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At least 19 recordsLinked to original sources
USGS2006

Aqueous geochemical data from the analysis of stream-water samples collected in June and July 2005 — Taylor Mountains 1:250,000 scale quadrangle, Alaska

We report on the chemical analysis of water samples collected from the Taylor Mountains 1:250,000-scale quadrangle. Parameters for which data are reported include pH, conductivity, water temperature, major cation and anion concentrations, trace-element concentrations, and dissolved organic-carbon concentrations. Samples were collected as part of a multiyear U.S. Geological Survey project "Geologic and Mineral Deposit Data for Alaskan Economic Development." Data presented here are from samples collected in June and July of 2005. The data are being released at this time with minimal interpretation. This is the second release of aqueous geochemical data from this project; 2004 aqueous geochemical data were published previously ( Wang and others, 2006 ). The data in this report augment but do not duplicate or supersede the previous data release. Site selection was based on a regional sampling strategy that focused on first- and second-order drainages. Water sample site selection was based on landscape parameters that included physiography, wetland extent, lithological changes, and a cursory field review of mineralogy from pan concentrates. Stream water in the Taylor Mountians quadrangle is dominated by bicarbonate (HCO 3- ), though in a few samples more than 50 percent of the anionic charge can be attributed to sulfate (SO 4 2- ). The major-cation chemistry ranges from Ca 2+ /Mg 2+ dominated to a mix of Ca 2+ /Mg 2+ /Na + +K + . In general, good agreement was found between the major cations and anions in the duplicate samples. Many trace elements in these samples were at or near the analytical method detection limit, but good agreement was found between duplicate samples for elements with detectable concentrations. With the exception of a total mercury concentration of 0.33 ng/L detected in a field blank, field blank major-ion and trace-elements concentrations were below detection.

Alaska↗
USGS2011

Aqueous geochemical data from the analysis of stream-water samples collected in June and July 2006 — Taylor Mountains 1:250,000-scale quadrangle, Alaska

We report on the chemical analysis of water samples collected from the Taylor Mountains 1:250,000-scale quadrangle, Alaska. Parameters for which data are reported include pH, conductivity, water temperature, major cation and anion concentrations, trace-element concentrations, and dissolved organic-carbon concentrations. Samples were collected as part of a multiyear U.S. Geological Survey project entitled ?Geologic and Mineral Deposit Data for Alaskan Economic Development.? Data presented here are from samples collected in June and July 2006. The data are being released at this time with minimal interpretation. This is the third release of aqueous geochemical data from this project; aqueous geochemical data from samples collected in 2004 and 2005 were published previously. The data in this report augment but do not duplicate or supersede the previous data release. Site selection was based on a regional sampling strategy that focused on first- and second-order drainages. Water sample site selection was based on landscape parameters that included physiography, wetland extent, lithological changes, and a cursory field review of mineralogy from pan concentrates. Stream water in the Taylor Mountains quadrangle is dominated by bicarbonate (HCO3-), although in a few samples more than 50 percent of the anionic charge can be attributed to sulfate (SO42-). The major-cation chemistry ranges from Ca2+/Mg2+ dominated to a mix of Ca2+/Mg2+/Na++K+. Generally, good agreement was found between the major cations and anions in the duplicate samples. Many trace elements in these samples were at or near the analytical method detection limit, but good agreement was found between duplicate samples for elements with detectable concentrations. All field blank major-ion and trace-element concentrations were below detection.

Alaska↗
USGS2011

Aqueous geochemical data from the analysis of stream-water samples collected in June and August 2008—Taylor Mountains 1:250,000- and Dillingham D-4 1:63,360-scale quadrangles, Alaska

We report on the chemical analysis of water samples collected from the Taylor Mountains 1:250,000- and Dillingham D-4 1:63,360-scale quadrangles, Alaska. Reported parameters include pH, conductivity, water temperature, major cation and anion concentrations, and trace-element concentrations. We collected the samples as part of a multiyear U.S. Geological Survey project entitled "Geologic and Mineral Deposit Data for Alaskan Economic Development." Data presented here are from samples collected in June and August 2008. Minimal interpretation accompanies this data release. This is the fourth release of aqueous geochemical data from this project; data from samples collected in 2004, 2005, and 2006 were published previously. The data in this report augment but do not duplicate or supersede the previous data releases. Site selection was based on a regional sampling strategy that focused on first- and second-order drainages. Water sample sites were selected on the basis of landscape parameters that included physiography, wetland extent, lithological changes, and a cursory field review of mineralogy from pan concentrates. Stream water in the study area is dominated by bicarbonate (HCO 3 - ), although in a few samples more than 50 percent of the anionic charge can be attributed to sulfate (SO 4 2- ). The major-cation chemistry of these samples ranges from Ca 2+ -Mg 2+ dominated to a mix of Ca 2+ -Mg 2+ -Na + +K 2+ . In most cases, analysis of duplicate samples showed good agreement for the major cation and major anions with the exception of the duplicate samples at site 08TA565. At site 08TA565, Ca, Mg, Cl, and CaCO 3 exceeded 25 percent and the concentrations of trace elements As, Fe and Mn also exceeded 25 percent in this duplicate pair. Chloride concentration varied by more than 25 percent in 5 of the 11 duplicated samples. Trace-element concentrations in these samples generally were at or near the detection limit for the method used and, except for Co at site 08TA565, generally good agreement was determined between duplicate samples for elements with detectable concentrations. Major-ion concentrations were below detection limits in all field blanks, and the trace-element concentrations also were generally below detection limits; however, Co, Mn, Na, Zn, Cl, and Hg were detected in one or more field blank samples.

Alaska↗
USGS2011

Magmatic-vapor expansion and the formation of high-sulfidation gold deposits: Chemical controls on alteration and mineralization

Large bulk-tonnage high-sulfidation gold deposits, such as Yanacocha, Peru, are the surface expression of structurally-controlled lode gold deposits, such as El Indio, Chile. Both formed in active andesite–dacite volcanic terranes. Fluid inclusion, stable isotope and geologic data show that lode deposits formed within 1500 m of the paleo-surface as a consequence of the expansion of low-salinity, low-density magmatic vapor with very limited, if any, groundwater mixing. They are characterized by an initial ‘Sulfate’ Stage of advanced argillic wallrock alteration ± alunite commonly with intense silicification followed by a ‘Sulfide’ Stage — a succession of discrete sulfide–sulfosalt veins that may be ore grade in gold and silver. Fluid inclusions in quartz formed during wallrock alteration have homogenization temperatures between 100 and over 500 °C and preserve a record of a vapor-rich environment. Recent data for El Indio and similar deposits show that at the commencement of the Sulfide Stage, ‘condensation’ of Cu–As–S sulfosalt melts with trace concentrations of Sb, Te, Bi, Ag and Au occurred at > 600 °C following pyrite deposition. Euhedral quartz crystals were simultaneously deposited from the vapor phase during crystallization of the vapor-saturated melt occurs to Fe-tennantite with progressive non-equilibrium fractionation of heavy metals between melt-vapor and solid. Vugs containing a range of sulfides, sulfosalts and gold record the changing composition of the vapor. Published fluid inclusion and mineralogical data are reviewed in the context of geological relationships to establish boundary conditions through which to trace the expansion of magmatic vapor from source to surface and consequent alteration and mineralization. Initially heat loss from the vapor is high resulting in the formation of acid condensate permeating through the wallrock. This Sulfate Stage alteration effectively isolates the expansion of magmatic vapor in subsurface fracture arrays from any external contemporary hydrothermal activity. Subsequent fracturing is localized by the embrittled wallrock to provide high-permeability fracture arrays that constrain vapor expansion with minimization of heat loss. The Sulfide Stage vein sequence is then a consequence of destabilization of metal-vapor species in response to depressurization and decrease in vapor density. The geology, mineralogy, fluid inclusion and stable isotope data and geothermometry for high-sulfidation, bulk-tonnage and lode deposits are quite different from those for epithermal gold–silver deposits such as McLaughlin, California that formed near-surface in groundwater-dominated hydrothermal systems where magmatic fluid has been diluted to less than about 30%. High sulfidation gold deposits are better termed ‘Solfataric Gold Deposits’ to emphasize this distinction. The magmatic-vapor expansion hypothesis also applies to the phenomenology of acidic geothermal systems in active volcanic systems and equivalent magmatic-vapor discharges on the flanks of submarine volcanoes.

Ore Geology Reviews↗
USGS2006

Aqueous geochemical data from the analysis of stream water samples collected in August 2004: Taylor Mountains 1:250,000 scale quadrangle, Alaska

We report on the chemical analysis of water samples collected from the Taylor Mountains 1:250,000 quadrangle. Samples were collected as part of the multi-year U.S. Geological Survey's project -- Geologic and Mineral Deposit Data for Alaskan Economic Development. Data presented here are from water samples collected primarily in the northeastern part of the Taylor Mountains quadrangle. The data include samples taken from the Taylor Mountains C1, C2, D1, D2, and D4 1:63,360 scale quadrangles. The data are being released at this time with minimal interpretation. Site selection was based on a regional sampling strategy that focused on first and second order drainages. Water sampling site selection was based on landscape parameters that included physiography, wetland extent, lithological changes, and the cursory field review of the mineralogy from the pan concentrates. Stream water in the Taylor Mountians quadrangle is dominated by bicarbonate (HCO3-), though in a few samples more than 50% of the anionic charge can be attibuted to sulfate ( SO42-). The major-cation chemistry range from Ca/Mg dominated to a mix of Ca/Mg/Na+K. Good agreement was found between the major cation and anions in the duplicate samples. Many trace elements were at or near the method detection limit in these samples but good agreement was found between duplicate samples for elements with detectable concentrations. Major ion concentrations were below detection in all field blanks and the trace elements concentrations generally were below detection. However, Ta (range 0.9 -.1 ug/L) and Zn (1 to 3.5 ug/L) were detected in all blanks and Ba ( 0.24 ug/L) and Th (0.2 ug/L) were detected in one blank. There was good agreement between dupilicate total- and methyl- mercury and DOC samples; however, total mercury, methyl-mercury and dissolve organic carbon (DOC) were detected in the blank at 2.35 ng/L, 0.07 ng/L and 0.57 mg/L, respectively.

Alaska↗
USGS2008

Thermometers and thermobarometers in granitic systems

The ability to determine the thermal and barometric history during crystallization and emplacement of granitic plutons has been enhanced by several new calibrations applicable to granitic mineral assemblages. Other existing calibrations for granitic plutons have continued to be popular and fairly robust. Recent advances include the trace element thermometers Ti-in-quartz, Ti-in-zircon, and Zr-in-sphene (titanite), which need to be further evaluated on the roles of reduced activities due to lack of a saturating phase, the effect of pressure dependence (particularly for the Ti-in-zircon thermometer), and how resistive these thermometers are to subsolidus reequilibration. As zircon and sphene are also hosts to radiogenic isotopes, these minerals potentially also provide new insights into the temperature - time history of magmas. When used in conjunction with pressure-sensitive mineral equilibria in the same rocks, a complete assessment of the P-T-t (pressure-temperature-time) path is possible given that the mineralogy of plutons can reflect crystallization over a range of pressure and temperature during ascent and emplacement and that many intrusions are now seen as forming over several millions of years during the protracted history of batholith construction. Accessory mineral saturation thermometers, such as those for zircon, apatite, and allanite, provide a different and powerful perspective, specifically that of the temperature of the onset of crystallization of these minerals, which can allow an estimate of the range of temperature between the liquidus and solidus of a given pluton. In assessment of the depth of crystallization and emplacement of granitic plutons, the Al-in-hornblende remains popular for metaluminous granites when appropriately corrected for temperature. For peraluminous granites, potential new calibrations exist for the assemblages bearing garnet, biotite, plagioclase, muscovite, and quartz. Other thermometers, based on oxygen abundance, and including Fe-Ti oxides, pyroxene, fayalitic olivine, quartz, sphene, and/or biotite, some of which have been recently revised, can provide additional information on temperature and oxygen fugacity. Oxygen fugacity can range over several orders of magnitude in different magmatic systems and can have profound influence on the mineralogy and mineral compositions in granitic magmas. It also forms the foundation of the popular magnetite- versus ilmenite-series granite classification. Copyright ?? Mineralogical Society of America.

Reviews in Mineralogy and Geochemistry↗
USGS2014

Arsenic associated with historical gold mining in the Sierra Nevada foothills: Case study and field trip guide for Empire Mine State Historic Park, California

The Empire Mine, together with other mines in the Grass Valley mining district, produced at least 21.3 million troy ounces (663 tonnes) of gold (Au) during the 1850s through the 1950s, making it the most productive hardrock Au mining district in California history ( Clark 1970 ). The Empire Mine State Historic Park (Empire Mine SHP or EMSHP), established in 1975, provides the public with an opportunity to see many well-preserved features of the historic mining and mineral processing operations ( CDPR 2014a ). A legacy of Au mining at Empire Mine and elsewhere is contamination of mine wastes and associated soils, surface waters, and groundwaters with arsenic (As), mercury (Hg), lead (Pb), and other metals. At EMSHP, As has been the principal contaminant of concern and the focus of extensive remediation efforts over the past several years by the State of California, Department of Parks and Recreation (DPR) and Newmont USA, Ltd. In addition, the site is the main focus of a multidisciplinary research project on As bioavailability and bioaccessibility led by the California Department of Toxic Substances Control (DTSC) and funded by the U.S. Environmental Protection Agency’s (USEPA’s) Brownfields Program. This chapter was prepared as a guide for a field trip to EMSHP held on June 14, 2014, in conjunction with a short course on “Environmental Geochemistry, Mineralogy, and Microbiology of Arsenic” held in Nevada City, California on June 15–16, 2014. This guide contains background information on geological setting, mining history, and environmental history at EMSHP and other historical Au mining districts in the Sierra Nevada, followed by descriptions of the field trip stops.

Reviews in Mineralogy and Geochemistry↗
USGS2014

The environmental geochemistry of Arsenic – An overview

Arsenic is one of the most prevalent toxic elements in the environment. The toxicity, mobility, and fate of arsenic in the environment are determined by a complex series of controls dependent on mineralogy, chemical speciation, and biological processes. The element was first described by Theophrastus in 300 B.C. and named arsenikon (also arrhenicon; Caley and Richards 1956 ) referring to its “potent” nature, although it was originally considered an alternative form of sulfur ( Boyle and Jonasson 1973 ). Arsenikon is believed to be derived from the earlier Persian, zarnik (online etymology dictionary, http://www.etymonline.com/index.php?term=arsenic ). It was not until the thirteenth century that an alchemist, Albertus Magnus, was able to isolate the element from orpiment, an arsenic sulfide (As 2 S 3 ). The complex chemistry required to do this led to arsenic being considered a “bastard metal” or what we now call a “metalloid,” having properties of both metals and non-metals. As a chemical element, arsenic is widely distributed in nature and can be concentrated in many different ways. In the Earth’s crust, arsenic is concentrated by magmatic and hydrothermal processes and has been used as a “pathfinder” for metallic ore deposits, particularly gold, tin, copper, and tungsten ( Boyle and Jonasson 1973 ; Cohen and Bowell 2014 ). It has for centuries been considered a potent toxin, is a common poison in actual and fictional crimes, and has led to significant impacts on human health in many areas of the world ( Cullen 2008 ; Wharton 2010 ).

Reviews in Mineralogy and Geochemistry↗
USGS2009

Approaches to modeling weathered regolith

Sustainable soils are a requirement for maintaining human civilizations ( Carter and Dale 1974 ; Lal 1989 ). However, as the “most complicated biomaterial on the planet” ( Young and Crawford 2004 ), soils represent one of the most difficult systems to understand and model with respect to chemical, physical, and biological coupling over time (Fig. 1 ). Despite the complexity of these interactions, certain patterns in soil properties and development are universally observed and have been used in soil science as a means for classification. Elemental, mineralogical, or isotopic concentrations in soils plotted versus depth beneath the land surface comprise such patterns. Soil depth profiles are often reported for solid soil materials, and, less frequently, for solutes in soil pore waters. These profiles cross a large range in spatial scales that traditionally have been studied by different disciplines. For example, shallow, biologically active horizons are commonly defined as the soil zone in agronomic studies whereas the mobile layer of the regolith is referred to as soil in geomorphological studies. In contrast, many geochemical studies target chemical weathering to tens or even hundreds of meters in depth, sometimes extending the definition of “soils” to include the entire regolith down to parent bedrock or alluvium. Soil profiles also exhibit a large range in temporal scales ( Amundson 2004 ; Brantley 2008b ). Solid-state profiles document chemical and mineralogical changes integrated over the time scales of evolution of regolith from protolith. This “geologic time” can vary from tens to hundreds of years for weathered material developed on moraines deposited by active glaciers ( Anderson et al. 1997 ), to millions or possibly hundreds of millions of years of regolith evolution as documented in laterites and bauxites on stable cratons ( Nahon 1986 ). In contrast, solute profiles reflect much shorter time scales corresponding to the residence time of the soil water which commonly ranges from days to decades ( Stonestrom et al. 1998 ). Factors impacting soil minerals can therefore be related to geologically old processes while those impacting pore waters are related to contemporary processes. We first discuss a geochemical frame work for modeling soil profiles, including a simple scheme that depends on the extent of enrichment or depletion. Such profiles are comprised of reaction fronts affected by chemical, hydrologic, geologic and biologic processes that control soil evolution. We then present a hierarchy of models that have been used to interpret both solid state and solute compositions in regolith. The more simple approaches to model depletion in soils, using analytical models, are first described. The most elementary of these is a linear model that calculates rate constants from the slopes of either solid or solute weathering gradients: these rate constants represent lumped parameters that describe weathering in terms of an integrated reaction rate. Two other analytical models are then presented that have been used to fit solid state elemental profiles with exponential and sigmoidal functions. All of these analytical approaches are derived for models of soils as containing a limited number of components, phases, and species. At a more complex level, numerical models are then presented to elucidate how kinetic and transport parameters as well as chemical, hydrologic, and physical soil data can be incorporated. We consider two forms of these models, first relatively simple spreadsheet calculators and then more sophisticated multi-component, multi-phase reactive-transport numerical codes. Our treatment of reactive transport modeling is relatively cursory, in recognition of the treatment in the chapter by Steefel and Maher (2009 , this volume). Because these models incorporate more phases, components, and species than the other approaches and explicitly model the more fundamental reaction mechanisms involved, they generally have a greater need for parameterization. In our conclusion section, we discuss how this hierarchy of approaches can yield generalizations about soils that are often complementary.

Reviews in Mineralogy and Geochemistry↗
USGS2003

The behavior of U- and Th-series nuclides in groundwater

Groundwater has long been an active area of research driven by its importance both as a societal resource and as a component in the global hydrological cycle. Key issues in groundwater research include inferring rates of transport of chemical constituents, determining the ages of groundwater, and tracing water masses using chemical fingerprints. While information on the trace elements pertinent to these topics can be obtained from aquifer tests using experimentally introduced tracers, and from laboratory experiments on aquifer materials, these studies are necessarily limited in time and space. Regional studies of aquifers can focus on greater scales and time periods, but must contend with greater complexities and variations. In this regard, the isotopic systematics of the naturally occurring radionuclides in the U- and Th- decay series have been invaluable in investigating aquifer behavior of U, Th, and Ra. These nuclides are present in all groundwaters and are each represented by several isotopes with very different half-lives, so that processes occurring over a range of time-scales can be studied (Table 1 ⇓ ). Within the host aquifer minerals, the radionuclides in each decay series are generally expected to be in secular equilibrium and so have equal activities (see Bourdon et al. 2003 ). In contrast, these nuclides exhibit strong relative fractionations within the surrounding groundwaters that reflect contrasting behavior during release into the water and during interaction with the surrounding host aquifer rocks. Radionuclide data can be used, within the framework of models of the processes involved, to obtain quantitative assessments of radionuclide release from aquifer rocks and groundwater migration rates. The isotopic variations that are generated also have the potential for providing fingerprints for groundwaters from specific aquifer environments, and have even been explored as a means for calculating groundwater ages.

Reviews in Mineralogy and Geochemistry↗
USGS2003

The behavior of U- and Th-series nuclides in the estuarine environment

Rivers carry the products of continental weathering, and continuously supply the oceans with a broad range of chemical constituents. This erosional signature is, however, uniquely moderated by biogeochemical processing within estuaries. Estuaries are commonly described as complex filters at land-sea margins, where significant transformations can occur due to strong physico-chemical gradients. These changes differ for different classes of elements, and can vary widely depending on the geographic location. U- and Th-series nuclides include a range of elements with vastly different characteristics and behaviors within such environments, and the isotopic systematics provide methods for investigating the transport of these nuclides and other analog species across estuaries and into the coastal ocean.

Reviews in Mineralogy and Geochemistry↗
USGS2001

Stable isotopes in seafloor hydrothermal systems: Vent fluids, hydrothermal deposits, hydrothermal alteration, and microbial processes

The recognition of abundant and widespread hydrothermal activity and associated unique life-forms on the ocean floor is one of the great scientific discoveries of the latter half of the twentieth century. Studies of seafloor hydrothermal processes have led to revolutions in understanding fluid convection and the cooling of the ocean crust, the chemical and isotopic mass balance of the oceans, the origin of stratiform and statabound massive-sulfide ore-deposits, the origin of greenstones and serpentinites, and the potential importance of the subseafloor biosphere. Stable isotope geochemistry has been a critical and definitive tool from the very beginning of the modern era of seafloor exploration.

Reviews in Mineralogy and Geochemistry↗
USGS2000

Stable isotope systematics of sulfate minerals

Stable isotope studies of sulfate minerals are especially useful for unraveling the geochemical history of geological systems. All sulfate minerals can yield sulfur and oxygen isotope data. Hydrous sulfate minerals, such as gypsum, also yield oxygen and hydrogen isotope data for the water of hydration, and more complex sulfate minerals, such as alunite and jarosite also yield oxygen and hydrogen isotope data from hydroxyl sites. Applications of stable isotope data can be divided into two broad categories: geothermometry and tracer studies. The equilibrium partitioning of stable isotopes between two substances, such as the isotopes of sulfur between barite and pyrite, is a function of temperature. Studies can also use stable isotopes as a tracer to fingerprint various sources of hydrogen, oxygen, and sulfur, and to identify physical and chemical processes such as evaporation of water, mixing of waters, and reduction of sulfate to sulfide. Studies of sulfate minerals range from low-temperature surficial processes associated with the evaporation of seawater to form evaporite deposits to high-temperature magmatic-hydrothermal processes associated with the formation of base-and precious-metal deposits. Studies have been conducted on scales from submicroscopic chemical processes associated with the weathering of pyrite to global processes affecting the sulfur budget of the oceans. Sulfate isotope studies provide important information to investigations of energy and mineral resources, environmental geochemistry, paleoclimates, oceanography (past and present), sedimentary, igneous, and metamorphic processes, Earth systems, geomicrobiology, and hydrology. One of the most important aspects of understanding and interpreting the stable isotope characteristics of sulfate minerals is the complex interplay between equilibrium and kinetic chemical and isotopic processes. With few exceptions, sulfate minerals are precipitated from water or have extensively interacted with water at some time in their history. Because of this nearly ubiquitous association with water, the kinetics of isotopic exchange reactions among dissolved species and solids are fundamental in dictating the isotopic composition of sulfate minerals. In general, the heavier isotope of sulfur is enriched in the higher oxidation state, such that under equilibrium conditions, sulfate minerals (e.g. barite, anhydrite) are expected to be enriched in the heavy isotope relative to disulfide minerals (e.g. pyrite, marcasite), which in turn are expected to be enriched relative to monosulfide minerals (e.g. pyrrhotite, sphalerite, galena) ( Sakai 1968 , Bachinski 1969 ). The kinetics of isotopic exchange among minerals with sulfur at the same oxidation state, such as sphalerite, and galena, are such that equilibrium is commonly observed. In contrast, isotopic equilibrium for exchange reactions between minerals of different oxidation states depends on factors such as the pH, time and temperature of reaction, the direction of reaction, fluid composition, and the presence or absence of catalysts ( Ohmoto and Lasaga 1982 ). The kinetics of oxygen isotope exchange between dissolved sulfate and water are extremely sluggish. Extrapolation of the high-temperature (100 to 300°C) isotopic exchange kinetic data of Chiba and Sakai (1985) to ambient temperatures suggests that it would take several billions of years for dissolved sulfate and seawater to reach oxygen isotopic equilibrium. In contrast, the residence time of sulfate in the oceans is only 7.9 million years ( Holland 1978 ). However, at higher temperatures (>200°C), oxygen isotopic exchange is sufficiently rapid to permit application of sulfate isotope geothermometry to geothermal systems and hydrothermal mineral deposits. In general, equilibrium prevails at low pH and high temperatures, whereas kinetic factors preclude equilibrium at low temperatures even at low pH. Thus, the sluggish kinetics of sulfur and oxygen isotope exchange reaction at low temperatures impair the use of these isotopes to understand the conditions of formation of sulfate minerals in these environments. However, because of these slow kinetics, the oxygen and sulfur isotopic compositions of sulfate minerals may preserve a record of the sources and processes that initially produced the dissolved sulfate, because the isotope ratios may not re-equilibrate during fluid transport and mineral precipitation. The first part of this chapter is designed to provide the reader with a basic understanding of the principles that form the foundations of stable isotope geochemistry. Next, an overview of analytical methods used to determine the stable isotope composition of sulfate minerals is presented. This overview is followed by a discussion of geochemical processes that determine the stable isotope characteristics of sulfate minerals and related compounds. The chapter then concludes with an examination of the stable isotope systematics of sulfate minerals in a variety of geochemical environments.

Reviews in Mineralogy and Geochemistry↗
USGS2000

Metal-sulfate salts from sulfide mineral oxidation

The observation of “efflorescences,” or the flowering of salts, associated with periods of dryness in soils, in closed-basin lakes, in rock outcrops, and in mines and mine wastes has been noted since early antiquity. The formation of metal-sulfate salts, in connection with the mining of metals, was a phenomenon well known to the early Greek and Roman civilizations. Alum, most commonly potash alum KAl(SO 4 ) 2 · 12H 2 O, which is from the Latin alumen , was extensively mined and used by goldsmiths, dyers, paper manufacturers, and physicians in ancient civilizations. It forms from the oxidation of pyrite in shales and slates and from oxidation of sulfurous gases in geothermal areas. The Greeks and the Romans described stalactites of atramentum (soluble metal-sulfate salts) that formed within mines and along rock faces (Agricola 1546, 1556). Furthermore, the toxic effects of these salts on animals were also noted. For example, in De Natura Fossilium , Agricola (1546) stated “….I mention the congealed acid juice which usually produces cadmia . It is white, hard, and so acrid that it can eat away walls, grills and even destroy all living matter.” Cadmia is thought to be derived from the oxidation of zinc, cobalt, and arsenic sulfides, such as cobaltite. He goes on to say that “Pyrite, unless it contains sulphates, is either a golden or silver color, rarely any other, while cadmia is black, yellow brown, or gray. The former will cure gatherings while the latter is a deadly poison and will destroy any living substance. It is used to kill grasshoppers, mice and flies.” These descriptions suggest the presence of arsenic compounds. The range of colors from white to black commonly is caused by different amounts of admixed pyrite with sulfate minerals. From the days of the Greek philosopher Theophrastus ( ca 325 BCE) and the Greek physician Dioscorides (first century CE), the efflorescent salts atramentum sutorium virida or melanterite (also called melanteria ) and atramentum sutorium caeruleum or chalcanthite were well known to form from the corrosion of pyrite and chalcopyrite by moisture (Agricola 1546, footnotes on p. 47–51). By the time of Pliny the Second (Caius Plinius Secundus, 23–79 CE), the names “green vitriol” for melanterite and “blue vitriol” for chalcanthite were in common use and continued to be used from the Middle Ages to the 20th century.

Reviews in Mineralogy and Geochemistry↗
USGS2000

Iron and aluminum hydroxysulfates from acid sulfate waters

Acid sulfate waters are produced mostly by the oxidation of common sulfide minerals such as pyrite, chalcopyrite, pyrrhotite, and marcasite in rocks, soils, sediments, and industrial wastes. This spontaneous process of mineral weathering plays a fundamental role in the supergene alteration of ore deposits, the formation of acid sulfate soils, and the mobilization and release of acidity and metals to surface and ground waters. The purely natural process of “acid rock drainage” is often intensified by human activities related to mining, mineral processing, construction, soil drainage, and dredging. Geochemical reaction rates are accelerated because physical disturbance gives greater exposure of mineral surfaces to air and water, and to microbes that catalyze the reaction process. Large quantities of reactive sulfides are also concentrated and exposed to air as a result of mining and mineral processing. Acid sulfate waters produce a number of fairly insoluble hydroxysulfate and oxyhydroxide minerals that precipitate during oxidation, hydrolysis, and neutralization. The objective of this chapter is to describe the formation, properties, fate, and environmental implications of the nano- to microphase hydroxy-sulfates of Fe and Al that are precipitated from acid sulfate waters. These minerals are commonly of poor crystallinity and difficult to characterize. Much remains to be learned about their occurrence, formation, and properties.

Reviews in Mineralogy and Geochemistry↗
USGS2000

Alunite-jarosite crystallography, thermodynamics, and geochronology

The alunite supergroup consists of more than 40 mineral species that have in common the general formula DG 3 ( T O 4 ) 2 (OH,H 2 O) 6 . The D sites are occupied by monovalent (e.g. K, Na, NH 4 , Ag, Tl, H 3 O), divalent (e.g. Ca, Sr, Ba, Pb), trivalent (e.g. Bi, REE) or more rarely quadrivalent (Th) ions; G is Al or Fe 3+ or rarely Ga or V; T is S 6+ , As 5+ , or P 5+ , and may include subordinate amounts of Cr 6+ or Si 4+ . Many of the minerals in this supergroup are exotic, having been described from relatively few localities worldwide, generally in association with ore deposits. Rarely are end-member compositions attained in these natural occurrences, and extensive solid solution is typical for one or more of the D , G , and T sites. In this chapter, the two solid-solution series considered in detail are alunite-natroalunite [KAl 3 (SO 4 ) 2 (OH) 6 – NaAl 3 (SO 4 ) 2 (OH) 6 ] and jarosite-natrojarosite [KFe 3 (SO 4 ) 2 (OH) 6 – NaFe 3 (SO 4 ) 2 (OH) 6 ]. These minerals are by far the most abundant naturally occurring species of the alunite supergroup. Minerals with the generalized formula cited above can be variously grouped, but the simplest initial subdivision is on the basis of Fe > Al versus Al > Fe. Further subdivision is generally made on the basis of the predominant cation within the two T O 4 sites. Thus, within the supergroup, the alunite group consists of minerals in which both of the T sites are occupied by sulfur. This leads to a total negative charge of four on the T O 4 sites. In the ideal formulas of some members of the supergroup [e.g. woodhouseite, CaAl 3 (PO 4 )(SO 4 )(OH) 6 ], half of the T sites are occupied by sulfur, and the other half by arsenic or phosphorus, which produces a total negative charge of five on the T O 4 sites. In still other end-members of the supergroup [e.g. crandallite, CaAl 3 (PO 4 ) 2 (OH) 5 (H 2 O), and arsenocrandallite, CaAl 3 (AsO 4 ) 2 (OH) 5 (H 2 O)], both of the T sites are occupied solely by phosphorus or arsenic, thus producing a total negative charge of six on the T O 4 sites (see Table 1 1 of Dutrizac and Jambor, this volume). In this chapter, however, the primary concern is with those minerals for which T O 4 is represented by SO 4 2− (Table 1 1 ). Precipitates with compositions near those of the end-members in the system alunite-natroalunite and jarosite-natrojarosite are readily prepared using sulfate salts. The products, however, almost invariably have a slight to appreciable deficiency in G 3+ , and have an apparent non-stoichiometry for D . The latter may reflect incorporation a H 3 O + , a solid solution that is difficult to prove because H 3 O + cannot be determined directly by wet-chemistry or microprobe methods. Nevertheless, the existence of two minerals in the alunite supergroup is dependent solely on their D -site predominance of H 3 O + , namely, hydronium jarosite [(H 3 O)Fe 3 (SO 4 ) 2 (OH) 6 ] and schlossmacherite [(H 3 O,Ca)Al 3 (SO 4 ) 2 (OH,H 2 O) 6 ]. This chapter is organized into four sections. In the first section, crystallographic data for alunite-natroalunite and jarosite-natrojarosite are presented and discussed. The second section describes available thermodynamic data for these two solid-solution series, in terms of properties of the end-members and mixing properties for intermediate compositions. The third section discusses the geochemistry and occurrences of alunite and jarosite, and the last section summarizes the published literature on the use of alunite and jarosite in geochronology.

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