-element-enriched source. Primitive spinel compositions and whole-rock trace-element variations indicate at least two distinct, relatively fertile lherzolite sources for these two basalt types. Weak crustal zones associated with an old fracture system beneath MSH likely provide conduits for fast and isolated ascent of distinct batches of magma, bypassing the lower crustal mush zone. The eruption of the basalts through the upper crustal magma system and main edifice is consistent with an offset plumbing system suggested by geophysical data.

Washington↗

USGS2004

Composition of water and suspended sediment in streams of urbanized subtropical watersheds in Hawaii

Urbanization on the small subtropical island of Oahu, Hawaii provides an opportunity to examine how anthropogenic activity affects the composition of material transferred from land to ocean by streams. This paper investigates the variability in concentrations of trace elements (Pb, Zn, Cu, Ba, Co, As, Ni, V and Cr) in streams of watersheds on Oahu, Hawaii. The focus is on water and suspended particulate matter collected from the Ala Wai Canal watershed in Honolulu and also the Kaneohe Stream watershed. As predicted, suspended particulate matter controls most trace element transport. Elements such as Pb, Zn, Cu, Ba and Co exhibit increased concentrations within urbanized portions of the watersheds. Particulate concentrations of these elements vary temporally during storms owing to input of road runoff containing elevated concentrations of elements associated with vehicular traffic and other anthropogenic activities. Enrichments of As in samples from predominantly conservation areas are interpreted as reflecting agricultural use of fertilizers at the boundaries of urban and conservation lands. Particulate Ni, V and Cr exhibit distributions during storm events that suggest a mineralogical control. Principal component analysis of particulate trace element concentrations establishes eigenvalues that account for nearly 80% of the total variance and separates trace elements into 3 factors. Factor 1 includes Pb, Zn, Cu, Ba and Co, interpreted to represent metals with an urban anthropogenic enrichment. Factor 2 includes Ni, V and Cr, elements whose concentrations do not appear to derive from anthropogenic activity and is interpreted to reflect mineralogical control. Another, albeit less significant, anthropogenic factor includes As, Cd and U and is thought to represent agricultural inputs. Samples collected during a storm derived from an offshore low-pressure system suggest that downstream transport of upper watershed material during tradewind-derived rains results in a 2-3-fold dilution of the particulate concentrations of Pb, Zn and Cu in the Ala Wai canal watershed. ?? 2004 Elsevier Ltd. All rights reserved.

Conference Paper↗

USGS2009

Relative spatial soil geochemical variability along two transects across the United States and Canada

To support the development of protocols for the proposed North American Soil Geochemical Landscapes project, whose objective is to establish baselines for the geochemistry of North American soils, two continental-scale transects across the United States and Canada were sampled in 2004. The sampling employed a spatially stratified random sampling design in order to estimate the variability between 40-km linear sampling units, within them, at sample sites, and due to sample preparation and analytical chemical procedures. The 40-km scale was chosen to be consistent with the density proposed for the continental-scale project. The two transects, north–south (N–S) from northern Manitoba to the USA–Mexico border near El Paso, Texas, and east–west (E–W) from the Virginia shore north of Washington, DC, to north of San Francisco, California, closely following the 38th parallel, have been studied individually. The purpose of this study was to determine if statistically significant systematic spatial variation occurred along the transects. Data for 38 major, minor and trace elements in A- and C-horizon soils where less than 5% of the data were below the detection limit were investigated by Analysis of Variance (ANOVA). A total of 15 elements (K, Na, As, Ba, Be, Ce, La, Mn, Nb, P, Rb, Sb, Th, Tl and W) demonstrated statistically significant ( p <0.05) variability at the between-40-km scale for both horizons along both transects. Only Cu failed to demonstrate significant variability at the between-40-km scale for both soil horizons along both transects. The patterns of relative variability differ by transect and horizon. The N–S transect A-horizon soils show significant between-40-km scale variability for 29 elements, with only 4 elements (Ca, Mg, Pb and Sr) showing in excess of 50% of their variability at the within-40-km and ‘at-site’ scales. In contrast, the C-horizon data demonstrate significant between-40-km scale variability for 26 elements, with 21 having in excess of 50% of their variability at the within-40-km and ‘at-site’ scales. In 36 instances, the ‘at-site’ variability is statistically significant in terms of the sample preparation and analysis variability. It is postulated that this contrast between the A- and C- horizons along the N–S transect, that is dominated by agricultural land uses, is due to the local homogenization of Ap-horizon soils by tillage reducing the ‘at-site’ variability. The spatial variability is distributed similarly between scales for the A- and C-horizon soils of the E–W transect. For all elements, there is significant variability at the within-40-km scale. Notwithstanding this, there is significant between-40-km variability for 28 and 20 of the elements in the A- and C-horizon data, respectively. The differences between the two transects are attributed to (1) geology, the N–S transect runs generally parallel to regional strikes, whereas the E–W transect runs across regional structures and lithologies; and (2) land use, with agricultural tillage dominating along the N–S transect. The spatial analysis of the transect data indicates that continental-scale maps demonstrating statistically significant patterns of geochemical variability may be prepared for many elements from data on soil samples collected on a 40 x 40 km grid or similar sampling designs resulting in a sample density of 1 site per 1600 km 2 .

Applied Geochemistry↗

USGS2012

Mineralogy and environmental geochemistry of historical iron slag, Hopewell Furnace National Historic Site, Pennsylvania, USA

The Hopewell Furnace National Historic Site in southeastern Pennsylvania, which features an Fe smelter that was operational in the 18th and 19th centuries, is dominated by three slag piles. Pile 1 slag, from the Hopewell Furnace, and pile 2 slag, likely from the nearby Cornwall Furnace, were both produced in cold-blast charcoal-fired smelters. In contrast, pile 3 slag was produced in an anthracite furnace. Ore samples from the nearby Jones and Hopewell mines that fed the smelter are mainly magnetite-rich with some sulfides (pyrite, chalcopyrite, sphalerite) and accessory silicates (quartz, garnet, feldspar, and clay minerals). Slag piles 1 and 2 are similar mineralogically containing predominantly skeletal and dendritic aluminian diopside and augite, skeletal forsteritic olivine, glass, rounded blebs of metallic Fe, and exotic quartz. Olivine is a major phase in all samples from pile 2, whereas it occurs in only a few samples from pile 1. Samples of the <2 mm-size fraction of surface composite slag material or crushed slag from at depth in piles 1 and 2 are mineralogically similar to the large surface slag fragments from those piles with the addition of phases such as feldspars, Fe oxides, and clay minerals that are either secondary weathering products or entrained from the underlying bedrock. Pile 3 slag contains mostly skeletal forsteritic olivine and Ti-bearing aluminian diopside, dendritic or fine-grained subhedral melilite, glass, euhedral spinel, metallic Fe, alabandite–oldhamite solid solution, as well as a sparse Ti carbonitride phase. The bulk chemistry of the slag is dominated by Al 2 O 3 (8.5–16.2 wt.%), CaO (8.2–26.2 wt.%), MgO (4.2–24.7 wt.%), and SiO 2 (36.4–59.8 wt.%), constituting between 81% and 97% of the mass of the samples. Piles 1 and 2 are chemically similar; pile 1 slag overall contains the highest Fe 2 O 3 , K 2 O and MnO, and the lowest MgO concentrations. Pile 3 slag is high in Al 2 O 3 , CaO and S, and low in Fe 2 O 3 , K 2 O and SiO 2 compared to the other piles. In general, piles 1 and 2 are chemically similar to each other, whereas pile 3 is distinct – a conclusion that reflects their mineralogy. The similarities and differences among piles in terms of mineralogy and major element chemistry result from the different smelting conditions under which the slag formed and include the fuel source, the composition of the ore and flux, the type of blast (cold versus hot), which affects the furnace temperature, and other beneficiation methods. The three distinct slag piles at Hopewell are enriched in numerous trace elements, such as As (up to 12 mg/kg), Cd (up to 0.4 mg/kg), Co (up to 31.8 mg/kg), Cu (up to 647 mg/kg), Mn (up to 0.69 wt.%), Pb (up to 172 mg/kg) and Zn (up to 393 mg/kg), together with Fe (13.9 wt.%), when compared to the average for the continental crust, with the <2 mm-size fraction commonly containing the highest concentrations. Enrichments in various elements (e.g., Cd, Co, Cu, Pb, Zn) were also found in the ore samples. Despite these enrichments, comparison of bulk chemistry trace-element concentrations to the environmental guidelines suggests most elements are likely not problematic with the exception of As, Co, Fe and Mn. Leachate tests that simulate weathering indicate Fe (up to 973 μg/L) and Mn (up to 133 μg/L) are readily released in potentially harmful concentrations compared to secondary drinking water and some aquatic ecosystem toxicity criteria. Aluminum and Cu, although not high in the solid compared to environmental guidelines, also exceed relevant criteria in leachate extracts with maximum concentrations of 2700 μg/L and 17.7 μg/L, respectively. In contrast, As and Co, which are significant in the solids, are not leached in concentrations that exceed guidelines (i.e., 3 μg/L or less for both elements). The weathering rates of the Fe metal and Fe oxides, which host Cu and some Fe, are likely higher than the silicate glass, which hosts the majority of Al, Mn and some Fe, and the crystalline silicates and spinels affecting which elements and how much are released into the environment and surrounding aquatic ecosystem. The mineral assemblages and their chemical composition, the bulk sample chemistry, and leachability of trace elements are all important components in understanding the potential environmental impacts of the slag piles.

Pennsylvania↗

USGS2010

A high-pyrite semianthracite of Late Permian age in the Songzao Coalfield, southwestern China: Mineralogical and geochemical relations with underlying mafic tuffs

The No. 12 Coal (Late Permian) in the Songzao Coalfield, Chongqing, southwestern China, is characteristically high in pyrite and some trace elements. It is uniquely deposited directly above mafic tuff beds. Samples of coal and tuffs have been studied for their mineralogy and geochemistry using inductively coupled plasma-mass spectrometry, X-ray fluorescence, plasma low-temperature ashing plus powder X-ray diffraction, and scanning electron microscopy equipped with energy-dispersive X-ray analysis.The results show that the minerals of the No. 12 Coal are mainly composed of pyrite, clay minerals (kaolinite, chamosite, and illite), ankerite, calcite, and trace amounts of quartz and boehmite. Kaolinite and boehmite were mainly derived from sediment source region of mafic tuffs. Chamosite was formed by the reaction of kaolinite with Fe-Mg-rich fluids during early diagenesis. The high pyrite (Sp,d=8.83%) in the coal was related to marine transgression over peat deposits and abundant Fe derived from the underlying mafic tuff bed. Ankerite and calcite were precipitated from epigenetic fluids.Chemical compositions of incompatible elements indicate that the tuffs were derived from enriched mantle and the source magmas had an alkali-basalt character. Compared to other coals from the Songzao Coalfield and common Chinese coals, the No. 12 Coal has a lower SiO2/Al2O3 (1.13) but a higher Al2O3/Na2O (80.1) value and is significantly enriched in trace elements including Sc (13.5??g/g), V (121??g/g), Cr (33.6??g/g), Co (27.2??g/g), Ni (83.5??g/g), Cu (48.5??g/g), Ga (17.3??g/g), Y (68.3??g/g), Zr (444??g/g), Nb (23.8??g/g), and REE (392??g/g on average). Above mineralogical compositions, as well as similar ratios of selected elements (e.g., SiO2/Al2O3 and Al2O3/Na2O) and similar distribution patterns of incompatible elements (e.g., the mantle-normalized diagram for incompatible elements and chondrite-normalized diagram for rare earth elements) of coal and tuff, indicated that enriched trace elements above were largely derived from mafic tuffs, in addition to a minor amount from the Kandian Oldland. ?? 2010 Elsevier B.V.

International Journal of Coal Geology↗

USGS2022

Juvenile continental crust evolution in a modern oceanic arc setting: Petrogenesis of Cenozoic felsic plutons in Fiji, SW Pacific

Viti Levu, Fiji, provides one of the best exposed Phanerozoic analogues for the formation of juvenile continental crust in an intra-oceanic setting. Tonalites and trondhjemites are present in several large (75–150 km 2 ) adjacent, mid-Cenozoic plutons. We report major and trace element data including rare earth element (REE) and high-precision high field strength element (HFSE) compositions, new Hf-Nd-Sr-Pb isotope data, and zircon U/Pb-ages, O-Hf isotopes, and trace elements, from five different plutons. The Eocene Yavuna pluton and the Miocene Colo plutons are mainly composed of tonalites and trondhjemites and represent the exposed middle crust of the former Vitiaz island arc. The plutons can be divided into three suites. One suite is light REE (LREE) depleted with some trace element ratios lower than average normal mid-ocean ridge basalts (N-MORB). A second suite has flat REE patterns similar to local island arc basalts. Both suites occur near the coast of Viti Levu, include a wide compositional spectrum from gabbro to tonalite, and can be produced mostly by fractional crystallization of mafic precursor melts. The third suite is characterized by LREE enrichments with higher La N /Yb N (2.3–4.9), higher Zr/Y (4.3–7.1), and lower Nb/Ta (9.6–12.4). They occur closer to the center of the island and are bimodal trondhjemite-gabbro intrusions. These characteristics are consistent with formation mostly by partial melting of mafic crust. Trace element modeling shows that the trace element ratios of the third suite can be produced by 10–20 % melting of the mafic crust in the presence of residual amphibole, resulting in the retention of the medium REE (MREE) and diagnostic trace element ratios including low Nb/Ta and high Zr/Y. Geochemical similarities of the LREE enriched suite to typical “low”-pressure Archean tonalites-trondhjemites-granodiorites (TTGs) imply a common petrogenetic origin and similar mechanisms for the generation of juvenile Archean and modern differentiated crust by partial melting of mafic crust with residual amphibole. In modern oceanic arcs, genetically unrelated felsic plutonic as well as volcanic rocks co-exist, and in this regard, the Fijian plutons accompany major tectonic disruptions to arc processes.

Geochimica et Cosmochimica Acta↗

USGS2009

Comparison of humus and till as prospecting material in areas of thick overburden and multiple ice-flow events: An example from northeastern New Brunswick

Thirty-nine elements in humus and till matrix were compared at 109 sites overlying Ag-As-Cu-Mo-Pb-Zn mineralized occurrences in northeastern New Brunswick to assess humus for anomaly identification. Humus element concentrations were not consistently correlative with maximum or minimum concentrations found in the underlying till or bedrock. The humus demonstrated significantly higher mean elemental concentrations than the till for six specific elements: 9 times greater for Mn, 6 times greater for Cd, 5 times greater for Ag and Pb, 3 times greater for Hg, and double the concentration of Zn. Spatial dispersal patterns for these elements were much larger for humus content than that exhibited by the till matrix analysis, but did not delineate a point source. For elements in till, the highest concentrations were commonly found directly overlying the underlying mineralized bedrock source or within one km down-glacier of the source. The complexity of the humus geochemical patterns is attributed to the effects of post-glacial biogenic, down-slope hydrodynamic and solifluction modification of dispersed mineralization in the underlying till, and the greater capacity of humus to adsorb cations and form complexes with some elements, relative to the till matrix. Humus sampling in areas of glaciated terrain is considered to be mostly valuable for reconnaissance exploration as elements can be spatially dispersed over a much larger area than that found in the till or underlying bedrock. ?? 2009 Elsevier B.V. All rights reserved.

Journal of Geochemical Exploration↗

USGS1998

Geochemical and isotopic (Nd-Pb-Sr-O) variations bearing on the genesis of volcanic rocks from Vesuvius, Italy

Alkaline volcanism produced by Monte Somma-Vesuvius volcano includes explosive plinian and subplinian activity in addition to effusive lava flows. Pumice, scoria, and lava (150 samples) exhibit major- and trace-element gradients as a function of SiO2 (58.9-47.2 wt%) and MgO (0-7.8 wt%); Mg value are ???50. Internally gradational chemical groups or cycles are distinguished by age: (1) 25 000 to 14 000 yr B.P.; (2) 8000 yr B.P. to A.D. 79; and (3) A.D. 79 to 1944. A small number of lavas, dikes and scora were also analysed from the Somma formation (~ 35 000 to 25 000 yr B.P.). Within each group, contents of Na2O + K2O increas with decreasing MgO along distinct rocks. Nb/Y values are variable from 0.66 to 3.14 (at SiO2 ??? 50 wt%) generally in the range of alkaline and ultra-alkaline rocks. Variations in contents of some majro elements (e.g., P and Ti), and trace elements (e.g., Th, Nb, Ta, Zr, Hf, Pb, La, and Sc), as well as contrasting trends in ratios of various elements (e.g., Ta/Yb, Hf/U, Th/Ta, Th/Hf, Th/Yb, etc.) are also generally consistent with the group subdivisions. For example, Th/Hf increases from ??? 5 to ??? 10 with decreasing age for the Vesuvius system as a whole, yielding similar compositions in the least evolved rocks (low-silica, high-MgO, imcompatible element-poor) erupted at the end of each cycle. Internal variations within individual eruptions also systematically changed generally towards a common mafic composition at the end of each cycle, thus reflecting the dominanit volume in the magma chamber. At the start of a new eruptive cycle, the rocks are relatively enriched in incompatible elements; younger groups also contain higher abundances than other groups. N-MORB-normalized multielement diagrams exhibit selective enrichments of Sr, K, Rb, Th, and the light rare-earth elements; deep Nb and Ta negative anomalies commonly seen in rocks generated at orogenic margins are absent in the light rare-earth elements; deep Nb and Ta netgative anomalies commonly seen in rocks generated at orogenic margins are absent in our samples. Sr isotopic compositions are known to be variable within some of the units, in agreement with our data (87Sr/86Sr ~ 0.70699 to 0.70803) and with contributions from several isotopic components. Isotopic compositions for ??18O (7.3 to 10.2%), Pb for mineral separates and whole rocks (206Pb/204Pb ~ 18.947 to 19.178, 207Pb/204/Pb ~ 15.617 to 15.769, 208Pb/204Pb ~38.915 to 39.345), and Nd (143Nd ~ 0.51228 to 0.51251) also show variability. Oxygen isotope data show that pumices have higher ??18O values than cogenetic lavas, and that ??18O values and SiO2 are correlated. Radiogenic and stable isotope data plot within range of isotopic compositions for the Roman comagmatic province. Fractional crystallization cannot account for the radiogenic isotopic compositions of the Vesuvius magmas. We favor instead the combined effects of heterogeneous magma sources, together with isotopic exchange near the roof of the magma chamber. We suggest that metasomatized continental mantle lithosphere is the principal source of the magmas. This kind of enriched mantle was melted and reactivated in an area of continental extension (incipient rift setting) without direct reliance on contemporaneous subduction processes but possibly with input from mantle sources that resemble those that produce ocean island basalts.

Journal of Volcanology and Geothermal Research↗

USGS2024

A multidisciplinary approach that considers occurrence, geochemistry, bioavailability, and toxicity to prioritize critical minerals for environmental research

Critical minerals (or critical elements) are minerals or elements that are essential to global security and development and have supply chains vulnerable to disruption. In general, knowledge of the environmental behavior and health effects of critical elements is needed to support the development of safe and environmentally responsible supplies. This knowledge includes identifying potential consequences of increased critical element production and use, alternative critical element sources such as mine wastes, and adverse effects of critical elements on ecosystem condition and organismal health. Here we identify significant data gaps in the understanding of critical elements in surficial and aquatic environments, and the need, given the large number of commodities (50) identified on the 2022 critical minerals list for the United States, for an approach to prioritize them for study of their environmental fate and effects. We propose a multidisciplinary approach for this prioritization, considering measures of occurrence, geochemistry, bioavailability, and toxicity. We describe relatively easy-to-obtain metrics for each of these topic areas and demonstrate the utility of this integrated prioritization approach using indium and zinc as examples. This approach facilitates prioritizing research with a focus on those critical elements that are most mobile in the environment, bioavailable, toxic, or simply lacking data in these categories.

Environmental Science & Technology↗

USGS2004

Ultramafic xenoliths from the Bearpaw Mountains, Montana, USA: Evidence for multiple metasomatic events in the lithospheric mantle beneath the Wyoming craton

Ultramafic xenoliths in Eocene minettes of the Bearpaw Mountains volcanic field (Montana, USA), derived from the lower lithosphere of the Wyoming craton, can be divided based on textural criteria into tectonite and cumulate groups. The tectonites consist of strongly depleted spinel lherzolites, harzbugites and dunites. Although their mineralogical compositions are generally similar to those of spinel peridotites in off-craton settings, some contain pyroxenes and spinels that have unusually low Al2O3 contents more akin to those found in cratonic spinel peridotites. Furthermore, the tectonite peridotites have whole-rock major element compositions that tend to be significantly more depleted than non-cratonic mantle spinel peridotites (high MgO, low CaO, Al2O3 and TiO2) and resemble those of cratonic mantle. These compositions could have been generated by up to 30% partial melting of an undepleted mantle source. Petrographic evidence suggests that the mantle beneath the Wyoming craton was re-enriched in three ways: (1) by silicate melts that formed mica websterite and clinopyroxenite veins; (2) by growth of phlogopite from K-rich hydrous fluids; (3) by interaction with aqueous fluids to form orthopyroxene porphyroblasts and orthopyroxenite veins. In contrast to their depleted major element compositions, the tectonite peridotites are mostly light rare earth element (LREE)-enriched and show enrichment in fluid-mobile elements such as Cs, Rb, U and Pb on mantle-normalized diagrams. Lack of enrichment in high field strength elements (HFSE; e.g. Nb, Ta, Zr and Hf) suggests that the tectonite peridotites have been metasomatized by a subduction-related fluid. Clinopyroxenes from the tectonite peridotites have distinct U-shaped REE patterns with strong LREE enrichment. They have 143Nd/144Nd values that range from 0??5121 (close to the host minette values) to 0??5107, similar to those of xenoliths from the nearby Highwood Mountains. Foliated mica websterites also have low 143Nd/144Nd values (0??5113) and extremely high 87Sr/86Sr ratios in their constituent phlogopite, indicating an ancient (probably mid-Proterozoic) enrichment. This enriched mantle lithosphere later contributed to the formation of the high-K Eocene host magmas. The cumulate group ranges from clinopyroxene-rich mica peridotites (including abundant mica wehrlites) to mica clinopyroxenites. Most contain >30% phlogopite. Their mineral compositions are similar to those of phenocrysts in the host minettes. Their whole-rock compositions are generally poorer in MgO but richer in incompatible trace elements than those of the tectonite peridotites. Whole-rock trace element patterns are enriched in large ion lithophile elements (LILE; Rb, Cs, U and Pb) and depleted in HFSE (Nb, Ta Zr and Hf as in the host minettes, and their Sr-Nd isotopic compositions are also identical to those of the minettes. Their clinopyroxenes are LREE-enriched and formed in equilibrium with a LREE-enriched melt closely resembling the minettes. The cumulates therefore represent a much younger magmatic event, related to crystallization at mantle depths of minette magmas in Eocene times, that caused further metasomatic enrichment of the lithosphere. ?? Oxford University Press 2004; all rights reserved.

Journal of Petrology↗

USGS1956

Geochemistry of sphalerite from the Star Mine, Coeur d'Alene district, Idaho

Forty sphalerite samples from the Star mine, Coeur d'Alene district, Idaho, and 19 sphalerite samples from other Coeur d'Alene mines have been quantitatively analyzed by spectrographic methods for Fe, Cu, Pb, Cd, Ga, Ge, In, Mn, Co, and Hg. The samples from the Star vein were collected over a strike length of 2,000 feet and a vertical distance of 5,300 feet.It is believed that Star mine sphalerite formed in equilibrium with Fe; consequently, following Kullerud's work, the Fe content may be used as a relative temperature scale. Relative Fe temperatures suggest that the lower portions of the Star ore body formed at lower temperatures than the upper portions of the ore body.Distribution of the minor elements in sphalerite is random within the ore body. Also, there is no correlation of Fe with minor elements other than Mn; therefore we believe temperature has had no influence on the distribution of minor elements, except Mn, in this ore body.The principal reason for this seems to be that equilibrium concentrations of the minor elements were not reached. Minor-element concentrations in sphalerite from the Coeur d'Alene district are similar to those in other districts throughout the world; consequently, the writers suggest that in general the minor-element content of sphalerite, other than perhaps Mn, cannot be an indicator of formation temperatures because equilibrium concentrations are rarely, if ever, attained.The average minor-element content in a district is probably that of the ore-forming solutions. Specific minor-element content in sphalerite is random.

Idaho↗

USGS2008

Analytical Results for Municipal Biosolids Samples from a Monitoring Program near Deer Trail, Colorado (U.S.A.), 2007

Since late 1993, the Metro Wastewater Reclamation District of Denver (Metro District), a large wastewater treatment plant in Denver, Colorado, has applied Grade I, Class B biosolids to about 52,000 acres of nonirrigated farmland and rangeland near Deer Trail, Colorado (U.S.A.). In cooperation with the Metro District in 1993, the U.S. Geological Survey (USGS) began monitoring ground water at part of this site. In 1999, the USGS began a more comprehensive monitoring study of the entire site to address stakeholder concerns about the potential chemical effects of biosolids applications to water, soil, and vegetation. This more comprehensive monitoring program recently has been extended through 2010. Monitoring components of the more comprehensive study include biosolids collected at the wastewater treatment plant, soil, crops, dust, alluvial and bedrock ground water, and streambed sediment. Streams at the site are dry most of the year, so samples of streambed sediment deposited after rain were used to indicate surface-water effects. This report will present only analytical results for the biosolids samples collected at the Metro District wastewater treatment plant in Denver and analyzed during 2007. We have presented earlier a compilation of analytical results for the biosolids samples collected and analyzed for 1999 through 2006. More information about the other monitoring components is presented elsewhere in the literature. Priority parameters for biosolids identified by the stakeholders and also regulated by Colorado when used as an agricultural soil amendment include the total concentrations of nine trace elements (arsenic, cadmium, copper, lead, mercury, molybdenum, nickel, selenium, and zinc), plutonium isotopes, and gross alpha and beta activity. Nitrogen and chromium also were priority parameters for ground water and sediment components. In general, the objective of each component of the study was to determine whether concentrations of priority parameters (1) were higher than regulatory limits, (2) were increasing with time, or (3) were significantly higher in biosolids-applied areas than in a similar farmed area where biosolids were not applied. Previous analytical results indicate that the elemental composition of the biosolids from the Denver plant was consistent during 1999-2006 and this consistency continues with the samples for 2007; total concentrations of regulated trace elements remained consistently lower than the regulatory limits for the entire monitoring period. Our previously reported data (1999-2006) and data presented in this report were used to compile an inorganic-chemical biosolids signature that can be contrasted with the geochemical signature for this site. The biosolids signature and an understanding of the geology and hydrology of the site can be used to separate biosolids effects from natural geochemical effects. Elements of particular interest for a biosolids signature include bismuth, copper, silver, mercury, phosphorus, and silver. An alternative method of digestion of biosolids was also recently investigated, and the results are presented in this report. A microwave digestion using only nitric acid at controlled elevated temperature and pressure was tested to replace the much more time-consuming and labor-intensive, traditional four-acid, hotplate method for the preparation of solutions to be analyzed by inductively coupled plasma-mass spectrometry (ICP-MS). Elements of concern determined by ICP-MS following digestion include cadmium, copper, lead, molybdenum, nickel, and zinc. The microwave 'digestion' proved to be a strong acid leach, and it was less efficient at digesting the biosolids samples with consistently lower recoveries (compared to the four-acid digestion value) for most elements, but especially for the elements of concern - copper, nickel, and zinc. Other elements traditionally associated with the silicate or oxide minerals demonstrated low recoveries, especially titaniu

Open-File Report↗

USGS1990

Reconnaissance investigation of water quality, bottom sediment, and biota associated with irrigation drainage in the American Falls Reservoir area, Idaho, 1988-89

Increased concern about the quality of irrigation drainage and its potential effects on human health, fish, and wildlife prompted the Department of the Interior to begin a program during late 1985 to identify irrigation-induced water-quality problems that might exist in the Western States. During `988, the Task Group on Irrigation Drainage selected the American Falls Reservoir area, Idaho, for study to determine whether potentially toxic concentrations of trace elements or organochlorine compounds existed in water, bottom sediment, and biota. The 91-square mile American Falls Reservoir has a total capacity of 1.7 million acre-feet and is used primarily for irrigation-water supply and power generation. Irrigated land upstream from the reservoir totals about 550,000 acres. Total water inflow to the reservoir is about 5.8 million acre-feet per year, of which about 63 percent is from surface-water runoff, 33 percent is from ground-water discharge, and about 4 percent is from ungaged tributaries, canals, ditches, sloughs, and precipitation. Ground-water discharge to the reservoir originates, in part, from irrigation of land upstream from and adjacent to the reservoir. The 1988 water year was a drought year, and water discharge was about 34 percent less than during 1939-88. Water samples were collected during the post-irrigation (October 1987) and irrigation (July 1988) seasons and were analyzed for major ions and trace elements. Bottom-sediment samples were collected during the irrigation season and were analyzed for trace elements and organochlorine compounds. Biota samples were collected during May, June, July, and August 1988 and were analyzed for trace elements and organochlorine compounds. Dissolved-solids concentrations in water ranged from 216 to 561 milligrams per liter. The similarity of dissolved-solids concentrations between the irrigation and post-irrigation seasons can be attributed to the large volume of ground-water discharge in the study area. Most trace-element concentrations in water were near analytical reporting limits; none exceeded State or Federal water-quality standards or criteria. Trace elements that were present at all sites in analytically detectable concentrations (in micrograms per liter) included arsenic (2 to 7), boron (40 to 130), uranium (0.7 to 3.5), vanadium (1 to 6) and zinc (less than 3 to 42). The ranges of arsenic, cadmium, and mercury concentrations in water analyzed during previous investigations. Selenium concentrations ranged from less than 1 (the reporting limit) to 6 micrograms per liter and did not exceed State of Federal water-quality standards or criteria. Concentrations of most trace elements in bottom sediment were similar to geometric mean concentrations in study area soils and were within the expected 95-percent range of concentrations in soils in the Western United States. Mercury concentrations in 9 of the 18 bottom-sediment samples exceeded the 95th-percentile concentration for mercury in area soils. Selenium concentration for selenium in area soils and, in 1 sample, exceeded the upper limit of the expected 95-percent range for selenium in Western United States soils. Most organochlorine compunds in bottom sediment were lower than analytical reporting limits. Only DDE (0.2 micrograms per kilogram) and DDT (0.3 micrograms per kilogram) were detected in bottom sediment from the Portneuf River. Except for mercury and selenium, concentrations of most trace elements in biota were not considered high enough to be harmful to humans or wildlife. Some mercury concentrations in fish exceeded the U.S. Fish and Wildlife Service National Contaminant Biomonitoring Program 85th-percentile concentration and were at levels that might not be safe for human consumption, especially for pregnant women. Elevated mercury concentrations in fish-eating waterbirds, such as double-crested cormorants, indicates biomagnification in the food chain. Selenium concentrations generally were low except in mallard livers (6.6 to 41.8 micrograms per gram, dry weight). This range is within the range of selenium concentrations (19 to 43 micrograms per gram, dry weight) reported in livers of ducks from Kesterson National Wildlife Refuge, California, where waterbird deformities, moralities, and reproductive impairment were observed. Selenium concentrations in mayfly nymphs were at or near dietary concentrations (5 to 8 micrograms per gram, dry weight) that had adverse reproductive effects on mallards during laboratory toxicity studies. p,p'DDE was detected in all waterbird eggs and juvenile mallared carcasses. Highest concentrations were in cormorant eggs (0.59 to 5.70 micrograms per gram, wet weight). p,p'DDE concentrations in four of five cormorant eggs exceeded the National Academy of Sciences, National Academy of Engineering criterion for protection of aquatic wildlife (1 microgram per gram, wet weight, for p,p'DDT and its metabolites). p,p'DDE was detected in all fish samples except rainbow trout. p,p'DDE was detected in one sample of Utah suckers. No concentrations of p,p'DDE or p,p'DDT in fish exceeded the criterion for protection of aquatic life. Total PCB's were detected in all cormorant eggs and all fish samples. PCB's were not detected in other waterbird eggs. PCB concentrations in cormorant eggs (0.28 to 1.8 micro per gram, wet weight) were lower than concentrations that would be expected to cause adverse effects. Two of the three carp samples contained PCB concntrations higher than the recommended level for protection of fish and wildlife (0.4 micrograms per gram, wet weight). Eggshell thinning was noted in cormorant and mallard eggs but was not considered great enough to cause reporductive problems. Observations of the general health of fish and waterbird populations during the study indicated that the area did not appear to have a serious contaminant problem that could be associated with irrigation grainage. No waterbird or fish die-offs were observed, and nesting waterbird populations were noted to be increasing. Selenium concentrations in mallard livers, however, are of concern, as are p,p'DDE residues in cormorant eggs.

Idaho↗

USGS2023

A novel non-destructive workflow for examining germanium and co-substituents in ZnS

A suite of complementary techniques was used to examine germanium (Ge), a byproduct critical element, and co-substituent trace elements in ZnS and mine wastes from four mineral districts where germanium is, or has been, produced within the United States. This contribution establishes a comprehensive workflow for characterizing Ge and other trace elements, which captures the full heterogeneity of samples through extensive pre-characterization. This process proceeded from optical microscopy, to scanning electron microscopy and cathodoluminescence (CL) imaging, to electron microprobe analysis, prior to synchrotron-based investigations. Utilizing non-destructive techniques enabled reanalysis, which proved essential for verifying observations and validating unexpected results. In cases where the Fe content was <0.3 wt% in ZnS, cathodoluminescence imaging proved to be an efficient means to qualitatively identify trace element zonation that could then be further explored by other micro-focused techniques. Micro-focused X-ray diffraction was used to map the distribution of the non-cubic ZnS polymorph, whereas micro-focused X-ray fluorescence (μ-XRF) phase mapping distinguished between Ge 4+ hosted in primary ZnS and a weathering product, hemimorphite [Zn 4 Si 2 O 7 (OH) 2 ·H 2 O]. Microprobe data and μ-XRF maps identified spatial relationships among trace elements in ZnS and implied substitutional mechanisms, which were further explored using Ge and copper (Cu) X-ray absorption near-edge spectroscopy (XANES). Both oxidation states of Ge (4+ and 2+) were identified in ZnS along with, almost exclusively, monovalent Cu. However, the relative abundance of Ge oxidation states varied among mineral districts and, sometimes, within samples. Further, bulk XANES measurements typically agreed with micro-focused XANES (μ-XANES) spectra, but unique micro-environments were detected, highlighting the importance of complementary bulk and micro-focused measurements. Some Ge μ-XANES utilized a high energy resolution fluorescence detector, which improved spectral resolution and spectral signal-to-noise ratio. This detector opens new opportunities for exploring byproduct critical elements in complex matrices. Overall, the non-destructive workflow employed here can be extended to other byproduct critical elements to more fully understand fundamental ore enrichment processes, which have practical implications for critical element exploration, resource quantification, and extraction.

Frontiers in Earth Science↗

USGS2026

The mineral chemistry networks of tin and tungsten reflect metallogenic eras of the Mesozoic

Continental remobilization is a crucial driver of metallogenesis and the formation of ore deposits. Some of the world’s largest mineral deposits of the economically valuable elements tin (Sn), tungsten (W), gold (Au), copper (Cu), lead (Pb), and zinc (Zn) formed during the Mesozoic Era. Additionally, the chemistry and distribution of the elements Sn and W have been investigated in previous studies to understand planetary formation and differentiation processes. These two elements are largely co-located during certain South China Mesozoic metallogenic events but are not co-located during other time periods in the same regions. Here, we investigated the mineral chemistry network similarities and dissimilarities of Sn and W to understand their mineral formation and distribution during the Mesozoic Era and throughout Earth history. Mineral chemistry network community detection analysis and electronegativity associations among mineral constituent elements of Sn minerals and W minerals indicate that the elements have similar chemistry among their oxide minerals. However, Sn forms a much wider range of minerals that also contain S compared to W, which occurs in a limited number of S-containing minerals. The divergent constituent element interactions among S-containing Sn minerals and W minerals reflect the redox sensitivity and importance of oxygen (O) fugacity in Sn mineral formation. Conversely, extensive W mineral deposits are known to form at both high and low O fugacities. The similarities and differences between the mineral chemistry networks of Sn and W reflect the mineral distribution of the two elements in the Sn-W mineralization event from 160 to 139 Ma vs. the Sn–uranium (U) mineralization event from 125 to 98 million years ago (Ma). The mineral chemistry and distribution of Mesozoic Sn and W deposits illustrate the contrasting importance of redox and O fugacity on the mineral formation of different elements, and the dynamic crustal evolution that took place during this period of Earth history.

Geosciences↗

USGS1982

Chemical and mineralogical analysis of devonian black-shale samples from Martin County, Kentucky; Carroll and Washington counties, Ohio; Wise County, Virginia; and Overton County, Tennessee, U.S.A.

Core samples of Devonian shales from five localities in the Appalachian basin have been analyzed chemically and mineralogically. The amounts of major elements are similar; however, the minor constituents, organic C, S, phosphate and carbonate show ten-fold variations in amounts. Trace elements Mo, Ni, Cu, V, Co, U, Zn, Hg, As and Mn show variations in amounts that can be related to the minor constituents. All samples contain major amounts of quartz, illite, two types of mixed-layer clays, and chlorite in differing quantities. Pyrite, calcite, feldspar and kaolinite are also present in many samples in minor amounts. Dolomite, apatite, gypsum, barite, biotite and marcasite are present in a few samples in trace amounts. Trace elements listed above are strongly controlled by organic C with the exception of Mn which is associated with carbonate minerals. Amounts of organic C generally range from 3 to 6%, and S is in the range of 2-5%. Amounts of trace elements show the following general ranges in ppm (parts per million): Co, 20-40; Cu, 40-70; U, 10-40; As, 20-40; V, 150-300; Ni, 80-150; high values are as much as twice these values. The organic C was probably the concentrating agent, and the organic C and sulfide S together created an environment that immobilized and preserved these trace elements. Closely spaced samples showing an abrupt transition in color also show changes in organic C, S and trace-element contents. Several associations exist between mineral and chemical content. Pyrite and marcasite are the only minerals found to contain sulfide-S. In general, the illite-chlorite mixed-layer clay mineral shows covariation with organic C if calcite is not present. The enriched trace elements are not related to the clay types, although the clay and organic matter are intimately associated as the bulk fabric of the rock. ?? 1982.

Chemical Geology↗