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The fate of cyanide in leach wastes at gold mines: an environmental perspective

This paper reviews the basic chemistry of cyanide, methods by which cyanide can be analyzed, and aspects of cyanide behavior that are most relevant to environmental considerations at mineral processing operations associated with gold mines. The emphasis is on research results reported since 1999 and on data gathered for a series of U.S. Geological Survey studies that began in the late 1990s. Cyanide is added to process solutions as the CN − anion, but ore leaching produces numerous other cyanide-containing and cyanide-related species in addition to the desired cyanocomplex of gold. These can include hydrogen cyanide (HCN); cyanometallic complexes of iron, copper, zinc, nickel, and many other metals; cyanate (CNO − ); and thiocyanate (SCN − ). The fate of these species in solid wastes and residual process solutions that remain once gold recovery activities are terminated and in any water that moves beyond the ore processing facility dictates the degree to which cyanide poses a risk to aquatic organisms and aquatic-dependent organisms in the local environment. Cyanide-containing and cyanide-related species are subject to attenuation mechanisms that lead to dispersal to the atmosphere, chemical transformation to other carbon and nitrogen species, or sequestration as cyanometallic precipitates or adsorbed species on mineral surfaces. Dispersal to the atmosphere and chemical transformation amount to permanent elimination of cyanide, whereas sequestration amounts to storage of cyanide in locations from which it can potentially be remobilized by infiltrating waters if conditions change. From an environmental perspective, the most significant cyanide releases from gold leach operations involve catastrophic spills of process solutions or leakage of effluent to the unsaturated or saturated zones. These release pathways are unfavorable for two important cyanide attenuation mechanisms that tend to occur naturally: dispersal of free cyanide to the atmosphere and sunlight-catalyzed dissociation of strong cyanometallic complexes, which produces free cyanide that can then disperse to the atmosphere. The widest margins of environmental safety will be achieved where mineral processing operations are designed so that time for offgassing, aeration, and sunlight exposure are maximized in the event that cyanide-bearing solutions are released inadvertently.

Applied Geochemistry↗

Review of samples of water, sediment, tailings, and biota at the Little Bonanza mercury mine, San Luis Obispo County, California

Background and Objectives The Little Bonanza mercury (Hg) mine, located in San Luis Obispo County, California, is a relatively small mine with, a historical total Hg production of about 1,000 flasks. The mine workings and tailings are located in the headwaters of the previously unnamed west fork of Las Tablas Creek (WF Las Tablas Creek), which flows into the Nacimiento Reservoir. Wasterock and tailings eroded from the Little Bonanza Hg Mine have contributed Hg-enriched mine wastes to the headwaters of WF Las Tablas Creek. The mine is located on Federal land managed by the U.S. Bureau of Land Management (BLM), which requested that the U.S. Geological Survey (USGS) measure and characterize Hg and other geochemical constituents in tailings, sediment, water, and biota at and downstream from the minesite. This report is in response that request, from the lead agency which is mandated to conduct a Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) - Removal Site Investigation (RSI). The RSI applies to removal of Hg-contaminated mine waste from the Little Bonanza minesite as a means of reducing Hg transport to WF Las Tablas Creek. This report summarizes data obtained from field sampling of mine tailings, wasterock, sediment, water, and biota at the Little Bonanza Mine that was completed on April 6, 2010. Conditions during sampling were dry and no rain had occurred in the watershed for several weeks. Our results permit a preliminary assessment of the mining sources of Hg and associated chemical constituents that could produce elevated levels of monomethyl mercury (MMeHg) in WF Las Tablas Creek and in biota. History and Geology The history of the Little Bonanza Hg mine is summarized here from Yates (1943) and other references as cited. The Little Bonanza Mine, located 20 mi west of Paso Robles, was discovered in 1862. Although production was minor until 1900, from 1900 to 1906, the mine produced about 1,000 flasks of Hg. Intermittent production continued into the 1940s but was relatively limited. Underground workings, now caved and inaccessible, include about 3,000 ft of drifts, crosscuts, and raises on three levels extending 260 ft downward. The workings at the Little Bonanza Mine explore a zone of fault breccia, which trends northwest. The breccia is composed of fragments of sandstone, greenstone, serpentine, and chert in a shale matrix. The serpentine has been hydrothermally altered to silica-carbonate rock, and the Hg deposit is hosted within the zone of alteration. The veins are discontinuous and irregular, but form a steplike pattern along the fault zone. The principal mineralization occurring in the veins is irregular, consisting of disseminated zones of cinnabar. Most of the veins in the mine area contain cinnabar. Sample Sites and Methods Samples were collected to assess the concentrations of Hg and biogeochemically relevant constituents in tailings and wasterock piles at the Little Bonanza Hg mine. Tailings are present adjacent to a three-pipe retort used to process the Hg ore. The tailings occur in the upper 15 cm of the soil adjacent to the retort and slag from the retort is present on the surface. An area of disturbed soil and rock uphill from the retort was likely formed during construction of a dam that provided water for mining activities. Wasterock in these piles was sampled. The largest amount of tailings is exposed to the west of the retort in the bank of WF Las Tablas Creek. Water, sediment, and biota were sampled from WF Las Tablas Creek, which flows through the mine area. Sample-site locations are shown in figures 10 and 11 and listed in table 1. Samples were collected when streamflow was low and no precipitation had occurred.

California↗

Improving ecological restoration to curb biotic invasion - A practical guide

Common practices for invasive species control and management include physical, chemical, and biological approaches. The first two approaches have clear limitations and may lead to unintended (negative) consequences, unless carefully planned and implemented. For example, physical removal rarely completely eradicates the targeted invasive species and can cause disturbances that facilitate new invasions by nonnative species from nearby habitats. Chemical treatments can harm native, and especially rare, species through unanticipated side effects. Biological methods may be classified as biocontrol and the ecological approach. Similar to physical and chemical methods, biocontrol also has limitations and sometimes leads to unintended consequences. Therefore, a relatively safer and more practical choice may be the ecological approach, which has two major components: (1) restoration of native species and (2) biomass manipulation of the restored community, such as selective grazing or prescribed burning (to achieve and maintain viable population sizes). Restoration requires well-planned and implemented planting designs that consider alpha-, beta-, and gamma-diversity and the abundance of native and invasive component species at local, landscape, and regional levels. Given the extensive destruction or degradation of natural habitats around the world, restoration could be most effective for enhancing ecosystem resilience and resistance to biotic invasions. At the same time, ecosystems in human-dominated landscapes, especially those newly restored, require close monitoring and careful intervention (e.g., through biomass manipulation), especially when successional trajectories are not moving as intended. Biomass management frequently uses prescribed burning, grazing, harvesting, and thinning to maintain overall ecosystem health and sustainability. Thus, the resulting optimal, balanced, and relatively stable ecological conditions could more effectively limit the spread and establishment of invasive species. Here we review the literature (especially within the last decade) on ecological approaches that involve biodiversity, biomass, and productivity, three key community/ecosystem variables that reciprocally influence one another. We focus on the common and most feasible ecological practices that can aid in resisting new invasions and/or suppressing the dominance of existing invasive species. We contend that, because of the strong influences from neighboring areas (i.e., as exotic species pools), local restoration and management efforts in the future need to consider the regional context and projected climate changes.

Invasive Plant Science and Management↗

Occurrence of human pharmaceuticals in water resources of the United States: A review

The widespread environmental presence of some pharmaceuticals and other organic wastewater compounds has been documented globally (e.g. Buser et al. 1998; Ternes 1998; Stumpf et al.1999; Heberer et al. 2001; Kümmerer 2001; Ternes et al. 2001; Scheytt et al. 2001; Golet et al. 2002; Kolpin et al. 2002; Boyd et al. 2003; Metcalf et al. 2003). Recently, there have been several literature reviews and summary studies of the occurrence, fate, transport, and treatment of targeted human pharmaceuticals in wastewater effluent and associated environmental waters across the globe (e.g. Daughton and Ternes 1999; Sedlak et al. 2000; Suter and Giger 2000; Daughton and Jones-Lepp 2001; Jones et al. 2001; Heberer 2002; and Drewes et al. 2002). The occurrence of pharmaceutical compounds in water resources is explained by their ubiquitous use, excretion of large percentages of the mass consumed, and incomplete removal during wastewater treatment (Stumpf et al.1999). The recent increase in detection of trace concentrations (typically less than a part per billion) of pharmaceuticals in water resources across the globe reflects improvements in laboratory analytical methods (Sedlak et al. 2000) and the associated increases in field surveys. The detection of pharmaceutical compounds in large rivers in Europe and in the North Sea (Buser et al. 1998; Ternes 1998; Stumpf et al. 1999) highlighted the fact that highly soluble, trace organic compounds, such as pharmaceuticals, may escape removal in wastewater treatment, and the mixing and concentration of wastewaters through conventional wastewater treatment processes could provide a means of delivering these chemicals to environmental waters in a manner that would contaminate water resources on a large scale at trace levels (Richardson and Bowron 1985). In the United States, some of the first detections of a limited number of pharmaceutically active compounds or their transformation products were found in waters associated with landfill leachates or sewage effluent (Tabak and Bunch 1970; Garrison et al. 1976; Hignite and Azarnoff 1977; Bouwer et al. 1982; Eckel et al. 1991) decades ago. At the time of these studies, other industrial contaminants were the focus of regulatory and scientific interest; therefore, further studies on the environmental occurrence and transport of pharmaceutical compounds were rare.

Book chapter↗

Chemistry and palynology of carbon seams and associated rocks from the Witwatersrand goldfields, South Africa

Carbon seams in the Witwatersrand System of South Africa host some of the richest gold concentrations in the world. A study of the microscopic characteristics in thin sections and acid residues, and of the chemical and physical nature of the carbon-bearing phases, was undertaken to gain some understanding of the biological precursors and thermal changes that have occurred since the seams were buried. The HCl HF acid-resistant organic tissues in this Early Proterozoic coal are filamentous and spherical, which are typical morphologies for microorganisms. The tissues are carbonized black as would be expected for metamorphic rocks, so usual palynological techniques were of limited use. Therefore, the chemical and physical nature of the organic remains was studied by H C "> HC ratios, X-ray diffraction (XRD), 13 C nuclear magnetic resonance (NMR), reductive chemistry, crosspolarization/magic angle spinning NMR (CP/MAS), and electron spin resonance (ESR). The H C "> HC ratios of the samples examined are similar to those of semi-anthracite and petroleum cokes from delayed cokers. XRD shows graphite is not present and that the gold is in elemental form, not chemically bound or intercalated between carbon planes. NMR shows that both aromatic and paraffinic carbons are present. Integration of the carbon NMR spectra suggests that 80% of the carbon is sp 2 -hybridized and 20% is sp 3 -hybridized. Reductive chemistry shows that the benzenoid entities are larger than common polynuclear aromatic hydrocarbons such as perylene and decacyclene. Dipolar dephasing CP/MAS NMR suggests the presence of two types of paraffinic carbons, a rigid methylene group and a rotating methyl group. The narrowing of the ESR linewidth between room temperature and 300°C shows that the materials examined have not previously been subjected to temperatures as high as 300°C.

Witwatersrand goldfields↗

Interbasin flow in the Great Basin with special reference to the southern Funeral Mountains and the source of Furnace Creek springs, Death Valley, California, U.S.

Interbasin flow in the Great Basin has been established by scientific studies during the past century. While not occurring uniformly between all basins, its occurrence is common and is a function of the hydraulic gradient between basins and hydraulic conductivity of the intervening rocks. The Furnace Creek springs in Death Valley, California are an example of large volume springs that are widely accepted as being the discharge points of regional interbasin flow. The flow path has been interpreted historically to be through consolidated Paleozoic carbonate rocks in the southern Funeral Mountains. This work reviews the preponderance of evidence supporting the concept of interbasin flow in the Death Valley region and the Great Basin and addresses the conceptual model of pluvial and recent recharge [Nelson, S.T., Anderson, K., Mayo, A.L., 2004. Testing the interbasin flow hypothesis at Death Valley, California. EOS 85, 349; Anderson, K., Nelson, S., Mayo, A., Tingey, D., 2006. Interbasin flow revisited: the contribution of local recharge to high-discharge springs, Death Valley, California. Journal of Hydrology 323, 276-302] as the source of the Furnace Creek springs. We find that there is insufficient modern recharge and insufficient storage potential and permeability within the basin-fill units in the Furnace Creek basin for these to serve as a local aquifer. Further, the lack of high sulfate content in the spring waters argues against significant flow through basin-fill sediments and instead suggests flow through underlying consolidated carbonate rocks. The maximum temperature of the spring discharge appears to require deep circulation through consolidated rocks; the Tertiary basin fill is of insufficient thickness to generate such temperatures as a result of local fluid circulation. Finally, the stable isotope data and chemical mass balance modeling actually support the interbasin flow conceptual model rather than the alternative presented in Nelson et al. [Nelson, S.T., Anderson, K., Mayo, A.L., 2004. Testing the interbasin flow hypothesis at Death Valley, California. EOS 85, 349] and Anderson et al. [Anderson, K., Nelson, S., Mayo, A., Tingey, D., 2006. Interbasin flow revisited: the contribution of local recharge to high-discharge springs, Death Valley, California. Journal of Hydrology 323, 276-302]. In light of these inconsistencies, interbasin flow is the only readily apparent explanation for the large spring discharges at Furnace Creek and, in our view, is the likely explanation for most large volume, low elevation springs in the Great Basin. An understanding of hydrogeologic processes that control the rate and direction of ground-water flow in eastern and central Nevada is necessary component of regional water-resource planning and management of alluvial and bedrock aquifers.

Journal of Hydrology↗

The changing shapes of active volcanoes: History, evolution, and future challenges for volcano geodesy

At the very heart of volcanology lies the search for the 'plumbing systems' that form the inner workings of Earth’s active volcanoes. By their very nature, however, the magmatic reservoirs and conduits that underlie these active volcanic systems are elusive; mostly they are observable only through circumstantial evidence, using indirect, and often ambiguous, surficial measurements. Of course, we can infer much about these systems from geologic investigation of materials brought to the surface by eruptions and of the exposed roots of ancient volcanoes. But how can we study the magmatic processes that are occurring beneath Earth’s active volcanoes? What are the geometry, scale, physical, and chemical characteristics of magma reservoirs? Can we infer the dynamics of magma transport? Can we use this information to better forecast the future behavior of volcanoes? These questions comprise some of the most fundamental, recurring themes of modern research in volcanology. The field of volcano geodesy is uniquely situated to provide critical observational constraints on these problems. For the past decade, armed with a new array of technological innovations, equipped with powerful computers, and prepared with new analytical tools, volcano geodesists have been poised to make significant advances in our fundamental understanding of the behavior of active volcanic systems. The purpose of this volume is to highlight some of these recent advances, particularly in the collection and interpretation of geodetic data from actively deforming volcanoes. The 18 papers that follow report on new geodetic data that offer valuable insights into eruptive activity and magma transport; they present new models and modeling strategies that have the potential to greatly increase understanding of magmatic, hydrothermal, and volcano-tectonic processes; and they describe innovative techniques for collecting geodetic measurements from remote, poorly accessible, or hazardous volcanoes. To provide a proper context for these studies, we offer a short review of the evolution of volcano geodesy, as well as a case study that highlights recent advances in the field by comparing the geodetic response to recent eruptive episodes at Mount St. Helens. Finally, we point out a few areas that continue to challenge the volcano geodesy community, some of which are addressed by the papers that follow and which undoubtedly will be the focus of future research for years to come.

Journal of Volcanology and Geothermal Research↗

Isotopic compositions of the elements, 2001

The Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry completed its last review of the isotopic compositions of the elements as determined by isotope-ratio mass spectrometry in 2001. That review involved a critical evaluation of the published literature, element by element, and forms the basis of the table of the isotopic compositions of the elements (TICE) presented here. For each element, TICE includes evaluated data from the “best measurement” of the isotope abundances in a single sample, along with a set of representative isotope abundances and uncertainties that accommodate known variations in normal terrestrial materials. The representative isotope abundances and uncertainties generally are consistent with the standard atomic weight of the element A r ( E ) "> A r ( E ) Ar(E) and its uncertainty U[A r ( E )] "> U[A r ( E )] U[Ar(E)] recommended by CAWIA in 2001.

Journal of Physical and Chemical Reference Data↗

Birds and polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAH) are present throughout the global environment and are produced naturally and by activities of humans. Effects of PAH on birds have been determined by studies employing egg injection, egg immersion, egg shell application, single and multiple oral doses, subcutaneous injection, and chemical analysis of field-collected eggs and tissue. The four-to six-ring aromatic compounds are the most toxic to embryos, young birds, and adult birds. For embryos, effects include death, developmental abnormalities, and a variety of cellular and biochemical responses. For adult and young birds, effects include reduced egg production and hatching, increased clutch or brood abandonment, reduced growth, increased organweights, and a variety of biochemical responses. Trophic level accumulation is unlikely. Environmental exposure to PAH in areas of high human population or habitats affected by recent petroleum spills might be sufficient to adversely affect reproduction. Evidence of long-term effects of elevated concentrations of environmental PAH on bird populations is very limited and the mechanisms of effect are unclear.

Avian and Poultry Biology Reviews↗

Agricultural drainwater effects on wildlife in central California

In California's San Joaquin Valley and in numerous other agricultural areas in the western U.S., irrigation wastewater may accumulate in confined shallow aquifers, eventually rising to levels that adversely affect crops. To sustain long-term agricultural productivity in these regions, systems for the drainage and disposal of this subsurface wastewater must be installed. 1,2 the drained water may contain an array of soluble chemicals that have been applied to the crops, as well as those that have been leached from native soils. Agricultural drainwater is frequently disposed of by discharging it to surface aquatic systems where these constituents may be directly toxic to aquatic organisms, or they may bioaccumulate through the aquatic food webs upon which birds and other wildlife feed. The focus of this chapter is research conducted since 1983 to assess the effects of wildlife exposure to subsurface agricultural drainwater in the San Joaquin Valley. Agricultural drainwater is discharged primarily to tributaries and wetlands of the San Joaquin River system or, especially in the southern San Joaquin Valley, to evaporation ponds. 3 Because of high nutrient content in the drainwater, evaporation ponds have high levels of biological productivity and provide an abundant food supply for aquatic birds. Aquatic birds (primarily waterfowl and shorebirds) have been the main focus of wildlife research at the evaporation ponds, and at managed wetlands (primarily hunting clubs) within the San Joaquin River system, but mammals, snakes, and frogs have also been studied. Findings of those studies are summarized in this chapter. Other studies have been conducted on fish and aquatic invertebrates in areas receiving agricultural drainwater, but in this review those findings are described only as they relate to dietary exposure of wildlife.

Book chapter↗

Hydrogeochemical processes governing the origin, transport and fate of major and trace elements from mine wastes and mineralized rock to surface waters

The formation of acid mine drainage from metals extraction or natural acid rock drainage and its mixing with surface waters is a complex process that depends on petrology and mineralogy, structural geology, geomorphology, surface-water hydrology, hydrogeology, climatology, microbiology, chemistry, and mining and mineral processing history. The concentrations of metals, metalloids, acidity, alkalinity, Cl - , F - and SO 4 2- found in receiving streams, rivers, and lakes are affected by all of these factors and their interactions. Remediation of mine sites is an engineering concern but to design a remediation plan without understanding the hydrogeochemical processes of contaminant mobilization can lead to ineffective and excessively costly remediation. Furthermore, remediation needs a goal commensurate with natural background conditions rather than water-quality standards that might bear little relation to conditions of a highly mineralized terrain. This paper reviews hydrogeochemical generalizations, primarily from US Geological Survey research, that enhance our understanding of the origin, transport, and fate of contaminants released from mined and mineralized areas. Mobility of potential or actual contaminants from mining and mineral processing activities depends on (1) occurrence : is the mineral source of the contaminant actually present? (2) abundance : is the mineral present in sufficient quantity to make a difference? (3) reactivity : what are the energetics, rates, and mechanisms of sorption and mineral dissolution and precipitation relative to the flow rate of the water? and (4) hydrology : what are the main flow paths for contaminated water? Estimates of relative proportions of minerals dissolved and precipitated can be made with mass-balance calculations if minerals and water compositions along a flow path are known. Combined with discharge, these mass-balance estimates quantify the actual weathering rate of pyrite mineralization in the environment and compare reasonably well with laboratory rates of pyrite oxidation except when large quantities of soluble salts and evaporated mine waters have accumulated underground. Quantitative mineralogy with trace-element compositions can substantially improve the identification of source minerals for specific trace elements through mass balances. Post-dissolution sorption and precipitation (attenuation) reactions depend on the chemical behavior of each element, solution composition and pH, aqueous speciation, temperature, and contact-time with mineral surfaces. For example, little metal attenuation occurs in waters of low pH (<3.5) and metals tend to maintain element ratios indicative of the main mineral or group of minerals from which they dissolved, except Fe, SiO 2 , and redox-sensitive oxyanions (As, Sb, Se, Mo, Cr, V). Once dissolved, metal and metalloid concentrations are strongly affected by redox conditions and pH. Iron is the most reactive because it is rapidly oxidized by bacteria and archaea and Fe(III) hydrolyzes and precipitates at low pH (1&ndash;3) which is related directly to its first hydrolysis constant, pK 1 = 2.2. Several insoluble sulfate minerals precipitate at low pH including anglesite, barite, jarosite, alunite and basaluminite. Aluminum hydrolyzes near pH 5 (pK 1 = 5.0) and provides buffering and removal of Al by mineral precipitation from pH 4&ndash;5.5. Dissolved sulfate behaves conservatively because the amount removed from solution by precipitation is usually too small relative to the high concentrations in the water column and relative to the flow rate of the water.

Applied Geochemistry↗

Hydrogeologic framework refinement, ground-water flow and storage, water-chemistry analyses, and water-budget components of the Yuma area, southwestern Arizona and southeastern California

The ground-water and surface-water system in the Yuma area in southwestern Arizona and southeastern California is managed intensely to meet water-delivery requirements of customers in the United States, to manage high ground-water levels in the valleys, and to maintain treaty-mandated water-quality and quantity requirements of Mexico. The following components in this report, which were identified to be useful in the development of a ground-water management model, are: (1) refinement of the hydrogeologic framework; (2) updated water-level maps, general ground-water flow patterns, and an estimate of the amount of ground water stored in the mound under Yuma Mesa; (3) review and documentation of the ground-water budget calculated by the Bureau of Reclamation, U.S. Department of the Interior (Reclamation); and (4) water-chemistry characterization to identify the spatial distribution of water quality, information on sources and ages of ground water, and information about the productive-interval depths of the aquifer. A refined three-dimensional digital hydrogeologic framework model includes the following hydrogeologic units from bottom to top: (1) the effective hydrologic basement of the basin aquifer, which includes the Pliocene Bouse Formation, Tertiary volcanic and sedimentary rocks, and pre-Tertiary metamorphic and plutonic rocks; (2) undifferentiated lower units to represent the Pliocene transition zone and wedge zone; (3) coarse-gravel unit; (4) lower, middle, and upper basin fill to represent the upper, fine-grained zone between the top of the coarse-gravel unit and the land surface; and (5) clay A and clay B. Data for the refined model includes digital elevation models, borehole lithology data, geophysical data, and structural data to represent the geometry of the hydrogeologic units. The top surface of the coarse-gravel unit, defined by using borehole and geophysical data, varies similarly to terraces resulting from the down cutting of the Colorado River. Clay A is nearly the same as the previous conceptual hydrogeologic model definition (Olmsted and others, 1973), except for a minor westward extension from the city of Yuma. Clay B is extended to the southerly international boundary and increased in areal extent by about two-thirds of the original extent (Olmsted and others, 1973). The other hydrogeologic units generally are the same as in the previous conceptual hydrogeologic model. Before development, the Colorado and Gila Rivers were the sources of nearly all the ground water in the Yuma area through direct infiltration of water from river channels and annual overbank flooding. After construction of upstream reservoirs and clearing and irrigation of the floodplains, the rivers now act as drains for the ground water. Ground-water levels in most of the Yuma area are higher now than they were in predevelopment time. A general gradient of ground-water flow toward the natural discharge area south of the Yuma area still exists, but many other changes in flow are evident. Ground water in Yuma Valley once flowed away from the Colorado River, but now has a component of flow towards the river and Mexicali Valley. A ground-water mound has formed under Yuma Mesa from long-term surface-water irrigation; about 600,000 to 800,000 acre-ft of water are stored in the mound. Ground-water withdrawals adjacent to the southerly international boundary have resulted in water-level declines in that area. The reviewed and documented water budget includes the following components: (1) recharge in irrigated areas, (2) evapotranspiration by irrigated crops and phreatophytes, (3) ground-water return flow to the Colorado River, and (4) ground-water withdrawals (including those in Mexicali Valley). Recharge components were calculated by subtracting the amount of water used by crops from the amount of water delivered. Evapotranspiration rates were calculated on the basis of established methods, thus were appropriate for input to the ground-water flow model developed by the Bureau of Reclamation (William Greer, hydrologist, Bureau of Reclamation, written commun., 2005). Evapotranspiration by crops and phreatophytes were calculated by using crop coefficient methods and meteorological data. Other methods of calculating evapotranspiration rates by using combinations of satellite imagery and ground-based data could be used for higher spatial and temporal resolution. Ground-water return flow during years of low flow on the Colorado River (1972–82, 1987–92, and 1994–96) averaged 79,000 acre-ft per year. Ground-water withdrawal data for 1970–99 were similar to other estimates made by the U.S. Geological Survey for the Yuma area. New water-chemistry data were collected in 12 wells and 8 canals/drains to characterize spatial patterns in chemical constituents, determine isotopic ages of water, infer possible sources of ground water, and locate the vertical intervals of the aquifer that contribute most water to wells. Depth-dependent samples were collected at one of the wells (YM-10). A large quantity of water-quality data were compiled from Bureau of Reclamation and U.S. Geological Survey records and merged into the U.S. Geological Survey National Water Information System database. New samples were analyzed for major ions, nutrients, stable isotopes of oxygen and hydrogen, tritium ( 3 H), and carbon-14 ( 14 C) (along with C 13 /C 12 ratios). Light values of oxygen-18 ( 18 O) and deuterium ( 2 H, D) in well 242-2 indicate recharge from the Colorado River. Heavy water samples from wells 242-22, CADC, and Mesa del Sol indicate local recharge sources. Tritium data indicate there is young water in wells in the valleys and near the edge of Yuma Mesa, while older water is found far from the Colorado River. 14 C data indicate that water from wells near the southerly international boundary is at least several thousand years old.

Arizona, California↗

Can kittiwakes smell? Experimental evidence in a larid species

Birds have long been thought to have a poor sense of smell, although they have the proper anatomical and neurological structures for detecting olfactory cues ( Roper 1999 ). However, in the past decade several bird species have been shown to use smell in various contexts, such as foraging ( Nevitt et al. 1995 ), navigation ( Wallraff 2004 ), selection of nest materials ( Petit et al. 2002 , Gwinner & Berger 2008 ), nest location ( Bonadonna & Bretagnolle 2002 ), predator avoidance ( Amo et al. 2008 , Roth et al. 2008 ) and recognition of conspecifics ( Hagelin et al. 2003 ) or mates ( Bonadonna & Nevitt 2004 , for reviews see Roper 1999 , Hagelin & Jones 2007 , Nevitt 2008 ). The evidence, however, mainly concerns the Procellariiformes (petrels, shearwaters and albatrosses), a group that has long been suspected of using olfaction because of their strong body odour, highly developed olfactory bulb, nocturnal habits and burrow‐nesting ( Nevitt & Bonadonna 2005 , Nevitt 2008 ). Evidence of olfactory ability is scarce in other avian taxa. Exceptions include, for instance, Turkey Vulture Cathartes aura ( Smith & Paselk 1986 ), Brown Kiwi Apteryx australis ( Wenzel 1968 ), Homing Pigeon Columba livia ( Wallraff 2004 ), Blue Tit Cyanistes caeruleus ( Petit et al. 2002 , Amo et al. 2008 ), Domestic Fowl Gallus domesticus ( McKeegan et al. 2005 ), Kakapo Strigops habroptilus ( Hagelin 2004 ), Yellow‐backed Chattering Lory Lorius garrulus flavopalliatus ( Roper 2003 ), African Penguin Spheniscus demersus ( Cunningham et al. 2008 ) and Crested Auklets Aethia cristatella ( Hagelin et al. 2003 ). The Laridae, including Black‐legged Kittiwakes Rissa tridactyla , are diurnal, have relatively small olfactory bulbs ( Bang & Cobb 1968 ) and do not appear to use olfaction to locate food ( Frings et al. 1955 , Lequette et al. 1989 , Verheyden & Jouventin 1994 ). Kittiwakes use vocal cues in mate and parent/offspring recognition ( Wooller 1978 , Mulard & Danchin 2008 ), suggesting that olfaction may be at best secondary in those contexts. However, mates commonly allopreen, potentially exposing them to their mate’s chemical compounds. Moreover, the relative size of the olfactory bulb may be a poor predictor of olfactory abilities ( Hagelin 2004 , Mennerat et al. 2005 ). The aim of this experimental study was to assess whether Black‐legged Kittiwakes are able to detect odours added to the nest.

Alaska↗

Groundwater quality of the Gulf Coast aquifer system, Houston, Texas, 2010

During March&ndash;December 2010, the U.S. Geological Survey, in cooperation with the city of Houston, collected source-water samples from 60 municipal supply wells in the Houston area. These data were collected as part of an ongoing study to determine concentrations, spatial extent, and associated geochemical conditions that might be conducive for mobility and transport of selected naturally occurring contaminants (selected trace elements and radionuclides) in the Gulf Coast aquifer system in the Houston area. In the summers of 2007 and 2008, a reconnaissance-level survey of these constituents in untreated water from 28 municipal supply wells was completed in the Houston area. Included in this report are the complete analytical results for 47 of the 60 samples collected in 2010&mdash;those results which were received from the laboratories and reviewed by the authors as of December 31, 2010. All of the wells sampled were screened in the Gulf Coast aquifer system; 22 were screened entirely in the Evangeline aquifer, and the remaining 25 wells contained screened intervals that intersected both Evangeline and Chicot aquifers. The data documented in this report were collected as part of an ongoing study to characterize source-water-quality conditions in untreated groundwater prior to drinking-water treatment. An evaluation of contaminant occurrence in source water provides background information regarding the presence of a contaminant in the environment. Because source-water samples were collected prior to any treatment or blending that potentially could alter contaminant concentrations, the water-quality results documented by this report represent the quality of the source water, not the quality of finished drinking water provided to the public. Samples were analyzed for major ions (calcium, magnesium, potassium, sodium, bromide, chloride, fluoride, silica, and sulfate), residue on evaporation (dissolved solids), trace elements (arsenic, barium, boron, chromium, iron, lithium, manganese, molybdenum, selenium, strontium, and vanadium), and selected radionuclides (gross alpha- and beta-particle activity [at 72 hours and 30 days], carbon-14, radium-226, radon-222, and uranium). Field measurements were made of selected physicochemical (relating to both physical and chemical) properties (oxidation-reduction potential, turbidity, dissolved-oxygen concentration, pH, specific conductance, water temperature, and alkalinity) and unfiltered sulfides. Similar to the results from the reconnaissance survey, physicochemical properties, major ions, and trace elements varied considerably. The ranges of selected physicochemical properties were as follows: oxidation-reduction potential ranged from -173 to 466 millivolts, dissolved oxygen ranged from less than 0.1 to 4.4 milligrams per liter, pH ranged from 7.2 to 7.8, specific conductance ranged from 439 to 724 microsiemens per centimeter at 25 degrees Celsius, and alkalinity ranged from 159 to 276 milligrams per liter as calcium carbonate. The largest ranges in concentration for filtered major ion constituents were obtained for cations sodium and calcium and for anions chloride and sulfate. Arsenic concentrations measured in samples from the 47 wells ranged from 1.6 to 23.5 micrograms per liter. The maximum concentration of arsenic (23.5 micrograms per liter) was measured in the source-water sample from well LJ-65-12-328. Quantifiable concentrations of barium, boron, lithium, molybdenum, and strontium were measured in all 47 filtered, source-water samples. Quantifiable concentrations of manganese were measured in 46 source-water samples, and an estimated concentration of manganese was measured in 1 sample. Chromium, iron, selenium, and vanadium were detected in 24 or more of the 47 source-water samples. Gross alpha-particle activities and beta-particle activities for all 47 samples were analyzed at 72 hours after sample collection and again at 30 days after sample collection, allowing for the measurement of the activity of short-lived isotopes. Gross alpha-particle activities reported in this report were not adjusted for activity contributions by radon or uranium and, therefore, are conservatively high estimates if compared to the U.S. Environmental Protection Agency National Primary Drinking Water Regulation for adjusted gross alpha-particle activity. The gross alpha-particle activities at 30 days in the samples ranged from R0.60 to 25.5 picocuries per liter and at 72 hours ranged from 2.58 to 39.7 picocuries per liter, and the "R" preceding the value of 0.60 picocuries per liter refers to a nondetected result less than the sample-specific critical level. Gross beta-particle activities measured at 30 days ranged from 1.17 to 14.4 picocuries per liter and at 72 hours ranged from 1.97 to 4.4 picocuries per liter. Filtered uranium was detected in quantifiable amounts in all of the 47 wells sampled. The uranium concentrations ranged from 0.03 to 42.7 micrograms per liter. One sample was analyzed for carbon-14, and the amount of modern atmospheric carbon was reported as 0.2 percent. Six source-water samples collected from municipal supply wells were analyzed for radium-226, and all of the concentrations were considered detectable concentrations (greater than their associated sample-specific critical level). Three source-water samples collected were analyzed for radon-222, and all of the concentrations were substantially greater than the associated sample-specific critical level.

Texas↗

Chapter 5: Impact of sedimentary-exhalative hydrothermal systems on marine chemistry and mass extinctions: Applications for ore genesis research and mineral exploration

Times of metal-rich brine discharge into ancient ocean basins, associated with the formation of sedimentary-exhalative (sedex) Zn-Pb-Ba ore deposits, coincided with short-duration positive excursions (“spikes”) in the global marine Sr isotope record. While these spikes are unexplained by conventional oceanic models, chronostratigraphic correlations, combined with mass balance evidence and oceanographic modeling, suggest that the flux of radiogenic Sr from sedex brines during ore formation is sufficient to explain these previously enigmatic 87 Sr/ 86 Sr spikes. We review existing 87 Sr/ 86 Sr data and present new data as verification of these global 87 Sr/ 86 Sr spikes and their correlations with the formation of giant sedex ore deposits. Major events include an 1 ×10 −4 (~0.7078–~0.7079) excursion contemporaneous with formation of the Rammelsberg deposit at ~389 Ma; spikes on the order of 1 to 3 × 10 −4 , coeval with formation of the Meggen deposit at ~381 Ma, several ore deposits in the Macmillan Pass district at ~379 to 375 Ma, and the Silvermines deposits at ~352 Ma; and two >6 × 10 −4 spikes coincident with formation of the giant Navan deposit at ~346 Ma and Red Dog deposits at ~337 Ma. Moreover, the timing of peak 87 Sr/ 86 Sr spikes correlates with global δ 13 C and δ 18 O spikes, deposition of metal-rich black shales and ironstones, metal-induced malformation (teratology) of marine organisms, and mass extinctions. The relationships among these features were poorly understood, but our new model explains how the flux of key biolimiting nutrients and metals contained in sedex brines, demonstrably equivalent to or exceeding that of the total modern riverine flux to the ocean, spurred ocean eutrophication, which, ultimately, through a series of positive feedback mechanisms, may have triggered global chemical and biological events. If, as we hypothesize, sedex hydrothermal systems are recorded in the global marine isotopic, geologic, and biological records, our findings define a new approach to the study of and exploration for sedex deposits. We demonstrate that fluid inclusion solute chemistry and isotopic and stratigraphic studies of sedex deposits, coupled with chronostratigraphic correlation and high-resolution 87 Sr/ 86 Sr isotope chemostratigraphy, can be used to answer long-standing questions about geologic processes responsible for formation of these extraordinary deposits. This approach provides evidence for the age, duration, and fluxes of fluids and metals vented into the ocean by these giant hydrothermal systems. Accordingly, the marine 87 Sr/ 86 Sr curve constitutes a global exploration tool that could be applied to assess the mineral potential of sedimentary basins. To illustrate the potential of this tool to identify favorable stratigraphic ages and basins with potential for undiscovered giant sedex deposits, we highlight several spikes, on par with those characteristic of the Red Dog and Navan deposits, which have not been correlated with known metal deposits. Given these strong temporal correlations, mass balance estimates, and results of ocean chemistry modeling, our study suggests that further work is warranted to determine the extent to which periodic venting of hydrothermal basinal brines into the ocean has influenced the evolution of marine chemistry. Ultimately, these global signatures can be applied to the study of and exploration for sedex deposits.

Book chapter↗

Inter-laboratory variation in the chemical analysis of acidic forest soil reference samples from eastern North America

Long-term forest soil monitoring and research often requires a comparison of laboratory data generated at different times and in different laboratories. Quantifying the uncertainty associated with these analyses is necessary to assess temporal changes in soil properties. Forest soil chemical properties, and methods to measure these properties, often differ from agronomic and horticultural soils. Soil proficiency programs do not generally include forest soil samples that are highly acidic, high in extractable Al, low in extractable Ca and often high in carbon. To determine the uncertainty associated with specific analytical methods for forest soils, we collected and distributed samples from two soil horizons (Oa and Bs) to 15 laboratories in the eastern United States and Canada. Soil properties measured included total organic carbon and nitrogen, pH and exchangeable cations. Overall, results were consistent despite some differences in methodology. We calculated the median absolute deviation (MAD) for each measurement and considered the acceptable range to be the median 6 2.5 3 MAD. Variability among laboratories was usually as low as the typical variability within a laboratory. A few areas of concern include a lack of consistency in the measurement and expression of results on a dry weight basis, relatively high variability in the C/N ratio in the Bs horizon, challenges associated with determining exchangeable cations at concentrations near the lower reporting range of some laboratories and the operationally defined nature of aluminum extractability. Recommendations include a continuation of reference forest soil exchange programs to quantify the uncertainty associated with these analyses in conjunction with ongoing efforts to review and standardize laboratory methods.

Ecosphere↗

A review of spatially resolved techniques and applications of organic petrography in shale petroleum systems

This review examines new techniques and applications of organic petrography in source-rock reservoir petroleum systems that have occurred along with development of the global ‘shale revolution’ in energy resources. The review is limited to techniques and instrumentation that provide spatially resolved information, typically at or below microscales, for dispersed organic matter occurring in situ in samples of shale and mudrock. A brief summary of ion beam sample preparation is followed by discussion of the most common analytical techniques and applications. Advantages and limitations of each technique, including requisite sample preparation, types of information generated [e.g., molecular or elemental (isotopic) abundance], sensitivity, and resolution are discussed. In a few cases, techniques not yet applied to organic petrology of shale or mudrock are described (e.g., X-ray photoelectron spectroscopy imaging), in anticipation of near-term future application. The most common in situ techniques applied for characterization of organic matter in shale and mudrock include optical (including fluorescence) and electron microscopies, Raman, fluorescence, and infrared spectroscopies, and surficial measurements via force microscopy. Techniques that show growing application to organic petrography of shale include tip-enhanced photothermal infrared spectroscopy, mass spectrometry imaging, and synchrotron-based spectroscopies, among others. It is anticipated that the future of dispersed organic matter petrography will hold continued development of integrated instrument techniques (e.g., simultaneous or sequential correlative microscopies and/or spectroscopies of the same location), increased instrumental resolution, increased use of multiscale and multimodal organic petrography investigations, and three-dimensional imaging and chemical speciation mapping applications via multiple analytical approaches.

International Journal of Coal Geology↗

Effects of vegetation manipulation on breeding waterfowl in prairie wetlands--a literature review

Literature on the effects of fire and grazing on the wetlands used by breeding prairie waterfowl is reviewed. Both dabbling and diving ducks and their broods prefer wetlands with openings in the marsh canopy. Decreased use is commonly associated with decreased habitat heterogeneity caused by tall, robust hydrophytes such as Typha spp. and other species adapted to form monotypes in the absence of disturbance. Nearly all previous studies indicate that reductions in height and density of tall, emergent hydrophytes by fire and grazing (unless very intensive) generally benefit breeding waterfowl. Such benefits are an increase in pair density, probably related to increased interspersion of cover and open water which decreases visibility among conspecific pairs, and improvements in their invertebrate food resources that result from increased habitat heterogeneity. Research needs are great because of the drastic changes that have accrued to prairie wetlands through fire suppression, cultivation, and other factors. The physical and biological environments preferred by species of breeding waterfowl during their seasonal and daily activities should be ascertained from future studies in wetland complexes that exist in the highest state of natural preservation. Long-term burning and grazing experiments should follow on specific vegetatively-degraded wetlands judged to be potentially important breeding areas. Seasonality, frequency, and intensity of treatments should be varied and combined and, in addition to measuring the response of the biotic community, the changes in the physical and chemical environment of the wetlands should be monitored to increase our knowledge of causative factors and possible predictive values.

Fish and Wildlife Technical Report↗