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Modeling low-temperature geochemical processes:
This chapter provides an overview of geochemical modeling that applies to water–rock interactions under ambient conditions of temperature and pressure. Topics include modeling definitions, historical background, issues of activity coefficients, popular codes and databases, examples of modeling common types of water–rock interactions, and issues of model reliability. Examples include speciation, microbial redox kinetics and ferrous iron oxidation, calcite dissolution, pyrite oxidation, combined pyrite and calcite dissolution, dedolomitization, seawater–carbonate groundwater mixing, reactive-transport modeling in streams, modeling catchments, and evaporation of seawater. The chapter emphasizes limitations to geochemical modeling: that a proper understanding and ability to communicate model results well are as important as completing a set of useful modeling computations and that greater sophistication in model and code development is not necessarily an advancement. If the goal is to understand how a particular geochemical system behaves, it is better to collect more field data than rely on computer codes.
Metal stable isotopes in weathering and hydrology
This chapter highlights some of the major developments in the understanding of the causes of metal stable isotope compositional variability in and isotope fractionation between natural materials and provides numerous examples of how that understanding is providing new insights into weathering and hydrology. At this stage, our knowledge of causes of stable isotope compositional variability among natural materials is greatest for the metals lithium, magnesium, calcium, and iron, the isotopes of which have already provided important information on weathering and hydrological processes. Stable isotope compositional variability for other metals such as strontium, copper, zinc, chromium, barium, molybdenum, mercury, cadmium, and nickel has been demonstrated but is only beginning to be applied to questions related to weathering and hydrology, and several research groups are currently exploring the potential. And then there are other metals such as titanium, vanadium, rhenium, and tungsten that have yet to be explored for variability of stable isotope composition in natural materials, but which may hold untold surprises in their utility. This impressive list of metals having either demonstrated or potential stable isotope signals that could be used to address important unsolved questions related to weathering and hydrology, constitutes a powerful toolbox that will be increasingly utilized in the coming decades.
The environmental and medical geochemistry of potentially hazardous materials produced by disasters
Many natural or human-caused disasters release potentially hazardous materials (HM) that may pose threats to the environment and health of exposed humans, wildlife, and livestock. This chapter summarizes the environmentally and toxicologically significant physical, mineralogical, and geochemical characteristics of materials produced by a wide variety of recent disasters, such as volcanic eruptions, hurricanes and extreme storms, spills of mining/mineral-processing wastes or coal extraction by-products, and the 2001 attacks on and collapse of the World Trade Center towers. In describing these characteristics, this chapter also illustrates the important roles that geochemists and other earth scientists can play in environmental disaster response and preparedness. In addition to characterizing in detail the physical, chemical, and microbial makeup of HM generated by the disasters, these roles also include (1) identifying and discriminating potential multiple sources of the materials; (2) monitoring, mapping, and modeling dispersal and evolution of the materials in the environment; (3) understanding how the materials are modified by environmental processes; (4) identifying key characteristics and processes that influence the materials' toxicity to exposed humans and ecosystems; (5) estimating shifts away from predisaster environmental baseline conditions; and (6) using geochemical insights learned from past disasters to help estimate, prepare for, and increase societal resilience to the environmental and related health impacts of future disasters.
11.12 - Volatile hydrocarbons and fuel oxygenates
Petroleum hydrocarbons and fuel oxygenates are among the most commonly occurring and widely distributed contaminants in the environment. This chapter presents a summary of the sources, transport, fate, and remediation of volatile fuel hydrocarbons and fuel additives in the environment. Much research has focused on the transport and transformation processes of petroleum hydrocarbons and fuel oxygenates, such as benzene, toluene, ethylbenzene, and xylenes and methyl tert‐butyl ether, in groundwater following release from underground storage tanks. Natural attenuation from biodegradation limits the movement of these contaminants and has received considerable attention as an environmental restoration option. This chapter summarizes approaches to environmental restoration, including those that rely on natural attenuation, and also engineered or enhanced remediation. Researchers are increasingly combining several microbial and molecular-based methods to give a complete picture of biodegradation potential and occurrence at contaminated field sites. New insights into the fate of petroleum hydrocarbons and fuel additives have been gained by recent advances in analytical tools and approaches, including stable isotope fractionation, analysis of metabolic intermediates, and direct microbial evidence. However, development of long-term detailed monitoring programs is required to further develop conceptual models of natural attenuation and increase our understanding of the behavior of contaminant mixtures in the subsurface.
13.3 – Stable Isotope Geochemistry of Mineral Deposits
In this chapter, the intent is to summarize the results of traditional stable isotope studies (mainly H, B, O, C, and S) that have greatly contributed to the understanding of ore-forming processes over the last 60 years and to provide an up-to-date assessment of the application of new nontraditional isotope systems (Fe, Cu, Zn, Se, Mo, Hg, and Tl).
Melt inclusions
Melt inclusions are small droplets of silicate melt that are trapped in minerals during their growth in a magma. Once formed, they commonly retain much of their initial composition (with some exceptions) unless they are re-opened at some later stage. Melt inclusions thus offer several key advantages over whole rock samples: (i) they record pristine concentrations of volatiles and metals that are usually lost during magma solidification and degassing, (ii) they are snapshots in time whereas whole rocks are the time-integrated end products, thus allowing a more detailed, time-resolved view into magmatic processes (iii) they are largely unaffected by subsolidus alteration. Due to these characteristics, melt inclusions are an ideal tool to study the evolution of mineralized magma systems. This chapter first discusses general aspects of melt inclusions formation and methods for their investigation, before reviewing studies performed on mineralized magma systems.
Deep-ocean ferromanganese crusts and nodules
Ferromanganese crusts and nodules may provide a future resource for a large variety of metals, including many that are essential for emerging high- and green-technology applications. A brief review of nodules and crusts provides a setting for a discussion on the latest (past 10 years) research related to the geochemistry of sequestration of metals from seawater. Special attention is given to cobalt, nickel, titanium, rare earth elements and yttrium, bismuth, platinum, tungsten, tantalum, hafnium, tellurium, molybdenum, niobium, zirconium, and lithium. Sequestration from seawater by sorption, surface oxidation, substitution, and precipitation of discrete phases is discussed. Mechanisms of metal enrichment reflect modes of formation of the crusts and nodules, such as hydrogenetic (from seawater), diagenetic (from porewaters), and mixed diagenetic–hydrogenetic processes.
Geochemistry of a marine phosphate deposit: A signpost to phosphogenesis
The Permian age Phosphoria Formation in southeastern Idaho and adjoining states represents possibly the largest marine phosphate deposit in the world. The Meade Peak Member, which contains the highest concentrations and amount of carbonate fluorapatite in the formation, was not significantly altered by mechanical reworking during deposition or subsequently by chemical weathering. Thus, its present composition reflects properties of the Phosphoria Sea that were critical to its accumulation and possibly to the accumulation of most major marine phosphate deposits. These properties included the chemistry of the water column, the hydrography, and the level of primary productivity. Calculated accumulation rates of the PO 4 3− and trace nutrients – Cd, Cu, Ni, and Zn – recorded a dynamic upwelling rate of c. 30 m year −1 that supported primary productivity of 2g C m −2 day −1 . High accumulation rates of the hydrogenous redox-sensitive trace metals – Cr, Mo, U, and V – reflect bottom-water redox conditions that were dominantly suboxic, maintained by a balance between the oxidation of ~ 8% of the organic detritus that settled out of the photic zone and advection of bottom water with a residence time of c .10 years. A limited flux into the basin of siliciclastic lithogenous debris contributed further to elevated concentrations of the seawater-derived sediment fractions.
Bioavailability and bioaccumulation of metal-based engineered nanomaterials in aquatic environments: Concepts and processes
Bioavailability of Me-ENMs to aquatic organisms links their release into the environment to ecological implications. Close examination shows some important differences in the conceptual models that define bioavailability for metals and Me-ENMs. Metals are delivered to aquatic animals from Me-ENMs via water, ingestion, and incidental surface exposure. Both metal released from the Me-ENM and uptake of the nanoparticle itself contribute to bioaccumulation. Some mechanisms of toxicity and some of the metrics describing exposure may differ from metals alone. Bioavailability is driven by complex interaction of particle attributes, environmental transformations, and biological traits. Characterization of Me-ENMs is an essential part of understanding bioavailability and requires novel methodologies. The relative importance of the array of processes that could affect Me-ENM bioavailability remains poorly known, but new approaches and models are developing rapidly. Enough is known, however, to conclude that traditional approaches to exposure assessment for metals would not be adequate to assess risks from Me-ENMs.
Methane hydrates
Gas hydrate is a solid, naturally occurring substance consisting predominantly of methane gas and water. Recent scientific drilling programs in Japan, Canada, the United States, Korea and India have demonstrated that gas hydrate occurs broadly and in a variety of forms in shallow sediments of the outer continental shelves and in Arctic regions. Field, laboratory and numerical modelling studies conducted to date indicate that gas can be extracted from gas hydrates with existing production technologies, particularly for those deposits in which the gas hydrate exists as pore-filling grains at high saturation in sand-rich reservoirs. A series of regional resource assessments indicate that substantial volumes of gas hydrate likely exist in sand-rich deposits. Recent field programs in Japan, Canada and in the United States have demonstrated the technical viability of methane extraction from gas-hydrate-bearing sand reservoirs and have investigated a range of potential production scenarios. At present, basic reservoir depressurisation shows the greatest promise and can be conducted using primarily standard industry equipment and procedures. Depressurisation is expected to be the foundation of future production systems; additional processes, such as thermal stimulation, mechanical stimulation and chemical injection, will likely also be integrated as dictated by local geological and other conditions. An innovative carbon dioxide and methane swapping technology is also being studied as a method to produce gas from select gas hydrate deposits. In addition, substantial additional volumes of gas hydrate have been found in dense arrays of grain-displacing veins and nodules in fine-grained, clay-dominated sediments; however, to date, no field tests, and very limited numerical modelling, have been conducted with regard to the production potential of such accumulations. Work remains to further refine: (1) the marine resource volumes within potential accumulations that can be produced through exploratory drilling programs; (2) the tools for gas hydrate detection and characterisation from remote sensing data; (3) the details of gas hydrate reservoir production behaviour through additional, well-monitored and longer duration field tests and (4) the understanding of the potential environmental impacts of gas hydrate resource development. The results of future production tests, in the context of varying market and energy supply conditions around the globe, will be the key to determine the ultimate timing and scale of the commercial production of natural gas from gas hydrates.
Seismic monitoring solutions for buildings
This chapter introduces seismic monitoring of structural systems for buildings and begins with a historical background of this topic in the United States. After providing the historical context, the chapter reviews common seismic instrumentation issues such as utilization of data, code versus extensive instrumentation, free-field instrumentation, record synchronization requirements and more. Recent developments in damage detection is examined including damage detection based on changes in natural frequencies, permanent deformations, and interstory drift. Finally, applications in Europe, the Middle East, and Japan of seismic monitoring of structural systems for buildings are discussed.
Natural gas hydrates: Status of potential as an energy resource
Gas hydrate is a widespread naturally-occurring combination of water and natural gases. Gas hydrate is found in shallow sediments of deepwater regions of the continental margins and in areas of continuous permafrost. Where gas supply is sufficient and migration pathways connect gas sources to favorable reservoirs, gas hydrate can accumulate to resource densities that may be attractive for gas production. Global research on the potential commercial viability of gas extraction from gas hydrates continues, predominantly in Asia and in the United States, where current efforts focus on the controlled destabilization of high-saturation deposits housed in sand and/or silt-rich reservoirs. This chapter reviews the current state of gas hydrate resource exploration and appraisal, the most promising production approaches identified to date, and the likely technical challenges to commercial production.
Porphyry and epithermal mineral deposits
Porphyry and epithermal mineral deposits form large economic ore bodies that provide the global economy with copper, molybdenum, gold, silver and other byproducts (Re, Te, Se). They form in the upper crust and are related to sulfur- and water-rich intermediate to silicic magmatic sources of hydrothermal fluids that move upward and produce extensive hydrolytic and alkali wall-rock alteration, quartz veins, and sulfides. Porphyry-type deposits are formed above magma chambers where fluids hydrofracture rock at 700–350 °C and at pressures ranging from supra-lithostatic to supra-hydrostatic. The depth of formation ranges from 2 to 10 km and influences orebody geometries and the types and mineralogy of veins, sulfides and wall-rock alteration. The temporal evolution of hydrothermal events is documented by cross-cutting veins and is commonly characterized by a decline in fluid temperature and concordant evolution from potassic alteration to sericitic alteration, with attendant increase in sulfidation state of copper-iron sulfides. In some localities porphyry copper deposits transition upwards to lower temperature base metal lodes (350–200 °C) and eventually the formation of near surface (<1.5 km depth) intermediate- and high-sulfidation epithermal deposits (~300–120 °C). Extensional environments are often characterized by porphyry molybdenum and low-sulfidation epithermal deposits. In the base metal lode and epithermal environments, mixtures of magmatic and meteoric fluids produce ore fluids at hydrostatic pressures that advect freely both vertically and laterally along permeability provided by faults, joints, and porous lithologies. Wall-rock alteration ranges from hydrolytic to alkali-carbonate, and from high- to low-sulfidation state sulfide assemblages, respectively. In porphyry, base metal lode, and epithermal environments, geology and the zonation of wall-rock alteration, veins, sulfide assemblages, and metals are useful for exploration.
Ocean floor manganese deposits
Much of the dissolved Mn delivered to the oceans is slowly oxidized and precipitated alongside varying amounts of Fe into Mn and ferromanganese (FeMn) mineral deposits that occur extensively in the deep ocean wherever sediment accumulation is low and substrate is available. FeMn crusts grow as pavements on rock outcrops throughout the global ocean whereas nodules form as individual FeMn-encrusted particles on the sediment-covered abyssal plains. Both crusts and nodules are composed predominantly of Fe and Mn oxide minerals that precipitate from seawater and for some nodules also from porewaters of deep-sea sediment. In contrast, hydrothermal oxide deposits consist predominantly of Mn or Fe oxide. FeMn crusts and nodules exhibit very high specific surface areas that allow them to scavenge abundant metals and other elements, recording the history of the source waters. Crusts especially serve as an important record of paleoceanographic conditions over the past 70 + million years. Critical metals essential to many computer, military, and green technologies are enriched in crust and nodule deposits to concentrations high enough to compare with, or exceed, typical terrestrial deposits, and they can be considered as potential resources for mining in the near future. Twenty-three contracts pertaining to exploration for nodules and crusts have been signed with the International Seabed Authority, and resource/reserve, baseline, and environmental impact assessments are underway. Many challenges remain to be addressed before full-scale mining of marine FeMn deposits will occur. However, their unique genesis and the growing worldwide need for rare and critical metals keep these deep-ocean deposits relevant to industry, scientists, and governments.
Dating by cosmogenic nuclides
Since the 1990s, cosmogenic nuclides have revolutionized the study of Earth surface processes, particularly the understanding of rates and dates. These nuclides, including 3 He, 10 Be, 14 C, 21 Ne, 26 Al, and 36 Cl, enable dating of landforms and the measurement of erosion rates both at the scale of drainage basins and at specific locations on Earth's surface. Cosmogenic nuclides are produced at low rates (several to hundreds of atoms per gram per year) by the interaction of cosmic rays with elements both in the atmosphere and in surficial materials, including in rock and soil. Measuring nuclide concentrations requires elemental separation from source geologic material followed by counting of atoms using sensitive accelerator mass spectrometers. Because nuclide production rates have been quantified, the measured concentration of these nuclides can be interpreted as a near-surface residence time. Here, we review the systematics of commonly used cosmogenic nuclides, describe how they are extracted and measured, and then present case studies focusing on the most commonly measured cosmogenic nuclide, 10 Be. We present common applications such as dating surface features, including moraines and outcrops shaped by glaciation, the use of cosmogenic nuclides for inferring tectonic and erosion processes in drainage basins, and the use of these nuclides to trace sediment sources in drainage basins. When multiple nuclides are measured in one sample, they can be used to model burial and exposure histories in stratigraphic sections. We conclude by exploring what the future might bring in terms of measurements and applications.
Monitoring volcanic deformation
Deformation signals recorded at volcanoes have long been used to infer the processes behind subsurface magma intrusions. Monitoring strategies vary greatly depending on several factors such as the activity of the individual volcano, access, available personnel, and funding. Certain geodetic monitoring methods, such as Electronic Distance Measurements, are inexpensive but require that scientists be dangerously close to active areas. Other techniques, such as telemetered geodetic measurements (Electronic Tiltmeters and Global Navigation Satellite System), or deformation images from Interferometric Synthetic Aperture Radar, can be collected remotely and with less risk. Observed surface deformation can be fit to the predictions of mathematical source models to obtain quantitative estimates of their parameters (e.g., location, depth, volume change and more). Combined deformation and gravity change measurements can be used to infer the density of subsurface intrusions and better constrain the source of unrest. To be effective, geodetic monitoring must be done before, during, and after eruptions and must be integrated with other monitoring techniques (e.g., seismology, geochemistry, physical volcanology, remote sensing). It requires the long-term commitment of time and resources. Done effectively, geodetic monitoring not only can provide timely warnings of escalating volcano hazards but may also lead to improved understanding of how volcanoes work. Even when a volcano is not active, monitoring generates baseline information against which changes in volcano behavior can be compared. Preserving the integrity and accessibility of geodetic data archives is thus essential if future volcanologists are to benefit from the decades-long records of geodetic data gathered by volcano observatories.
Application of models to conservation planning for terrestrial birds in North America
Partners in Flight (PIF), a public–private coalition for the conservation of land birds, has developed one of four international bird conservation plans recognized under the auspices of the North American Bird Conservation Initiative (NABCI). Partners in Flight prioritized species most in need of conservation attention and set range-wide population goals for 448 species of terrestrial birds. Partnerships are now tasked with developing spatially explicit estimates of the distribution, and abundance of priority species across large ecoregions and identifying habitat acreages needed to support populations at prescribed levels. The PIF Five Elements process of conservation design identifies five steps needed to implement all bird conservation at the ecoregional scale. Habitat assessment and landscape characterization describe the current amounts of different habitat types and summarize patch characteristics, and landscape configurations that define the ability of a landscape to sustain healthy bird populations and are a valuable first step to describing the planning area before pursuing more complex species-specific models. Spatially linked database models, landscape-scale habitat suitability models, and statistical models are viable alternatives for predicting habitat suitability or bird abundance across large planning areas to help assess conservation opportunities, design landscapes to meet population objectives, and monitor change in habitat suitability or bird numbers over time. Bird conservation in the United States is a good example of the use of models in large-scale wildlife conservation planning because of its geographic extent, focus on multiple species, involvement of multiple partners, and use of simple to complex models. We provide some background on the recent development of bird conservation initiatives in the United States and the approaches used for regional conservation assessment and planning. We focus on approaches being used for landscape characterization and assessment, and bird population response modeling.