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Rationale: The reasons for resurgent coal workers' pneumoconiosis and its most severe forms, rapidly progressive pneumoconiosis and progressive massive fibrosis (PMF), in the United States are not yet fully understood. Objectives: To compare the pathologic and mineralogic features of contemporary coal miners with severe pneumoconiosis with those of their historical counterparts. Methods: Lung pathology specimens from 85 coal miners with PMF were included for evaluation and analysis. We compared the proportion of cases with pathologic and mineralogic findings in miners born between 1910 and 1930 (historical) with those in miners born in or after 1930 (contemporary). Results: We found a significantly higher proportion of silica-type PMF (57% vs. 18%; P < 0.001) among contemporary miners compared with their historical counterparts. Mineral dust alveolar proteinosis was also more common in contemporary miners compared with their historical counterparts (70% vs. 37%; P < 0.01). In situ mineralogic analysis showed that the percentage (26.1% vs. 17.8%; P < 0.01) and concentration (47.3310(8) vs. 25.8310(8) particles/cm(3); P = 0.036) of silica particles were significantly greater in specimens from contemporary miners compared with their historical counterparts. The concentration of silica particles was significantly greater when silica-type PMF, mineral dust alveolar proteinosis, silicotic nodules, or immature silicotic nodules were present (P < 0.05). Conclusions: Exposure to respirable crystalline silica appears causal in the unexpected surge of severe disease in contemporary miners. Our findings underscore the importance of controlling workplace silica exposure to prevent the disabling and untreatable adverse health effects afflicting U.S. coal miners. Alpha Foundation for the Improvement of Mine Safety and Health [AFC417-1] Published version Supported by Alpha Foundation for the Improvement of Mine Safety and Health grant AFC417-1. The findings and conclusions in this report are those of the authors and do not necessarily represent the official position of the National Institute for Occupational Safety and Health, Centers for Disease Control and Prevention, or Alpha Foundation for the Improvement of Mine Safety and Health, Inc. Any use of trade, firm, or product names is for descriptive purposes only and does not imply endorsement by the U.S. government.

Tellurium-rich (Te) adularia-sericite epithermal Au-Ag deposits are an important current and future source of precious and critical metals. However, the source and evolution of ore-forming fluids in these deposits are masked by traditional bulk analysis of quartz oxygen isotope ratios that homogenize fine-scale textures and growth zones. To advance understanding of the source of Te and precious metals, herein, we use petrographic and cathodoluminescence (CL) images of such textures and growth zones to guide high spatial resolution secondary ion mass spectroscopy (SIMS) oxygen isotope analyses (10 µm spot) and spatially correlated fluid inclusion microthermometric measurements on successive quartz bands in contemporary Te-rich and Te-poor adularia-sericite (-quartz) epithermal Au-Ag vein deposits in northeastern China. The results show that large positive oxygen isotope shifts from –7.1 to +7.7‰ in quartz rims are followed by precipitation of Au-Ag telluride minerals in the Te-rich deposit, whereas small oxygen isotope shifts of only 4‰ (–2.2 to +1.6‰) were detected in quartz associated with Au-Ag minerals in the Te-poor deposits. Moreover, fluid-inclusion homogenization temperatures are higher in comb quartz rims (avg. 266.4 to 277.5 °C) followed by Au-Ag telluride minerals than in previous stages (~250 °C) in the Te-rich deposit. The Te-poor deposit has a consistent temperature (~245 °C) in quartz that pre- and postdates Au-Ag minerals. Together, the coupled increase in oxygen isotope ratios and homogenization temperatures followed by precipitation of Au-Ag tellurides strongly supports that inputs of magmatic fluid containing Au, Ag, and Te into barren meteoric water-dominated flow systems are critical to the formation of Te-rich adularia-sericite epithermal Au-Ag deposits. In contrast, Te-poor adularia-sericite epithermal Au-Ag deposits show little or no oxygen isotope or fluid-inclusion evidence for inputs of magmatic fluid.

Each year, the Microanalysis Society (MAS) bestows several major awards during the Microscopy & Microanalysis annual meeting. Regrettably, there is never enough time on stage to detail these awardees’ contributions to the science of microanalysis and the Society, which we hope to rectify here and in future articles. The shift of the 2020 M&M meeting to a virtual format meant that our awardees did not receive their accolades on a physical main stage. These recipients were selected for recognition by a variety of mechanisms, of which many Society members may not be aware. For example, the MAS Awards Committee solicits nominations for annual Outstanding Paper Awards from M&M meeting attendees and symposium organizers via a simple webform (https://the-mas.org/mm-outstanding-paper-recommendation/), whereas the Duncumb Award requires a full nomination package from Society members, and other awards are selected solely at the discretion of the MAS President or Council. Additional description of the various MAS awards, including lists of previous award winners, can be found at https://the-mas.org/awards.

Textural, geochronological, and geochemical data are presented here for cassiterite from the giant (149.7 million tonnes [Mt]) Mesoproterozoic Sullivan Pb-Zn-Ag deposit, which has been subjected to several tectonothermal events. These data provide constraints on the age and origin of the tin concentrations and new insights into related base metal mineralization. Sullivan is rare among sediment-hosted, stratiform Pb-Zn-Ag deposits in having high tin contents in ore (up to 2.5 wt %; avg 310 ppm Sn). Cassiterite occurs in all facies of this deformed and metamorphosed deposit, including (1) high-grade veins with arsenopyrite and pyrrhotite, (2) bedded Pb-Zn-Ag ores, (3) massive pyrrhotite, (4) footwall and hanging-wall tourmalinites, and (5) other altered wall rocks. New in situ U-Pb dates for Sullivan cassiterite obtained by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) are modeled by a multicomponent-based algorithm that yields three age peaks: 1475 ± 4 Ma (51% of the data), 1366 ± 10 Ma (25%), and 1074 ± 7 Ma (24%). These dates are attributed, respectively, to primary tin mineralization at ca. 1475 Ma, the East Kootenay orogeny at ca. 1370 to 1300 Ma, and the Grenvillian orogeny at ca. 1100 to 980 Ma. Based on the presence and local abundance of cassiterite in all ore and ore-related rocks at Sullivan, the U-Pb date of 1475 ± 4 Ma reported here represents the first direct age for ore mineralization in the deposit. Occurrence of texturally discordant rims on Sullivan cassiterite grains having U-Pb dates coeval with the East Kootenay and Grenvillian orogenies suggests that these young dates reflect dissolution-reprecipitation processes associated with channelized metamorphic fluid flow. LA-ICP-MS U-Pb dates obtained on low-U ( Aqueous transport conditions for tin are evaluated to gain insights into the cassiterite mineralization at Sullivan. Based on fO2-pH topology of aqueous tin species at 250°C, tin transport was dominated by an SnCl3− complex at fO2 of about –40 and pH of

The Lower to Middle Ordovician Toyen Shale in southern Sweden, a biostratigraphically well-dated siliciclastic mudstone unit, shows 18 distinct authigenic cements that include sulfides, carbonates, silicates, clays, and phosphates. Marcasite, sphalerite, galena, and six texturally distinct types of pyrite characterize the sulfides whereas only one type of dolomite and three different generations of calcite are observed in this unit. Quartz, phosphate, and organic matter occur as only one generation each. Authigenic clay minerals are represented by chlorite and kaolinite. The paragenetic sequence of cements is subdivided into the two pre-burial carbonates, succeeded by ten relatively early burial cements, and six late burial cements, the kaolinite being the latest of them all and potentially being of Cretaceous age. Based on textural relationships, the paragenetic sequence of alterations started with dolomite precipitation followed by calcite, and then five different generations of pyrite. All eleven other phases post-date these initial seven cements in the Toyen Shale. (Less)

Humans accumulate large numbers of inorganic particles in their lungs over a lifetime. Whether this causes or contributes to debilitating disease over a normal lifespan depends on the type and concentration of the particles. We developed and tested a protocol for in situ characterization of the types and distribution of inorganic particles in biopsied lung tissue from three human groups using field emission scanning electron microscopy (FE-SEM) combined with energy dispersive spectroscopy (EDS). Many distinct particle types were recognized among the 13 000 particles analyzed. Silica, feldspars, clays, titanium dioxides, iron oxides and phosphates were the most common constituents in all samples. Particles were classified into three general groups: endogenous, which form naturally in the body; exogenic particles, natural earth materials; and anthropogenic particles, attributed to industrial sources. These in situ results were compared with those using conventional sodium hypochlorite tissue digestion and particle filtration. With the exception of clays and phosphates, the relative abundances of most common particle types were similar in both approaches. Nonetheless, the digestion/filtration method was determined to alter the texture and relative abundances of some particle types. SEM/EDS analysis of digestion filters could be automated in contrast to the more time intensive in situ analyses.

High-U hydrothermal apatite with complex U Pb systematics is closely spatially associated with mineralization at the Coles Hill deposit, the largest unmined uranium deposit known in the United States. The deposit is hosted in metasomatized rocks of the 450- to 430-Ma-old Martinsville Intrusive Complex in south-central Virginia. Direct dating of metamict uranium-ore minerals, mostly coffinite, is not possible due to open-system radon loss. Instead, U Pb isotopes in cogenetic apatite were investigated as a means of evaluating the age of mineralization. Here we report in situ electron probe microanalyses (EPMA) of coffinite, isotope-dilution thermal-ionization mass spectrometry (ID-TIMS) U Pb data for mineralized whole rock samples, and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) U Pb isotope data for apatite in both unmineralized and U-mineralized host rocks. Massive deficits in radiogenic Pb preclude reliable U Pb “chemical ages” calculated from EPMA data obtained from coffinite. In contrast, LA-ICPMS data for secondary apatite in unmineralized rocks indicate low-U concentrations (100–102 ppm), “normal” (consistent with models of terrestrial Pb isotopic evolution) initial Pb isotope compositions, and U Pb age estimates of ~330 Ma, which is consistent with dates previously proposed for the regional Paleozoic shear zone that hosts the deposit. Ore-stage apatite associated with coffinite has high-U concentrations (typically 102–103 ppm but up to 2.4 wt% U) and large excesses of 206Pb (207Pb/206Pb Pb dating of hydrothermal apatite. Excess 206Pb in apatite is derived from decay products of 222Rn lost from coffinite and mobilized by Na-, P-, and U-enriched metasomatic fluids during the main mineralizing event at ~230 Ma. Ore-stage alteration did not uniformly reset the U Pb systematics in host rocks precluding a well-constrained whole-rock isochron age. However, whole-rock isotope data imply U mobility at ~200–220 Ma and support a Triassic age for the final stages of mineralization. Results also indicate that apatite with up to several weight percent uranium is able to retain U and its decay products for hundreds of millions of years; an important consideration when assessing this mineral as a potential matrix for long-term storage of radioactive waste.

The transformation of kerogen to hydrocarbons in the early stages of oil generation is critical for understanding the resource potential of liquid-rich shale plays. Organic petrology commonly is used for visual evaluation of type, quality, and thermal maturity of organic matter, but the relationship of visual petrographic changes to chemical transformations is not well characterized. To improve understanding of these processes, organic-walled microfossils of the unicellular green alga Tasmanites (composed of algaenan) in Upper Devonian Ohio Shale (Huron Member, Appalachian Basin) were analyzed by micro-spectroscopy techniques including micro-Fourier transform infrared (micro-FTIR), X-ray photoelectron (XPS), electron probe microanalysis (EPMA), and fluorescence. Immature to mid-oil window maturation sequences of core and outcrop samples with solid bitumen reflectance (BR) and vitrinite reflectance (VR) values ranging from 0.45 to 0.80 %Ro were used. Hydrous pyrolysis was applied to low-maturity (BR: 0.25–0.39 %Ro) Huron and time-correlative New Albany shale samples to create similar artificial maturation sequences for comparison. Micro-FTIR spectroscopy revealed a decrease in the CH2/CH3 ratio with increasing maturity, indicating Tasmanites aliphatic chains become shorter and more branched. Oxygenated functional groups decreased relative to aliphatic stretching bands and increased aromaticity was noted at the highest maturities. In samples that were pyrolyzed for 72 h at temperatures of 300–320 °C (BR: 0.56–0.68 %Ro), Tasmanites showed similar trends, whereas at pyrolysis temperatures of 340 °C and higher (BR > 1.0 %Ro), Tasmanites was pseudomorphed by accumulations of solid bitumen, carbonate and sulfide. Replacement of Tasmanites by these phases in hydrous pyrolysis experiments ≥340 °C and its absence at higher maturities (peak oil, VR and BR ≥ 0.9 %Ro) in naturally matured samples, as documented in a previous study, implies that a large fraction of the algaenan component of original organic carbon is converted to petroleum during thermal maturation. XPS analysis indicated the molar proportion of aliphatic carbon increases with increasing thermal maturity, accompanied by decreases in oxygenated functional groups and olefinic carbon. EPMA of Tasmanites showed highest concentrations of S, with concentrations of redox-sensitive trace elements U, Mo, Ni and V generally at or below detection limits. Decrease in organic S with increasing thermal maturity may be related to cleavage of Tasmanites at C S linkages; however, this relationship was inconsistent and presence of adjacent or entrained nanoscale silicate or sulfide phases may impact measured trace element concentrations. Fluorescence microscopy and spectroscopy showed a red shift in spectral maxima and decreased emission intensities with increasing maturity, interpreted as due to non-radiative energy loss possibly because of increased aromaticity. Collectively, these results provide new insights into the in situ chemical transformations that accompany petrographic changes as oil-prone kerogen converts to petroleum with thermal advance from immature conditions into the mid-oil window.

The Lower Mississippian upper shale member of the Bakken Formation in the Williston Basin, North Dakota, consists of organic-rich, black, siliciclastic mudstones deposited offshore on a low-gradient shelf; 12 fine-grained facies are recognized and grouped into 5 facies associations (FAs). Very fine-grained, massive to faintly laminated mudstone (FA1) records deposition in the deepest, calmest parts of the basin, whereas well-laminated mudstones (FA2a); well-laminated, clay-clast–bearing mudstones (FA2b); burrow-mottled mudstone with shells (FA3); and interlaminated siltstone and mudstone (FA4) suggest deposition in the shallower, less calm, and more proximal offshore environment. These proximal-offshore mudstones (FA2a, FA2b, FA3, and FA4) reflect (1) variation in bottom-water oxygen levels and (2) lateral changes in the input of silt and clay clasts. Ubiquitous Phycosiphon fecal strings, patches of shells, burrows, and rare agglutinated foraminifera indicate dysoxic to suboxic basinal deposition and not a persistently anoxic environment. In all FAs, storm-event laminae are sparse to ubiquitous. Repeated stacking of FAs defines up to 10 coarsening-upward parasequences mostly 0.15–0.60 m (0.49–1.97 ft) thick. Individual parasequences can be correlated for 300 km (180 mi) through the basin. The lower half of the succession (interval 1) represents a transgressive systems tract and shows high radiolarian productivity with minor silt input. The upper half of the succession (interval 2) represents the base of a highstand systems tract. In contrast to interval 1, interval 2 mudstones are characterized by high clay content, low radiolarian productivity, and intermittent colonization of the sea floor during higher-order sea-level lowstands.

Magnetite is a common mineral in igneous rocks and has been used as an important petrogenetic indicator as its compositions and textures reflect changing physiochemical parameters such as temperature, oxygen fugacity and melt compositions. In upper crustal settings, igneous rocks are often altered by hydrothermal fluids such that the original textures and compositions of igneous magnetite may be partly or completely obliterated, posing interpretive problems in petrological and geochemical studies. In this paper, we present textural and compositional data of magnetite from variably albitized granitoid rocks in the Handan-Xingtai district, North China Craton to characterize the hydrothermal reequilibration of igneous magnetite. Four types of magnetite have been identified in the samples studied: pristine igneous magnetite (type 1), reequilibrated porous magnetite (type 2), reequilibrated nonporous magnetite (type 3), and hydrothermal magnetite (type 4). Pristine igneous magnetite contains abundant well-developed ilmenite exsolution lamellae that are largely replaced by titanite during subsequent hydrothermal alteration. The titanite has a larger molar volume than its precursor ilmenite and thus causes micro-fractures in the host magnetite grains, facilitating dissolution and reprecipitation of magnetite. During sodic alteration, the igneous magnetite is extensively replaced by type 2 and type 3 magnetite via fluid-induced dissolution and reprecipitation. Porous type 2 magnetite is the initial replacement product of igneous magnetite and is subsequently replaced by the nonoporous type 3 variety as its surface area is reduced and compositional equilibrium with the altering fluid is achieved. Hydrothermal type 4 magnetite is generally euhedral and lacks exsolution lamellae and porosity, and is interpreted to precipitate directly from the ore-forming fluids. Hydrothermal reequilibration of igneous magnetite has led to progressive chemical purification, during which trace elements such as Ti, Al, Mg, Zn, and Cr contents decrease dramatically (up to 2–3 orders of magnitude different), coupled with significant increase in iron concentrations from less than 64 wt.% to higher than 70 wt.%. Results presented here show that magnetite is much more susceptible to textural and compositional reequilibration than previously thought. The reequilibrated magnetite has geochemical patterns that may be distinctively different from its precursor, making existing discrimination plots questionable when applied to genetic interpretation. Based on textural characterization and high-resolution in situ compositional analyses, we propose that the Fe versus V/Ti diagram can be more confidently used to discriminate between pristine igneous magnetite, reequilibrated magnetite, and hydrothermal magnetite.

Detailed diagenetic studies of the late Cambrian Alum Shale in southern Sweden were undertaken across an interval that includes the peak Steptoean Positive Carbon Isotope Excursion (SPICE) event to evaluate the pyrite mineralization history in the formation. Samples were collected from the Andrarum-3 core (Scania, Sweden); here the Alum was deposited in the distal, siliciclastic mudstone-rich end of a shelf system. Abundant cryptobioturbation is observed in the Alum, which points to oxic–dysoxic conditions prevailing during deposition. Petrographic examination of polished thin sections (n = 65) reveals the presence of numerous texturally distinct types of pyrite, including matrix framboids, two different types of framboid concretions (those with rims of iron-dolomite and those lacking rims), disseminated euhedral pyrite crystals, concretions of euhedral pyrite crystals, overgrowths of pyrite on these different pyrite generations, anhedral pyrite intergrown with bedding parallel mineralized fractures (i.e., “beef”), and massive vertical/subvertical accumulations of pyrite.Paragenetic relationships outline the relative timing of formation of the texturally distinct pyrite. Framboids and framboid concretions formed prior to precipitation of any euhedral pyrite crystals, and these pyrite generations precipitated prior to the pyrite overgrowths on them. As Alum Shale sediments are all distorted by these texturally different pyrite generations, they are likely to have formed early in the postdepositional history of the formation. In contrast, pyrite associated with “beef” is likely temporally related to the onset of hydrocarbon generation, which in this part of Sweden is thought to have been many tens of millions of years after deposition. Because vertical/subvertical massive pyrite features distort “beef,” they clearly postdate it. Of all these pyrite textures, only framboid concretions appear to be restricted to the SPICE interval.The texturally distinct nature of the pyrite generations, along with evidence of their formation at different times in the postdepositional history of the Alum Shale, is the key outcome of this petrographic study. Because the petrographic data presented herein point to a postdeposition origin for all generations of pyrite, diagenetic processes—not those processes associated with deposition—were responsible for the complex pyritization history observed in the Alum, in the Andrarum-3 core. (Less)

Mineral thermometry and fluid inclusion studies were conducted on variably altered and mineralized samples from the Mesoproterozoic Pea Ridge iron oxide-apatite (IOA)-rare earth element (REE) deposit in order to constrain P-T conditions, fluid chemistry, and the source of salt and volatiles during early magnetite and later REE mineralization. Scanning electron microscopy (SEM)-cathodoluminescence and SEM-backscatter electron images show that quartz and rutile precipitated before, during, and after magnetite and REE mineral growth. Ti-in-quartz and Zr-in-rutile equilibration temperatures range from ≤350° to 750°C in the amphibole, magnetite, hematite, and silicified zones where T increased during magnetite and quartz growth and dropped precipitously after fracturing and brecciation. Late drusy quartz cements within a REE-rich breccia pipe record the lowest T (≤315°–400°C). Liquid-, vapor-rich, and hypersaline (±hematite, calcite) fluid inclusions are common and liquid CO 2 is present locally. Salinities define three populations: saline (10–27 wt % NaCl equiv), hypersaline (34–>60 wt % NaCl equiv), and dilute (0–10 wt % NaCl equiv ). The wide range of eutectic melting temperatures (−67° to −19°C) suggests that saline inclusions trapped variable proportions of a CaCl-MgCl-FeCl-bearing fluid end member and an NaCl-KCl fluid end member. Homogenization temperatures and pressures of these saline inclusions suggest they were trapped when fluids unmixed into brine and vapor at T The Na/Cl, Na/K, and Cl/Br ratios of fluid inclusion extracts provide evidence for mixtures of magmatic hydrothermal fluids and evaporated seawater. Extracts from magnetite, hematite, and pyrite plot in the magmatic-hydrothermal field, indicating that Fe was derived from a magmatic source. Their enrichments in Mg and Ca are consistent with a mafic magmatic source. The positive correlation between Na/Mg and Na/Ca ratios may be due to halite saturation or albitization of igneous rocks. Extracts from barite in the REE-rich breccia pipes are enriched in Na and Br and plot near the seawater evaporation trend. He is highly enriched relative to Ne and Ar in fluid inclusion extracts, which precludes air as a source of He. Although the He is mostly of crustal origin, pyrite with a 3 He/ 4 He (R/R A ) of 0.1 contains up to 12% mantle He. Many extracts have low 20 Ne/ 22 Ne ratios due to nucleogenic production of 22 Ne in high F/O minerals such as fluorapatite or F biotite. The arrays of data for 3 He/ 4 He (R/R A ) and 22 Ne/ 20 Ne suggest that volatiles were derived from two sources, a moderate F mafic magma containing mantle He and a high F silicic magma with crustal He. Together with other evidence cited in this report, these data (1) support a magmatic hydrothermal origin for the Mesoproterozoic magnetite-apatite deposit with ore fluids derived from a concealed mafic to intermediate-composition intrusion, (2) suggest that the REE minerals in breccia pipes were either derived from apatite or precipitated in response to decompression and cooling during breccia pipe formation, (3) provide evidence for the influx of basinal brine, magmatic fluids from granitic intrusions, and meteoric water after breccia pipe formation, and (4) show that Pea Ridge was relatively unaffected by the late Paleozoic Mississippi Valley-type (MVT) Pb-Zn system in overlying Cambrian sedimentary rocks.

Rare earth element (REE) resources are currently of great interest because of their importance as raw materials for high-technology manufacturing. The REE-phosphates monazite (light REE enriched) and xenotime (heavy REE enriched) resist weathering and can accumulate in placer deposits as part of the heavy mineral assemblage. The Atlantic and Gulf coastal plains of the southeastern United States are known to host heavy mineral deposits with economic concentrations of zircon, ilmenite and rutile. This study provides a perspective on the distribution and composition of REE phosphate minerals in the region. The elemental chemistry and mineralogy of sands and associated heavy-mineral assemblages from new and archived sediment samples across the coastal plains are examined, along with phase-specific compositions of monazite, xenotime and zircon. Both monazite and xenotime are present across the coastal plains. The phase-specific compositions allow monazite content to be estimated using La as a geochemical proxy. Similarly, both Y and Yb are geochemical proxies for xenotime, but their additional presence in zircon and monazite require a correction to prevent overestimation of xenotime content. Applying this correction, maps of monazite and xenotime content across the coastal plains were generated using sample coverage from the National Geochemical Database (NGS) and National Uranium Resource Evaluation (NURE). The NGS and NURE approach of sampling stream sediments in small watersheds links samples to nearby lithologies. The results show an approximately 40 km-wide band of primarily Cretaceous, marine sediments bordering the Piedmont province from North Carolina to Alabama in which monazite and xenotime content are relatively high (up to 4.4 wt. % in

A comparison study of selected static leaching and acid–base accounting (ABA) methods using a mineralogically diverse set of 12 modern-style, metal mine waste samples was undertaken to understand the relative performance of the various tests. To complement this study, in-depth mineralogical studies were conducted in order to elucidate the relationships between sample mineralogy, weathering features, and leachate and ABA characteristics. In part one of the study, splits of the samples were leached using six commonly used leaching tests including paste pH, the U.S. Geological Survey (USGS) Field Leach Test (FLT) (both 5-min and 18-h agitation), the U.S. Environmental Protection Agency (USEPA) Method 1312 SPLP (both leachate pH 4.2 and leachate pH 5.0), and the USEPA Method 1311 TCLP (leachate pH 4.9). Leachate geochemical trends were compared in order to assess differences, if any, produced by the various leaching procedures. Results showed that the FLT (5-min agitation) was just as effective as the 18-h leaching tests in revealing the leachate geochemical characteristics of the samples. Leaching results also showed that the TCLP leaching test produces inconsistent results when compared to results produced from the other leaching tests. In part two of the study, the ABA was determined on splits of the samples using both well-established traditional static testing methods and a relatively quick, simplified net acid–base accounting (NABA) procedure. Results showed that the traditional methods, while time consuming, provide the most in-depth data on both the acid generating, and acid neutralizing tendencies of the samples. However, the simplified NABA method provided a relatively fast, effective estimation of the net acid–base account of the samples. Overall, this study showed that while most of the well-established methods are useful and effective, the use of a simplified leaching test and the NABA acid–base accounting method provide investigators fast, quantitative tools that can be used to provide rapid, reliable information about the leachability of metals and other constituents of concern, and the acid-generating potential of metal mining waste.

Mineral maps based on Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) data were used to study late Miocene advanced argillic alteration at Cuprite, Nevada. Distributions of Fe-bearing minerals, clays, micas, sulfates, and carbonates were mapped using the Tetracorder spectral-shape matching system. The Al content of white micas increases toward altered areas and near intrusive rocks. Alunite composition varies from pure K to intimate mixtures of Na-K endmembers with subpixel occurrences of huangite, the Ca analogue of alunite. Intimately mixed Na-K alunite marks areas of relatively lower alteration temperature, whereas co-occurring Na-alunite and dickite may delineate relict hydrothermal conduits. The presence of dickite, halloysite, and well-ordered kaolinite, but absence of disordered kaolinite, is consistent with acidic conditions during hydrothermal alteration. Partial lichen cover on opal spectrally mimics chalcedony, limiting its detection to lichen-free areas. Pods of buddingtonite are remnants of initial quartz-adularia-smectite alteration. Thus, spectral maps provide a synoptic view of the surface mineralogy, and define a previously unrecognized early steam-heated hydrothermal event. Faulting and episodes of hydrothermal alteration at Cuprite were intimately linked to upper plate movements above the Silver Peak-Lone Mountain detachment and growth, collapse, and resurgence of the nearby Stonewall Mountain volcanic complex between 8 and 5 Ma. Isotopic dating indicates that hydrothermal activity started at least by 7.61 Ma and ended by about 6.2 Ma. Spectral and stable isotope data suggest that Cuprite is a late Miocene low-sulfidation adularia-sericite type hot spring deposit overprinted by late-stage, steam-heated advanced argillic alteration formed along the margin of the Stonewall Mountain caldera.

Hyperacidic lakes and associated solfatara in active volcanoes are the expression of magmatic gas expansion from source to surface. Here we show for the first time, that the vein system that comprises the ~ 2 Ma high-sulfidation, Lepanto copper–gold deposit in the Mankayan district (Philippines) was associated with a contemporary hyperacidic volcanic lake complex—possibly the first such lake recognized in the geological record. A 15–20‰ difference in sulfur isotopic composition between barite and sulfides and sulfosalts in the vent fumarole encrustations supports the interpretation that SO 2 -rich volcanic gas vented into the base of the lake and marginal to it and ties the mineralization directly to magmatic gas expansion, fracture propagation, and mineralization that occurred through a series of decompression steps within the feeder fracture network. These data confirm that crater lake environments such as Kawah Ijen (Java, Indonesia) provide modern day analogs of the Lepanto and other high sulfidation Cu–Au depositing environments. We also provide extensive analysis of sulfosalt–sulfide reactions during vein formation within the hyperacidic lake complex. Pyrite ± silica deposited first at high temperature followed by enargite that preserves the vapor–solid diffusion of, for example, antimony, tin, and tellurium into the vapor from the crystallizing solid. Subsolidus, intra-crystalline diffusion continued as temperature declined. Pyrite and enargite are replaced by Fe-tennantite in the lodes which initially has low Sb/(Sb + As) atomic ratios around 13.5% close to the ideal tennantite formula, but evolves to higher ratios as crystallization proceeds. Fumarole encrustation clasts and sulfosalts in the lake sediment are more highly evolved with a larger range of trace element substitutions, including antimony. Substitution of especially Zn, Te, Ag, and Sn into tennantite records metal and semi-metal fractionation between the expanding magmatic gas and deposited sulfide sublimates provides a rare insight into the fate of metals and semi-metals in the shallower parts of fracture arrays that feed modern hyperacidic lakes. These data support a growing understanding of the formation of high-sulfidation gold deposits as the consequence of single-phase expansion of gas from magmatic-gas reservoirs beneath the surface of active volcanoes without the intervention of a later aqueous fluid including groundwater. Aggressive sulfide–sulfosalt reactions, including pitting and the almost complete dissolution of earlier minerals, are persistent characteristics of the vein assemblages and precious metals typically occur late in pits or along brittle fractures. These characteristics support a hypothesis of mineral deposition at temperatures of the order of 600 °C in contrast to available fluid inclusion data from enargite that record temperatures following phase transitions in the sulfosalt during the retrograde devolution of the deposit in the presence of groundwater.

Six epizonal gold deposits in the 30-km-long Yangshan gold belt, Gansu Province are estimated to contain more than 300 t of gold at an average grade of 4.76 g/t and thus define one of China's largest gold resources. Detailed paragenetic studies have recognized five stages of sulfide mineral precipitation in the deposits of the belt. Syngenetic/diagenetic pyrite (Py0) has a framboidal or colloform texture and is disseminated in the metasedimentary host rocks. Early hydrothermal pyrite (Py1) in quartz veins is disseminated in metasedimentary rocks and dikes and also occurs as semi-massive pyrite aggregates or bedding-parallel pyrite bands in phyllite. The main ore stage pyrite (Py2) commonly overgrows Py1 and is typically associated with main ore stage arsenopyrite (Apy2). Late ore stage pyrite (Py3), arsenopyrite (Apy3), and stibnite occur in quartz ± calcite veins or are disseminated in country rocks. Post-ore stage pyrite (Py4) occurs in quartz ± calcite veins that cut all earlier formed mineralization. Electron probe microanalyses and laser ablation-inductively coupled plasma mass spectrometry analyses reveal that different generations of sulfides have characteristic of major and trace element patterns, which can be used as a proxy for the distinct hydrothermal events. Syngenetic/diagenetic pyrite has high concentrations of As, Au, Bi, Co, Cu, Mn, Ni, Pb, Sb, and Zn. The Py0 also retains a sedimentary Co/Ni ratio, which is distinct from hydrothermal ore-related pyrite. Early hydrothermal Py1 has high contents of Ag, As, Au, Bi, Cu, Fe, Sb, and V, and it reflects elevated levels of these elements in the earliest mineralizing metamorphic fluids. The main ore stage Py2 has a very high content of As (median value of 2.96 wt%) and Au (median value of 47.5 ppm) and slightly elevated Cu, but relatively low values for other trace elements. Arsenic in the main ore stage Py2 occurs in solid solution. Late ore stage Py3, formed coevally with stibnite, contains relatively high As (median value of 1.44 wt%), Au, Fe, Mn, Mo, Sb, and Zn and low Bi, Co, Ni, and Pb. The main ore stage Apy2, compared to late ore stage arsenopyrite, is relatively enriched in As, whereas the later Apy3 has high concentrations of S, Fe, and Sb, which is consistent with element patterns in associated main and late ore stage pyrite generations. Compared with pyrite from other stages, the post-ore stage Py4 has relatively low concentrations of Fe and S, whereas As remains elevated (2.05∼3.20 wt%), which could be interpreted by the substitution of As− for S in the pyrite structure. These results suggest that syngenetic/diagenetic pyrite is the main metal source for the Yangshan gold deposits where such pyrite was metamorphosed at depth below presently exposed levels. The ore-forming elements were concentrated into the hydrothermal fluids during metamorphic devolatilization, and subsequently, during extensive fluid–rock interaction at shallower levels, these elements were precipitated via widespread sulfidation during the main ore stage.

Background: In 2010, Médecins Sans Frontières discovered a lead poisoning outbreak linked to artisanal gold processing in northwestern Nigeria. The outbreak has killed approximately 400 young children and affected thousands more. Objectives: Our aim was to undertake an interdisciplinary geological- and health-science assessment to clarify lead sources and exposure pathways, identify additional toxicants of concern and populations at risk, and examine potential for similar lead poisoning globally. Methods: We applied diverse analytical methods to ore samples, soil and sweep samples from villages and family compounds, and plant foodstuff samples. Results: Natural weathering of lead-rich gold ores before mining formed abundant, highly gastric-bioaccessible lead carbonates. The same fingerprint of lead minerals found in all sample types confirms that ore processing caused extreme contamination, with up to 185,000 ppm lead in soils/sweep samples and up to 145 ppm lead in plant foodstuffs. Incidental ingestion of soils via hand-to-mouth transmission and of dusts cleared from the respiratory tract is the dominant exposure pathway. Consumption of water and foodstuffs contaminated by the processing is likely lesser, but these are still significant exposure pathways. Although young children suffered the most immediate and severe consequences, results indicate that older children, adult workers, pregnant women, and breastfed infants are also at risk for lead poisoning. Mercury, arsenic, manganese, antimony, and crystalline silica exposures pose additional health threats. Conclusions: Results inform ongoing efforts in Nigeria to assess lead contamination and poisoning, treat victims, mitigate exposures, and remediate contamination. Ore deposit geology, pre-mining weathering, and burgeoning artisanal mining may combine to cause similar lead poisoning disasters elsewhere globally.

Pennsylvanian coals in the Appalachian Basin host pyrite that is locally enriched in potentially toxic trace elements such as As, Se, Hg, Pb, and Ni. A comparison of pyrite-rich coals from northwestern Alabama, eastern Kentucky, and West Virginia reveals differences in concentrations and mode of occurrence of trace elements in pyrite. Pyrite occurs as framboids, dendrites, or in massive crystalline form in cell lumens or crosscutting veins. Metal concentrations in pyrite vary over all scales, from microscopic to mine to regional, because trace elements are inhomogeneously distributed in the different morphological forms of pyrite, and in the multiple generations of sulfide mineral precipitates. Early diagenetic framboidal pyrite is usually depleted in As, Se, and Hg, and enriched in Pb and Ni, compared to other pyrite forms. In dendritic pyrite, maps of As distribution show a chemical gradient from As-rich centers to As-poor distal branches, whereas Se concentrations are highest at the distal edges of the branches. Massive crystalline pyrite that fills veins is composed of several generations of sulfide minerals. Pyrite in late-stage veins commonly exhibits As-rich growth zones, indicating a probable epigenetic hydrothermal origin. Selenium is concentrated at the distal edges of veins. A positive correlation of As and Se in pyrite veins from Kentucky coals, and of As and Hg in pyrite-filled veins from Alabama coals, suggests coprecipitation of these elements from the same fluid. In the Kentucky coal samples (n = 18), As and Se contents in pyrite-filled veins average 4200 ppm and 200 ppm, respectively. In Alabama coal samples, As in pyrite-filled veins averages 2700 ppm (n = 34), whereas As in pyrite-filled cellular structures averages 6470 ppm (n = 35). In these same Alabama samples, Se averages 80 ppm in pyrite-filled veins, but was below the detection limit in cell structures. In samples of West Virginia massive pyrite, As averages 1700 ppm, and Se averages 270 ppm (n = 24). The highest concentration of Hg (≤ 102 ppm) is in Alabama pyrite veins. Improved detailed descriptions of sulfide morphology, sulfide mineral paragenesis, and trace-element concentration and distribution allow more informed predictions of: (1) the relative rate of release of trace elements during weathering of pyrite in coals, and (2) the relative effectiveness of various coal-cleaning procedures of removing pyrite. For example, trace element-rich pyrite has been shown to be more soluble than stoichiometric pyrite, and fragile fine-grained pyrite forms such as dendrites and framboids are more susceptible to dissolution and disaggregation but less amenable to removal during coal cleaning.

Re–Os geochronology of fractions composed of unsized, coarse, and fine molybdenite from a pod of unusual monazite–xenotime gneiss within a granulite facies paragneiss, Hudson Highlands, NY, yielded dates of 950.5 ± 2.5, 953.8 ± 2.6, and 941.2 ± 2.6 Ma, respectively. These dates are not recorded by co-existing zircon, monazite, or xenotime. SEM–BSE imagery of thin sections and separated grains reveals that most molybdenite grains are composed of core and rim plates that are approximately perpendicular. Rim material invaded cores, forming irregular contacts, probably reflecting dissolution/reprecipitation. EPMA and LA-ICP-MS analyses show that cores and rims have different trace element concentrations (for example, cores are relatively enriched in W). On the basis of inclusions of zircon with metamorphic overgrowths, we conclude that molybdenite cores and rims formed after high-grade regional metamorphism. The discovery of cores and rims in individual molybdenite grains is analogous to multi-component U-Pb geochronometers such as zircon, monazite, and titanite; thus, molybdenite should be carefully examined before dating to ensure that the requirement of age homogeneity is fulfilled.

The U.S. Geological Survey (USGS) has been producing reference materials since the 1950s. Over 50 materials have been developed to cover bulk rock, sediment, and soils for the geological community. These materials are used globally in geochemistry, environmental, and analytical laboratories that perform bulk chemistry and/or microanalysis for instrument calibration and quality assurance testing. To answer the growing demand for higher spatial resolution and sensitivity, there is a need to create a new generation of microanalytical reference materials suitable for a variety of techniques, such as scanning electron microscopy/X-ray spectrometry (SEM/EDS), electron probe microanalysis (EPMA), laser ablation inductively coupled mass spectrometry (LA-ICP-MS), and secondary ion mass spectrometry (SIMS). As such, the microanalytical reference material (MRM) needs to be stable under the beam, be homogeneous at scales of better than 10–25 micrometers for the major to ultra-trace element level, and contain all of the analytes (elements or isotopes) of interest. Previous development of basaltic glasses intended for LA-ICP-MS has resulted in a synthetic basaltic matrix series of glasses (USGS GS-series) and a natural basalt series of glasses (BCR-1G, BHVO-2G, and NKT-1G). These materials have been useful for the LA-ICP-MS community but were not originally intended for use by the electron or ion beam community. A material developed from start to finish with intended use in multiple microanalytical instruments would be useful for inter-laboratory and inter-instrument platform comparisons.This article summarizes the experiments undertaken to produce a basalt glass reference material suitable for distribution as a multiple-technique round robin material. The goal of the analytical work presented here is to demonstrate that the elemental homogeneity of the new glass is acceptable for its use as a reference material. Because the round robin exercise is still underway, only nominal compositional ranges for each element are given in the article.

Cathodoluminescent (CL) textures in quartz reveal successive histories of the physical and chemical fluctuations that accompany crystal growth. Such CL textures reflect trace element concentration variations that can be mapped by electron microprobe or laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Trace element maps in hydrothermal quartz from four different ore deposit types (Carlin-type Au, epithermal Ag, porphyry-Cu, and MVT Pb-Zn) reveal correlations among trace elements and between trace element concentrations and CL textures. The distributions of trace elements reflect variations in the physical and chemical conditions of quartz precipitation. These maps show that Al is the most abundant trace element in hydrothermal quartz. In crystals grown at temperatures below 300 °C, Al concentrations may vary by up to two orders of magnitude between adjacent growth zones, with no evidence for diffusion. The monovalent cations Li, Na, and K, where detectable, always correlate with Al, with Li being the most abundant of the three. In most samples, Al is more abundant than the combined total of the monovalent cations; however, in the MVT sample, molar Al/Li ratios are ~0.8. Antimony is present in concentrations up to ~120 ppm in epithermal quartz (~200–300 °C), but is not detectable in MVT, Carlin, or porphyry-Cu quartz. Concentrations of Sb do not correlate consistently with those of other trace elements or with CL textures. Titanium is only abundant enough to be mapped in quartz from porphyry-type ore deposits that precipitate at temperatures above ~400 °C. In such quartz, Ti concentration correlates positively with CL intensity, suggesting a causative relationship. In contrast, in quartz from other deposit types, there is no consistent correlation between concentrations of any trace element and CL intensity fluctuations.

Quartz occurs in a wide range of geologic environments throughout the Earth's crust. The concentration and distribution of trace elements in quartz provide information such as temperature and other physical conditions of fomation. Trace element analySes with modern electron-probe microanalysis (EPMA) instruments can achieve 99% confidence detection of - 100 ppm with fairly minimal effort for many elements in samples of low to moderate aVerage atomic number such as mauy common oxides and silicates. HoweVer, trace element measurements below 100 ppm in many materials are limited, not ouly by the precision of the background measurement, but also by the accuracy with which background levels are determined. A new "blank" correction algorithm has been developed and tested on both Cameca and JEOL instruments, which applies a quantitative correction to the emitted X-ray intensities duriug the iteration of the sample matrix correction based on a zero level (or known trace) abundance calibration standard. This iterated blank correction, when combined with improved background fit models, and an "aggregate'' intensity calculation utilizing multiple spectrometer intensities in software for greater geometric efficiency, yields a detection limit of 2 to 3 ppm for Ti and 6 to 7 ppm for AI in quartz at 99% t-test confidence with similar levels for absolute accuracy.