Chapter 1-Introduction to Pathways of Metal Transfer from Mineralized Sources to Bioreceptors By Roger P. Ashley, Elizabeth A. Bailey, Laurie S. Balistrieri, Andrea L. Foster, Larry P. Gough, Floyd Gray, Randolph A. Koski, James J. Rytuba, Robert R. Seal II, Kathleen S. Smith, Lisa L. Stillings, and Richard B. Wanty Since 1995, the Mineral Resources Program of the U.S. Geological Survey has funded a number of studies in the western United States that address environmental issues associated with mineral deposits. Projects with environmental components in the western United States include Geoenvironmental Impacts of Hg and As; Humboldt River Basin Assessment; Coeur d'Alene Life-Cycle Models; Southwest Mineral and Environmental Investigations; and Geologic and Geoenvironmental Studies of the Western Phosphate Field. Toxicity to humans and other biota is a primary issue in these studies. Such toxicity is related to high concentrations of environmentally significant elements released during natural weathering prior to mining, during mining of mineral deposits, and during modern weathering of historic mine wastes. Environmentally significant elements, including but not limited to Al, As, Cd, Cu, Fe, Hg, Mo, Pb, Sb, Se, and Zn, are defined to be elements that are essential to or adversely impact the health of organisms. Allowable concentrations of many environmentally significant elements are regulated by state and Federal agencies. Toxicity is also related to the speciation and location of elements in the ecosystem. The term "speciation" in this context means the exact chemical forms in which an element occurs and the quantitative distribution of different coexisting forms. Results of these studies provide a scientific basis for local, state, and Federal agencies charged with minimizing the impacts of trace and potentially toxic elements on the environment and health of biota to make decisions, develop strategy, and assess mitigation alternatives. As some of these projects draw to a close, we want to summarize, in a consistent manner, the results of these studies, identify gaps in our knowledge, and propose topics for future research. This collection of papers aims to meet those goals. The common themes among the various environmental studies are (1) determining the distributions and concentrations of environmentally significant elements throughout the study areas, (2) understanding how elements move through the environmental systems, and (3) identifying the relationships between geochemical behavior of these elements and impacts on biota. These themes provide a framework for examining and comparing the various studies. This framework or conceptual model, presented in figure 1, has the advantage of being transferable among ecosystems of widely varying scales. It is composed of three linked components: source, processes, and bioreceptors. The component includes natural and anthropogenic entities such as mineralized terranes, mineral deposits and mines, mine tailings, and waste rock. Characterization of the source component involves determining the concentrations of elements in the source, identifying the phases where trace elements reside, assessing the speciation of the trace elements (for example, oxidation state and type of bonding to the mineral structure), and determining the rates and mechanism of release from the source. The processes component of the model includes all of the physical and biogeochemical processes that act either to redistribute or chemically transform trace elements among sources and secondary phases. For example, particulate phases such as mine tailings can be physically moved away from the source by hydrologic transport, taken up by bioreceptors (for instance, ingestion of particulate Pb by humans or birds), or transformed into dissolved species by oxidation, reduction, dissolution, or desorption and exchange reactions. Dissolved species can be physically transported by advection or diffusion away from the source, taken up by bioreceptors (for instance, assimilation of methyl mercury by algae), or incorporate into particulates through precipitation and adsorption reactions. The cycling of elements between particulate and dissolved phases is a recurring process in a given ecosystem. The third component of the model is bioreceptors (including humans, livestock, wildlife, plants, and microorganisms). Information in this component addresses the biogeochemical factors (for example, molecular speciation of elements in host phases and mechanisms of uptake) that control the accessibility and availability of trace elements to biota. Using this three-component conceptual framework, table 1 presents an overview of the individual study areas, summarizing their locations; characteristics (that is, deposit types, ecoregions and climates, elements of interest, and relative ranges of pH); documented processes operating within the systems; bioreceptors and probable mechanisms of uptake; and topics that need further research. These studies encompass a range of deposit types, climate regimes, and elements of interest. Many of the critical processes affecting element distributions and behavior are similar in these diverse environments and include those related to physical movement (for example, aeolian transport, erosion, hydrologic transport and mixing, and fluxes across interfaces) and to transformations between dissolved and particulate phases (for example, adsorption and desorption, mineral precipitation and dissolution, and organic matter production and oxidation). Microorganisms mediate many of the geochemical reactions. Bioreceptors that have been identified in these systems include humans, livestock, game animals, fish, amphibians, birds, aquatic and benthic invertebrates, and plants. The chapters that follow discuss the geologic setting of each study area and answer the following questions, most of which are directly related to the conceptual framework: 1. What is known about the distributions, concentrations, and speciation of environmentally significant elements in the system? 2. What is known about the processes that mobilize elements from their sources and then act to physically and biogeochemically redistribute them? 3. What is known about impacts to biota, and can specific processes be identified that influence the accessibility or availability of trace elements, acid, and other chemical species to biota? 4. What are the major gaps in knowledge (that is, new directions for research) remaining from the study? The ability to answer the above questions varies among study areas because of the scope of ongoing work, the level of involvement of collaborative partners, and the length of time that research has been done. One study is just starting, whereas others are in their fifth or sixth year of study. From examination of this collective work, we propose to focus our future research on the processes component of the conceptual model. The following research themes have been identified: 1. Speciation of dissolved and solid phases and the influence of speciation upon geoavailability (that is, biogeochemical mobility and accessibility) and bioavailability (that is, uptake by humans and wildlife) of trace elements. 2. Microbial activities and transformations. 3. Processes at physical, geochemical, and biological interfaces. 4. Precipitation and transformations of metal oxyhydroxides and metal oxyhydroxysulfates and associated interactions with trace elements. 5. Physical transport and dispersion of trace elements. 6. Conceptual and quantitative modeling of element behavior in mineralized ecosystems and understanding how elements and ecosystems respond to natural and anthropogenic perturbations. Research to address these themes is now being done in the Pathways Project, which is funded by the Mineral Resources Program. Specific tasks of the Pathways project (and the related themes from above) include: 1. Impact of Hg from placer gold mine tailings on bioreceptors (themes 1 and 2). 2. Biogeochemical and biochemical pathway investigations of Cd in subarctic ecosystems using a hyperaccumulator species (willow) (theme 1). 3. Effect of microbially mediated Fe, Mn, and SO4 reducing conditions on Hg and As transformation in a historic mining environment (themes 1, 2, 3, and 4). 4. Mobility and bioavailability of As and Se in the Great Basin as a function of redox conditions (themes 1, 2, 3, and 4). 5. Modeling the underlying processes that determine the concentrations and distributions of elements in environmental systems as a function of time (themes 1 through 6). Results from these tasks will advance our understanding of specific processes that link geoavailability of environmentally significant elements to bioavailability in large-scale systems where mineralized areas are a long-term source of metals and other elements to the systems. By determining the dominance and influence of particular physical, chemical, and biological processes that control metal mobility and accessibility to biota, we will be able to identify which specific processes should be targeted during remediation or management of these systems to best minimize the impacts of trace and toxic elements on the environment and the health of biota.