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USGS1979

Surface faults in the gulf coastal plain between Victoria and Beaumont, Texas

Displacement of the land surface by faulting is widespread in the Houston-Galveston region, an area which has undergone moderate to severe land subsidence associated with fluid withdrawal (principally water, and to a lesser extent, oil and gas). A causative link between subsidence and fluid extraction has been convincingly reported in the published literature. However, the degree to which fluid withdrawal affects fault movement in the Texas Gulf Coast, and the mechanism(s) by which this occurs are as yet unclear. Faults that offset the ground surface are not confined to the large (>6000-km 2 ) subsidence “bowl” centered on Houston, but rather are common and characteristic features of Gulf Coast geology. Current observations and conclusions concerning surface faults mapped in a 35,000-km 2 area between Victoria and Beaumont, Texas (which area includes the Houston subsidence bowl) may be summarized as follows: (1) Hundreds of faults cutting the Pleistocene and Holocene sediments exposed in the coastal plain have been mapped. Many faults lie well outside the Houston-Galveston region; of these, more than 10% are active, as shown by such features as displaced, fractured, and patched road surfaces, structural failure of buildings astride faults, and deformed railroad tracks. (2) Complex patterns of surface faults are common above salt domes. Both radial patterns (for example, in High Island, Blue Ridge, Clam Lake, and Clinton domes) and crestal grabens (for example, in the South Houston and Friendswood-Webster domes) have been recognized. Elongate grabens connecting several known and suspected salt domes, such as the fault zone connecting Mykawa, Friendswood-Webster, and Clear Lake domes, suggest fault development above rising salt ridges. (3) Surface faults associated with salt domes tend to be short (<5 km in length), numerous, curved in map view, and of diverse trend. Intersecting faults are common. In contrast, surface faults in areas unaffected by salt diapirism are frequently mappable for appreciable distances (>10 km), occur singly or in simple grabens, have gently sinuous traces, and tend to lie roughly parallel to the ENE-NE “coastwise” trend common to regional growth faults identified in subsurface Tertiary sediments. (4) Evidence to support the thesis that surface scarps are the shallow expression of faults extending downward into the Tertiary section is mostly indirect, but nonetheless reasonably convincing. Certainly the patterns of crestal grabens and radiating faults mapped on the surface above salt domes are more than happenstance; analogous fault patterns have been documented around these structures at depth. Similarly, some of the long surface faults not associated with salt domes seem to have subsurface counterparts among known regional growth faults documented through well logs and seismic data. Correlations between surface scarps and faults offsetting subsurface data are not conclusive because of the large vertical distances (1900- 3800 m) involved in making the most of the inferred connections. Nevertheless, the large number of successful correlations - in trend, movement sense, and position - suggests that many surface scarps represent merely the most recent displacements on faults formed during the Tertiary. (5) Upstream-facing fault scarps in this region of low relief can be significant impediments to streams. Locally, both abandoned, mud-filled Pleistocene distributary channels and, more commonly, Holocene drainage lines still occupied by perennial streams reflect the influence of faulting on their development. Some bend sharply near faults and have tended to flow along or pond against the base of scarps; others meander within topographically expressed grabens. Such evidence for Quaternary displacement of the ground surface is widespread in the Texas Gulf coast. In the general, however, streams in areas now offset by faulting show no disruption of their courses where they cross fault scarps. Such scarps are probably very young, and where they can be demonstrated to partly or wholly predate fluid withdrawal, very recent natural fault activity is indicated. (6) Early aerial photographs (1930) of the entire region and topographic maps (1915-16 surveys) of Harris County (Houston and vicinity) show that many faults had already displaced the land surface at a time when appreciable pressure declines in subjacent strata were localized to relatively few areas of large-scale pumping. Prehistoric faulting of the land surface, as noted above, appears to have affected much of the Texas Gulf Coast. (7) A relation between groundwater extraction and current motion on active faults is suspected because of the increased incidence of ground failure in the Houston-Galveston subsidence bowl. This argument is weakened somewhat by recognition of numerous surface faults, some of them active today, far beyond the periphery of the strongly subsiding area. Moreover, tilt beam records from two monitored faults in northwest Houston and accounts of fault damage from local residents demonstrate a complex, episodic nature of fault creep which can only partially be correlated with groundwater production. Nevertheless, although specific mechanisms are in doubt, the extraction of groundwater from shallow (<800-m) sands is probably a major factor in contributing to current displacement of the ground surface in the Houston-Galveston region. Within this large area, the number of faults recognizable from aerial photographs has increased at least tenfold between 1930 and 1970. Elsewhere in the Texas Gulf Coast only a moderate increase has been noted, some of which is possibly attributable to oil and gas production. Surface fault density in the Houston-Galveston region is far greater than in any other area of the Texas Gulf Coast investigated to date. A plausible explanation for these differences is that large overdrafts of groundwater over an extended period of time in the Houston-Galveston region have stimulated fault activity there. Throughout the Texas Gulf Coast, however, a natural contribution to fault motion remains a distinct possibility.

Texas↗

USGS1993

The pyramid system for multiscale raster analysis

Geographical research requires the management and analysis of spatial data at multiple scales. As part of the U.S. Geological Survey's global change research program a software system has been developed that reads raster data (such as an image or digital elevation model) and produces a pyramid of aggregated lattices as well as various measurements of spatial complexity. For a given raster dataset the system uses the pyramid to report: (1) mean, (2) variance, (3) a spatial autocorrelation parameter based on multiscale analysis of variance, and (4) a monofractal scaling parameter based on the analysis of isoline lengths. The system is applied to 1-km digital elevation model (DEM) data for a 256-km2 region of central California, as well as to 64 partitions of the region. PYRAMID, which offers robust descriptions of data complexity, also is used to describe the behavior of topographic aspect with scale. ?? 1993.

Computers & Geosciences↗

USGS1993

Rotational reflectance properties of Arkoma Basin dispersed vitrinite: Insights for understanding reflectance populations in high thermal maturity regions

Analysis and interpretation of dispersed vitrinite reflectance data in regions of high thermal maturity (> 2% vitrinite reflectance) have been equivocal partly because of an increase in width and complexity of reflectance histograms with increasing mean reflectance. Such complexity is illustrated by random reflectance ( R ran ) data from the Arkoma Basin that display a linear increase in standard deviation of R ran with an increase in mean R ran from 1 to 5%. Evaluating how much of the dispersion in these data is the result of vitrinite anisotropy and how much is the result of mixing of kerogen populations by sedimentary processes and/or sampling procedures has been problematic. Automated collection of reflectance data during polarizer rotation provides preliminary data for solution of this problem. Rotational reflectance data collected from a subset of Arkoma Basin samples reveal positive, linear relationships among maximum ( R ′ max ), random ( R ran ), rotational ( R rot ), and minimum ( R ′ min ) reflectance, as well as a systematic increase in bireflectance ( R ′ max – R ′ min ) with increasing reflectance. R ′ max and R rot display lower standard deviations and narrower, more nearly unimodal histograms than R ran and R ′ min , suggesting that R ′ max and R rot are superior (less ambiguous) indices of thermal maturity. These data patterns are inferred to be mostly an indication of increasing vitrinite anisotropy with increasing thermal maturity, suggesting that the linear covariance observed between mean R ran and standard deviation in dispersed organic data sets from regions of high thermal maturity may be explained mostly as the result of increasing vitrinite anisotropy with increasing thermal maturity.

Arkansas, Oklahoma↗

USGS1990

Studies of angiospermous woods in Australian brown coal by nuclear magnetic resonance and analytical pyrolysis: new insight into early coalification

Many Tertiary coals contain abundant fossilized remains of angiosperms, which commonly dominated the ancient peat-swamp environments; modern analogs of such swamps can be found in tropical and subtropical regions of the world. Comparisons of angiospermous wood from Australian brown coal with similar wood buried in modern peat swamps of Indonesia have provided some new insights into coalification reactions. These comparisons were made by using solid-state 13 C nuclear magnetic resonance (NMR) techniques and pyrolsis-gas chromatography-mass spectrometry (py-gc-ms). These two modern techniques are especially suited for detailed structural evaluation of the complex macromolecules in coal. The earliest transformation (peatification) of organic matter in angiospermous wood is the degradation and removal of cellulosic components and the concomitant selective preservation of lignin-derived components. The angiospermous lignin that becomes enriched in wood as a result of cellulose degradation also is modified by coalification reactions; this modification, however, does not involve degradation and removal of the lignin. Rather, the early coalification process transforms the lignin phenols (guiacyl and syringyl) to eventually yield the aromatic structures typically found in brown coal. One such transformation, which is determined from NMR data, involves the cleavage of aryl-ether bonds that link guaiacyl and syringyl units in lignin, and this transformation leads to the formation of free lignin phenols. Another transformation, which is also determined from the NMR data, involves the loss of methoxyl groups, probably via demethylation, to produce catechol-like structures. Coincident with ether-cleavage and demethylation, the aromatic rings derived from lignin phenols become more carbon-substituted and cross linked, as determined by dipolar-dephasing NMR studies. This cross linking is probably responsible for preventing the lignin phenols, which are freed from the lignin macromolecule by ether cleavage, from being removed from the coal by dissolution. Pyrolysis data suggest that the syringyl units are altered more readily than are guaiacyl units, and this difference in resistance leads to an enrichment of the guaiacyl units in fossil angiospermous woods. Many of the coalification reactions noted above occur to some degree in all angiospermous fossil wood examined; however, some significant differences are observed in the degree of coalification of the fossil wood samples from the same burial depth in the brown coal. These differences indicate that the depth and duration of burial are probably not entirely responsible for the variations in degree of coalification. Different rates of degradation in peat may have contributed to the variations in the apparent degree of coalification; some woods may have been altered more rapidly at the peat stage than others. Although preliminary, this systematic study of botanically related wood in peat and coal results in a more detailed differentiation of coalification reactions than have previous investigations. The combined use of solid-state 13 C NMR and py-gc-ms has facilitated this detailed insight into the coalification of angiospermous wood.

International Journal of Coal Geology↗

USGS1987

Evolution and petroleum geology of Amlia and Amukta intra-arc summit basins, Aleutian Ridge

Amlia and Amukta Basins are the largest of many intra-arc basins formed in late Cenozoic time along the crest of the Aleutian Arc. Both basins are grabens filled with 2-5 km of arc-derived sediment. A complex system of normal faults deformed the basinal strata. Although initial deposits of late Micocene age may be non-marine in origin, by early Pliocene time, most of the basinfill consisted of pelagic and hemipelagic debris and terrigenous turbidite deposits derived from wavebase and subaerial erosion of the arc's crestal areas. Late Cenozoic volcanism along the arc commenced during or shortly after initial subsidence and greatly contributed to active deposition in Amlia and Amukta Basins. Two groups of normal faults occur: major boundary faults common to both basins and 'intra-basin' faults that arise primarily from arc-parallel extension of the arc. The most significant boundary fault, Amlia-Amukta fault, is a south-dipping growth fault striking parallel to the trend of the arc. Displacement across this fault forms a large half-graben that is separated into the two depocentres of Amlia and Amukta Basins by the formation of a late Cenozoic volcanic centre, Seguam Island. Faults of the second group reflect regional deformation of the arc and offset the basement floor as well as the overlying basinal section. Intra-basin faults in Amlia Basin are predominantly aligned normal to the trend of the arc, thereby indicating arc-parallel extension. Those in Amukta basin are aligned in multiple orientations and probably indicate a more complex mechanism of faulting. Displacement across intra-basin faults is attributed to tectonic subsidence of the massif, aided by depositional loading within the basins. In addition, most intra-basin faults are listric and are associated with high growth rates. Although, the hydrocarbon potential of Amlia and Amukta Basins is difficult to assess based on existing data, regional considerations imply that an adequate thermal history conducive to hydrocarbon generation has prevailed during the past 6-5 my. The possibility for source rocks existing in the lower sections of the basins is suggested by exposures of middle and upper Miocene carbonaceous mudstone on nearby Atka Island and the implication that euxinic conditions may have prevailed during the initial formation of the basins. Large structures have evolved to trap migrating hydrocarbons, but questions remain concerning the preservation of primary porosity in a sedimentary section rich in reactive volcaniclastic debris. ?? 1987.

Marine and Petroleum Geology↗

USGS1989

Hydrocarbon gas seeps of the convergent Hikurangi margin, North Island, New Zealand

Two hydrocarbon gas seeps, located about 13 km apart, have distinctive molecular and isotopic compositions. These seeps occur within separate tectonic melange units of narrow parallel trending and structurally complex zones with incorporated upper Cretaceous and Palaeogene passive continental margin deposits which are now compressively deformed and imbricated along the convergent Hikurangi margin of North Island, New Zealand. At Brookby Station within the Coastal High, the seeping hydrocarbon gas has a methane/ethane ratio of 48 and ??13C and ??D values of methane of -45.7 and -188???, respectively (relative to the PDB and SMOW standards). Within the complex core of the Elsthorpe Anticline at Campbell Station seep, gas has a methane/ethane ratio of about 12000, and the methane has ??13C and ??D values of -37.4 and -170???, respectively. The source of the gases cannot be positively identified, but the gases probably originate from the thermal decomposition of organic matter in tectonically disturbed upper Cretaceous and/or lower Tertiary sedimentary rocks of passive margin affinity and reach the surface by migration along thrust faults associated with tectonic melange. The geochemical differences between the two gases may result from differences in burial depths of similar source sediment. ?? 1989.

Marine and Petroleum Geology↗

USGS1979

Regional and local networks of horizontal control, Cerro Prieto geothermal area

The Cerro Prieto geothermal area in the Mexicali Valley 30 km southeast of Mexicali, Baja California, is probably deforming due to (1) the extraction of large volumes of steam and hot water, and (2) active tectonism. Two networks of precise horizontal control were established in Mexicali Valley by the U.S. Geological Survey in 1977 - 1978 to measure both types of movement as they occur. These networks consisted of (1) a regional trilateration net brought into the mountain ranges west of the geothermal area from survey stations on an existing U.S. Geological Survey crustal-strain network north of the international border, and (2) a local net tied to stations in the regional net and encompassing the area of present and planned geothermal production. Survey lines in this net were selected to span areas of probable ground-surface movements in and around the geothermal area. Electronic distance measuring (EDM) instruments, operating with a modulated laser beam, were used to measure the distances between stations in both networks. The regional net was run using a highly precise long-range EDM instrument, helicopters for transportation of men and equipment to inaccessible stations on mountain peaks, and a fixed wing airplane flying along the line of sight. Precision of measurements with this complex long-range system approached 0-2 ppm of line length. The local net was measured with a medium-range EDM instrument requiring minimal ancillary equipment. Precision of measurements with this less complex system approached 3 ppm for the shorter line lengths. The detection and analysis of ground-surface movements resulting from tectonic strains or induced by geothermal fluid withdrawal is dependent on subsequent resurveys of these networks. ?? 1979.

Geothermics↗

USGS1995

The Geysers-Clear Lake geothermal area, California - An updated geophysical perspective of heat sources

The Geysers-Clear Lake geothermal area encompasses a large dry-steam production area in The Geysers field and a documented high-temperature, high-pressure, water-dominated system in the area largely south of Clear Lake, which has not been developed. Both systems have been extensively studied with geophysical techniques, drilling, and geological mapping during the past 20 years. An updated view is presented of the geological/geophysical complexities of the crust in The Geysers-Clear Lake region in order to address key unanswered questions about the heat source and tectonics. Early geophysical interpretations used a gravity low centered in the area between Clear Lake and The Geysers to suggest that a large magma chamber existed at depths starting at about 7 km. This first-order assumption of a large magma chamber expressed in the gravity data was used as a guide in subsequent geophysical and geological interpretations. Drill-hole temperature evidence is strongly suggestive of a shallow, hot-intrusive body, but in this paper the complexities are documented of the geological and geophysical data sets that make it difficult to pinpoint the location of “magma” or hot, solidified intrusive material. Forward modeling, multidimensional inversions, and ideal body analysis of the gravity data, new electromagnetic sounding models, and arguments made from other geophysical data sets suggest that many of the geophysical anomalies have significant contributions from rock property and physical state variations in the upper 7 km and not from ”magma“ at greater depths. Regional tectonic and magmatic processes are analyzed to develop an updated scenario for pluton emplacement that differs substantially from earlier interpretations. In addition, a rationale is outlined for future exploration for geothermal resources in The Geysers-Clear Lake area.

Geothermics↗

USGS1993

Aquatic photolysis: photolytic redox reactions between goethite and adsorbed organic acids in aqueous solutions

Photolysis of mono and di-carboxylic acids that are adsorbed onto the surface of the iron oxyhydroxide (goethite) results in an oxidation of the organic material and a reduction from Fe(III) to Fe(II) in the iron complex. There is a subsequent release of Fe2+ ions into solution. At constant light flux and constant solution light absorption, the factors responsible for the degree of photolytic reaction include: the number of lattice sites that are bonded by the organic acid; the rate of acid readsorption to the surface during photolysis; the conformation and structure of the organic acid; the degree of oxidation of the organic acid; the presence or absence of an ??-hydroxy group on the acid, the number of carbons in the di-acid chain and the conformation of the di-acid. The ability to liberate Fe(III) at pH 6.5 from the geothite lattice is described by the lyotropic series: tartrate>citrate> oxalate > glycolate > maleate > succinate > formate > fumarate > malonate > glutarate > benzoate = butanoate = control. Although a larger amount of iron is liberated, the series is almost the same at pH 5.5 except that oxalate > citrate and succinate > maleate. A set of rate equations are given that describe the release of iron from the goethite lattice. It was observed that the pH of the solution increases during photolysis if the solutions are not buffered. There is evidence to suggest the primary mechanism for all these reactions is an electron transfer from the organic ligand to the Fe(III) in the complex. Of all the iron-oxyhydroxide materials, crystalline goethite is the least soluble in water; yet, this study indicates that in an aqueous suspension, iron can be liberated from the goethite lattice. Further, it has been shown that photolysis can occur in a multiphase system at the sediment- water interface which results in an oxidation of the organic species and release of Fe2+ to solution where it becomes available for further reaction. ?? 1993.

Journal of Photochemistry and Photobiology A: Chem↗

USGS2009

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.

Book chapter↗

USGS2013

Interactions among hydrogeomorphology, vegetation, and nutrient biogeochemistry in floodplain ecosystems

Hydrogeomorphic, vegetative, and biogeochemical processes interact in floodplains resulting in great complexity that provides opportunities to better understand linkages among physical and biological processes in ecosystems. Floodplains and their associated river systems are structured by four dimensional gradients of hydrogeomorphology: longitudinal, lateral, vertical, and temporal components. These four dimensions create dynamic hydrologic and geomorphologic mosaics that have a large imprint on the vegetation and nutrient biogeochemistry of floodplains. Plant physiology, population dynamics, community structure, and productivity are all very responsive to floodplain hydrogeomorphology. The strength of this relationship between vegetation and hydrogeomorphology is evident in the use of vegetation as an indicator of hydrogeomorphic processes. However, vegetation also influences hydrogeomorphology by modifying hydraulics and sediment entrainment and deposition that typically stabilize geomorphic patterns. Nitrogen and phosphorus biogeochemistry commonly influence plant productivity and community composition, although productivity is not limited by nutrient availability in all floodplains. Conversely, vegetation influences nutrient biogeochemistry through direct uptake and storage as well as production of organic matter that regulates microbial biogeochemical processes. The biogeochemistries of nitrogen and phosphorus cycling are very sensitive to spatial and temporal variation in hydrogeomorphology, in particular floodplain wetness and sedimentation. The least studied interaction is the direct effect of biogeochemistry on hydrogeomorphology, but the control of nutrient availability over organic matter decomposition and thus soil permeability and elevation is likely important. Biogeochemistry also has the more documented but indirect control of hydrogeomorphology through regulation of plant biomass. In summary, the defining characteristics of floodplain ecosystems are determined by the many interactions among physical and biological processes. Conservation and restoration of the valuable ecosystem services that floodplains provide depends on improved understanding and predictive models of interactive system controls and behavior.

Book chapter↗

USGS2014

1.13 – Emerging contaminants

Since the Industrial Revolution, a diversity of large-scale chemical innovations has impacted aquatic systems in urban environments. Beginning in the 1990s, there has been a growing scientific interest and public awareness of the effects of the chemicals used in domestic, commercial, industrial, and agricultural applications, referred to in this article as ‘emerging contaminants’ (ECs), on ecosystem and human health. The growing global population and its increasing demands on water supplies in conjunction with climate-induced changes in hydrologic regimes place stress on freshwater resources, resulting in a greater reliance on reuse of reclaimed municipal wastewater treatment plant (WWTP) effluents to meet human and environmental needs. WWTP effluents are a major source of ECs, and it is important to have an understanding of the chemical composition of the reclaimed water, because many ECs are biologically active and the effects of chronic exposure to low concentration complex mixtures are unknown. Several classes of ECs that have been shown to be widespread in the aquatic environment are discussed in this chapter, including surfactants, complexing agents, fragrances, antimicrobials, industrial chemicals, pharmaceuticals, natural and synthetic estrogens, and disinfection byproducts. All of these compounds are biologically active via a variety of modes of action, and can occur in aquatic systems at concentrations ranging from <0.001 to >100 μg l −1 .

Book chapter↗

USGS2005

Development of a solenoid pumped in situ zinc analyzer for environmental monitoring

A battery powered submersible chemical analyzer, the Zn-DigiScan (Zn Digital Submersible Chemical Analyzer), has been developed for near real-time, in situ monitoring of zinc in aquatic systems. Microprocessor controlled solenoid pumps propel sample and carrier through an anion exchange column to separate zinc from interferences, add colorimetric reagents, and propel the reaction complex through a simple photometric detector. The Zn-DigiScan is capable of self-calibration with periodic injections of standards and blanks. The detection limit with this approach was 30 μg L −1 . Precision was 5–10% relative standard deviation (R.S.D.) below 100 μg L −1 , improving to 1% R.S.D. at 1000 μg L −1 . The linear range extended from 30 to 3000 μg L −1 . In situ field results were in agreement with samples analyzed by inductively coupled plasma mass spectrometry (ICPMS). This pump technology is quite versatile and colorimetric methods with complex online manipulations such as column reduction, preconcentration, and dilution can be performed with the DigiScan. However, long-term field deployments in shallow high altitude streams were hampered by air bubble formation in the photometric detector.

Analytica Chimica Acta↗

USGS2009

Assessing the impact of land use change on hydrology by ensemble modelling (LUCHEM) II: Ensemble combinations and predictions

This paper reports on a project to compare predictions from a range of catchment models applied to a mesoscale river basin in central Germany and to assess various ensemble predictions of catchment streamflow. The models encompass a large range in inherent complexity and input requirements. In approximate order of decreasing complexity, they are DHSVM, MIKE-SHE, TOPLATS, WASIM-ETH, SWAT, PRMS, SLURP, HBV, LASCAM and IHACRES. The models are calibrated twice using different sets of input data. The two predictions from each model are then combined by simple averaging to produce a single-model ensemble. The 10 resulting single-model ensembles are combined in various ways to produce multi-model ensemble predictions. Both the single-model ensembles and the multi-model ensembles are shown to give predictions that are generally superior to those of their respective constituent models, both during a 7-year calibration period and a 9-year validation period. This occurs despite a considerable disparity in performance of the individual models. Even the weakest of models is shown to contribute useful information to the ensembles they are part of. The best model combination methods are a trimmed mean (constructed using the central four or six predictions each day) and a weighted mean ensemble (with weights calculated from calibration performance) that places relatively large weights on the better performing models. Conditional ensembles, in which separate model weights are used in different system states (e.g. summer and winter, high and low flows) generally yield little improvement over the weighted mean ensemble. However a conditional ensemble that discriminates between rising and receding flows shows moderate improvement. An analysis of ensemble predictions shows that the best ensembles are not necessarily those containing the best individual models. Conversely, it appears that some models that predict well individually do not necessarily combine well with other models in multi-model ensembles. The reasons behind these observations may relate to the effects of the weighting schemes, non-stationarity of the climate series and possible cross-correlations between models. Crown Copyright ?? 2008.

Advances in Water Resources↗

USGS2006

A review of isotopic composition as an indicator of the natural and anthropogenic behavior of mercury

There are seven stable isotopes of Hg that can be fractionated as a result of inorganic and organic interactions. Important inorganic reactions involve speciation changes resulting from variations in environmental redox conditions, and phase changes resulting from variations in temperature and/or atmospheric pressure. Important organic reactions include methylation and demethylation, reactions that are bacterially mediated, and complexing with organic anions in soils. The measurement of Hg isotopes by multi-collector-inductively coupled plasma-mass spectrometry (MC-ICP-MS) is now sufficiently precise and sensitive that it is potentially possible to develop the systematics of Hg isotopic fractionation. This provides an opportunity to evaluate the utility of Hg isotopes in identifying source processes, transport mechanisms, and sinks. New values are provided for, 201Hg/198Hg, 200Hg/198Hg, 199Hg/198Hg for three standard materials (IRMM-AE639, SRM 1641c, SRM 3133) that can be used to make inter-laboratory data comparisons, and these values are tabulated with published isotopic information. Overall, the isotopic data for these standards agree to approximately 0.2???. The paper reviews Hg isotope studies that deal with hydrothermal ore deposits, sediments, coal and organic complexing. ?? 2006 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

USGS2008

Dissolved and labile concentrations of Cd, Cu, Pb, and Zn in the South Fork Coeur d'Alene River, Idaho: Comparisons among chemical equilibrium models and implications for biotic ligand models

In order to evaluate thermodynamic speciation calculations inherent in biotic ligand models, the speciation of dissolved Cd, Cu, Pb, and Zn in aquatic systems influenced by historical mining activities is examined using equilibrium computer models and the diffusive gradients in thin films (DGT) technique. Several metal/organic-matter complexation models, including WHAM VI, NICA-Donnan, and Stockholm Humic model (SHM), are used in combination with inorganic speciation models to calculate the thermodynamic speciation of dissolved metals and concentrations of metal associated with biotic ligands (e.g., fish gills). Maximum dynamic metal concentrations, determined from total dissolved metal concentrations and thermodynamic speciation calculations, are compared with labile metal concentrations measured by DGT to assess which metal/organic-matter complexation model best describes metal speciation and, thereby, biotic ligand speciation, in the studied systems. Results indicate that the choice of model that defines metal/organic-matter interactions does not affect calculated concentrations of Cd and Zn associated with biotic ligands for geochemical conditions in the study area, whereas concentrations of Cu and Pb associated with biotic ligands depend on whether the speciation calculations use WHAM VI, NICA-Donnan, or SHM. Agreement between labile metal concentrations and dynamic metal concentrations occurs when WHAM VI is used to calculate Cu speciation and SHM is used to calculate Pb speciation. Additional work in systems that contain wide ranges in concentrations of multiple metals should incorporate analytical speciation methods, such as DGT, to constrain the speciation component of biotic ligand models.

Idaho↗

USGS2015

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↗

USGS2014

Assessing the solubility controls on vanadium in groundwater, northeastern San Joaquin Valley, CA

The solubility controls on vanadium (V) in groundwater were studied due to concerns over possible harmful health effects of ingesting V in drinking water. Vanadium concentrations in the northeastern San Joaquin Valley ranged from <3 μg/L to 70 μg/L with a median of 21 μg/L. Concentrations of V were highest in samples collected from oxic groundwater (49% > 25 μg/L) and lowest in samples collected from anoxic groundwater (70% < 0.8 μg/L). In oxic groundwater, speciation modeling (SM) using PHREEQC predicted that V exists primarily as the oxyanion H 2 VO 4 − . Adsorption/desorption reactions with mineral surfaces and associated oxide coatings were indicated as the primary solubility control of V 5+ oxyanions in groundwater. Environmental data showed that V concentrations in oxic groundwater generally increased with increasing groundwater pH. However, data from adsorption isotherm experiments indicated that small variations in pH (7.4–8.2) were not likely as an important a factor as the inherent adsorption capacity of oxide assemblages coating the surface of mineral grains. In suboxic groundwater, accurate SM modeling was difficult since Eh measurements of source water were not measured in this study. Vanadium concentrations in suboxic groundwater decreased with increasing pH indicating that V may exist as an oxycationic species [e.g. V(OH) 3 + ]. Vanadium may complex with dissolved inorganic and organic ligands under suboxic conditions, which could alter the adsorption behavior of V in groundwater. Speciation modeling did not predict the existence of V-inorganic ligand complexes and organic ligands were not collected as part of this study. More work is needed to determine processes governing V solubility under suboxic groundwater conditions. Under anoxic groundwater conditions, SM predicts that aqueous V exists as the uncharged V(OH) 3 molecule. However, exceedingly low V concentrations show that V is sparingly soluble in anoxic conditions. Results indicated that V may be precipitating as V 3+ - or mixed V 3+ /Fe 3+ -oxides in anoxic groundwater, which is consistent with results of a previous study. The fact that V appears insoluble in anoxic (Fe reducing) redox conditions indicates that the behavior of V is different than arsenic (As) in aquifer systems where the reductive dissolution of Fe-oxides with As adsorbed to the surface is a well-documented mechanism for increasing As concentrations in groundwater. This hypothesis is supported by the relation of V to As concentrations in oxic versus anoxic redox conditions. Sequential extraction procedures (SEP) applied to aquifer material showed that the greatest amount of V was recovered by the nitric acid (HNO 3 ) extract (37–71%), followed by the oxalate-ascorbic acid extract (19–60%) and the oxalate extract (3–14%). These results indicate that V was not associated with the solid phase as an easily exchangeable fraction. Although the total amount of V recovered was greatest for the HNO 3 extract that targets V adsorbed to sorption sites of crystalline Al, Fe and Mn oxides, the greatest V saturation of sorption sites appeared to occur on the amorphous and poorly crystalline oxide solid phases targeted by the oxalate and oxalate-ascorbic acid extracts respectively. Adsorption isotherm experiments showed no correlation between V sorption and any of the fractions identified by the SEP. This lack of correlation indicates the application of an SEP alone is not adequate to estimate the sorption characteristics of V in an aquifer system.

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