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At least 19 recordsLinked to original sources
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

Thermodynamic properties for arsenic minerals and aqueous species

Quantitative geochemical calculations are not possible without thermodynamic databases and considerable advances in the quantity and quality of these databases have been made since the early days of Lewis and Randall (1923) , Latimer (1952) , and Rossini et al. (1952) . Oelkers et al. (2009) wrote, “ The creation of thermodynamic databases may be one of the greatest advances in the field of geochemistry of the last century .” Thermodynamic data have been used for basic research needs and for a countless variety of applications in hazardous waste management and policy making ( Zhu and Anderson 2002 ; Nordstrom and Archer 2003 ; Bethke 2008 ; Oelkers and Schott 2009 ). The challenge today is to evaluate thermodynamic data for internal consistency, to reach a better consensus of the most reliable properties, to determine the degree of certainty needed for geochemical modeling, and to agree on priorities for further measurements and evaluations.

Reviews in Mineralogy and Geochemistry↗
USGS2014

Arsenic speciation in solids using X-ray absorption spectroscopy

Synchrotron-based X-ray absorption spectroscopy (XAS) is an in situ , minimally-destructive, element-specific, molecular-scale structural probe that has been employed to study the chemical forms (species) of arsenic (As) in solid and aqueous phases (including rocks, soils, sediment, synthetic compounds, and numerous types of biota including humans) for more than 20 years. Although several excellent reviews of As geochemistry and As speciation in the environment have been published previously (including recent contributions in this volume), the explosion of As-XAS studies over the past decade (especially studies employing microfocused X-ray beams) warrants this new review of the literature and of data analysis methods. This review has two main sections. The first is a presentation of methods for sample preparation and for the collection, processing and analysis of As-XAS spectra. Since several more comprehensive reviews of the X-ray absorption theory and data collection methodology exist, this section is brief and focused specifically on As. The second section is a critical review of the As-XAS literature, arranged by sample type and accompanied by summary tables (collected as appendices at the end of the chapter). One of the most important aims of this review is to clarify the different types of analysis that are performed on As-XAS spectra, and to describe the benefits, drawbacks, and limitations of each. Arsenic XAS spectra are analyzed to obtain one or more of the following types of information (in increasing order of sophistication):

Reviews in Mineralogy and Geochemistry↗
USGS2014

Arsenic speciation and sorption in natural environments

Aqueous arsenic speciation, or the chemical forms in which arsenic exists in water, is a challenging, interesting, and complicated aspect of environmental arsenic geochemistry. Arsenic has the ability to form a wide range of chemical bonds with carbon, oxygen, hydrogen, and sulfur, resulting in a large variety of compounds that exhibit a host of chemical and biochemical properties. Besides the intriguing chemical diversity, arsenic also has the rare capacity to capture our imaginations in a way that few elements can duplicate: it invokes images of foul play that range from sinister to comedic (e.g., “inheritance powder” and arsenic-spiked elderberry wine). However, the emergence of serious large-scale human health problems from chronic arsenic exposure in drinking water has placed a high priority on understanding environmental arsenic mobility, toxicity, and bioavailability, and chemical speciation is key to these important questions. Ultimately, the purpose of arsenic speciation research is to predict future occurrences, mitigate contamination, and provide successful management of water resources.

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↗
USGS2006

The toxicological geochemistry of Earth materials: An overview of processes and the interdisciplinary methods used to understand them

A broad spectrum of earth materials have been linked to, blamed for, and/or debated as sources for disease. In some cases, the links are clear. For example, excessive exposures to mineral dusts have long been recognized for their role in diseases such as: asbestosis, mesothelioma, and lung cancers (asbestos); silicosis and lung cancer (silica dusts); and coal-workers pneumoconiosis (coal dust). Lead poisoning, particularly in toddlers and young children, has been conclusively linked to involuntary ingestion of soils or other materials contaminated with lead-rich paint particles, leaded gasoline combustion byproducts, and some types of lead-rich mine wastes or smelter particulates. Waters with naturally elevated arsenic contents are common in many regions of the globe, and consumption of these waters has been documented as the source of arsenic-related diseases affecting thousands of people in south Asia and other regions. Exposure to dusts or soils containing pathogens has been documented as the cause of regionally common diseases such as valley fever (coccidioidomycosis) and much rarer diseases such as anthrax. Links between many other earth materials and specific diseases, although suspected, are less clear or are debated. For example, it has been suggested that geographic clusters of diseases such as leukemia are related to exposures to waters or atmospheric particulates containing organic or metal contaminants; however, for many clusters the exact causal relationships between disease and environmental exposure are difficult to prove conclusively. Even for many diseases in which the causal relationship is clear, such as in asbestosis and mesothelioma triggered by asbestos exposure, the minimum exposures needed to trigger disease, the influence of genetic factors, and the exact mechanisms of toxicity are still incompletely understood and are the focus of considerable debate within the public health community. Hence, understanding the health effects resulting from occupational and environmental exposures to a wide variety of earth materials remains a very active and fruitful area of research.

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↗
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↗
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↗
USGS2013

Geochemical monitoring for potential environmental impacts of geologic sequestration of CO 2

Carbon dioxide sequestration is now considered an important component of the portfolio of options for reducing greenhouse gas emissions to stabilize their atmospheric levels at values that would limit global temperature increases to the target of 2 °C by the end of the century (Pacala and Socolow 2004; IPCC 2005, 2007; Benson and Cook 2005; Benson and Cole 2008; IEA 2012; Romanak et al. 2013). Increased anthropogenic emissions of CO2 have raised its atmospheric concentrations from about 280 ppmv during pre-industrial times to ~400 ppmv today, and based on several defined scenarios, CO2 concentrations are projected to increase to values as high as 1100 ppmv by 2100 (White et al. 2003; IPCC 2005, 2007; EIA 2012; Global CCS Institute 2012). An atmospheric CO2 concentration of 450 ppmv is generally the accepted level that is needed to limit global temperature increases to the target of 2 °C by the end of the century. This temperature limit likely would moderate the adverse effects related to climate change that could include sea-level rise from the melting of alpine glaciers and continental ice sheets and from the ocean warming; increased frequency and intensity of wildfires, floods, droughts, and tropical storms; and changes in the amount, timing, and distribution of rain, snow, and runoff (IPCC 2007; Sundquist et al. 2009; IEA 2012). Rising atmospheric CO2 concentrations are also increasing the amount of CO2 dissolved in ocean water lowering its pH from 8.1 to 8.0, with potentially disruptive effects on coral reefs, plankton and marine ecosystems (Adams and Caldeira 2008; Schrag 2009; Sundquist et al. 2009). Sedimentary basins in general and deep saline aquifers in particular are being investigated as possible repositories for the large volumes of anthropogenic CO2 that must be sequestered to mitigate global warming and related climate changes (Hitchon 1996; Benson and Cole 2008; Verma and Warwick 2011).

Reviews in Mineralogy and Geochemistry↗
USGS2014

Spectroscopy from Space

This chapter reviews detection of materials on solid and liquid (lakes and ocean) surfaces in the solar system using ultraviolet to infrared spectroscopy from space, or near space (high altitude aircraft on the Earth), or in the case of remote objects, earth-based and earth-orbiting telescopes. Point spectrometers and imaging spectrometers have been probing the surfaces of our solar system for decades. Spacecraft carrying imaging spectrometers are currently in orbit around Mercury, Venus, Earth, Mars, and Saturn, and systems have recently visited Jupiter, comets, asteroids, and one spectrometer-carrying spacecraft is on its way to Pluto. Together these systems are providing a wealth of data that will enable a better understanding of the composition of condensed matter bodies in the solar system. Minerals, ices, liquids, and other materials have been detected and mapped on the Earth and all planets and/or their satellites where the surface can be observed from space, with the exception of Venus whose thick atmosphere limits surface observation. Basaltic minerals (e.g., pyroxene and olivine) have been detected with spectroscopy on the Earth, Moon, Mars and some asteroids. The greatest mineralogic diversity seen from space is observed on the Earth and Mars. The Earth, with oceans, active tectonic and hydrologic cycles, and biological processes, displays the greatest material diversity including the detection of amorphous and crystalline inorganic materials, organic compounds, water and water ice. Water ice is a very common mineral throughout the Solar System and has been unambiguously detected or inferred in every planet and/or their moon(s) where good spectroscopic data has been obtained. In addition to water ice, other molecular solids have been observed in the solar system using spectroscopic methods. Solid carbon dioxide is found on all systems beyond the Earth except Pluto, although CO 2 sometimes appears to be trapped in other solids rather than as an ice on some objects. The largest deposits of carbon dioxide ice are found on Mars. Sulfur dioxide ice is found in the Jupiter system. Nitrogen and methane ices are common beyond the Uranian system. Saturn’s moon Titan probably has the most complex active extra-terrestrial surface chemistry involving organic compounds. Some of the observed or inferred compounds include ices of benzene (C 6 H 6 ), cyanoacetylene (HC 3 N), toluene (C 7 H 8 ), cyanogen (C 2 N 2 ), acetonitrile (CH 3 CN), water (H 2 O), carbon dioxide (CO 2 ), and ammonia (NH 3 ). Confirming compounds on Titan is hampered by its thick smoggy atmosphere, where in relative terms the atmospheric interferences that hamper surface characterization lie between that of Venus and Earth. In this chapter we exclude discussion of the planets Jupiter, Saturn, Uranus, and Neptune because their thick atmospheres preclude observing the surface, even if surfaces exist. However, we do discuss spectroscopic observations on a number of the extra-terrestrial satellite bodies. Ammonia was predicted on many icy moons but is notably absent among the definitively detected ices with possible exceptions on Charon and possible trace amounts on some of the Saturnian satellites. Comets, storehouses of many compounds that could exist as ices in their nuclei, have only had small amounts of water ice definitively detected on their surfaces from spectroscopy. Only two asteroids have had a direct detection of surface water ice, although its presence can be inferred in others.

Reviews in Mineralogy and Geochemistry↗
USGS2023

The lunar cratering chronology

This chapter provides an introduction to crater-size frequency distribution (CSFD) measurements and presents a review of the work performed on dating lunar geological units using CSFDs since the last New Views of the Moon volume (2006), including various volcanic and tectonic features, as well as individual impact craters. At the end of the chapter, implications for the new CSFD age determinations for the geologic history and evolution of the Moon are discussed.

Reviews in Mineralogy and Geochemistry↗
USGS2023

Lunar mare basaltic volcanism: Volcanic features and emplacement processes

Volcanism is a fundamental process in the geological evolution of the Moon, providing clues to the composition and structure of the mantle, the location and duration of interior melting, the nature of convection and lunar thermal evolution. Progress in understanding volcanism has been remarkable in the short 60-year span of the Space Age. Before Sputnik 1 in 1957, the lunar farside was unknown, the origin of the dark lunar maria was debated (sedimentary or volcanic), and significant controversy surrounded the question of how the multitude of craters on the surface formed. Was the Moon formed hot or cold, was the lunar surface young or old, were the craters of impact or volcanic origin? A lunar farside deficient in the darker maria was revealed by Luna 3 in 1959 ( Lipsky 1965a , b ). The Ranger, Lunar Orbiter, Surveyor, Luna and Zond missions significantly augmented pre-Sputnik telescopic observations and began to reveal the diversity of lunar geologic landforms. Return of lunar soil and rock samples from the lunar surface by Apollo (11–12, 14–17) ( Compton 1989 ) and Luna (16, 20, 24) missions ( Harvey 2007a , b ; Huntress and Marov 2011 ) changed the debates overnight ( Hinners 1971 ; Taylor 1975 ). The lunar rocks were igneous and extremely ancient, all from the first half of Solar System history; the oldest, highland anorthosites, were overlain by relatively younger, but still extremely old, extrusive basalts forming the maria.

Reviews in Mineralogy and Geochemistry↗
USGS2024

The early Earth as an analogue for exoplanetary biogeochemistry

Planet Earth has evolved over the past 4.5 billion years from an entirely anoxic planet with possibly a different tectonic regime to the oxygenated world with horizontal plate tectonics that we know today. For most of this time, Earth has been inhabited by a purely microbial biosphere albeit with seemingly increasing complexity over time. A rich record of this geobiological evolution over most of Earth’s history thus provides insights into the remote detectability of microbial life under a variety of planetary conditions. Here we leverage Earth’s geobiological record with the aim of (a) illustrating the current state of knowledge and key knowledge gaps about the early Earth as a reference point in exoplanet science research; (b) compiling biotic and abiotic mechanisms that controlled the evolution of the atmosphere over time; and (c) reviewing current constraints on the detectability of Earth’s early biosphere with state-of-the-art telescope technology. We highlight that life may have originated on a planet with a different (stagnant lid) tectonic regime and strong hydrothermal activity, and under these conditions, biogenic CH 4 gas was perhaps the most detectable atmospheric biosignature. Oxygenic photosynthesis, which is responsible for essentially all O 2 gas in the modern atmosphere, appears to have emerged concurrently with the establishment of modern plate tectonics and the emergence of continental crust, but O 2 accumulation to modern levels only occurred late in Earth’s history, perhaps tied to the rise of land plants. Nutrient limitation in anoxic oceans, promoted by hydrothermal Fe fluxes, may have limited biological productivity and O 2 production. N 2 O is an alternative biosignature that was perhaps significant on the redox-stratified Proterozoic Earth. We conclude that the detectability of atmospheric biosignatures on Earth was not only dependent on biological evolution but also strongly controlled by the evolving tectonic context.

Reviews in Mineralogy and Geochemistry↗