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At least 91 records · Page 5Linked to original sources

Comparison of machine learning approaches used to identify the drivers of Bakken oil well productivity

Geologists and petroleum engineers have struggled to identify the mechanisms that drive productivity in horizontal hydraulically fractured oil wells. The machine learning algorithms of Random Forest (RF), gradient boosting trees (GBT) and extreme gradient boosting (XGBoost) were applied to a dataset containing 7311 horizontal hydraulically fractured wells drilled into the middle member of the Bakken Formation from 2010 through 2017. The initial goal is to use these data‐driven machine learning algorithms to identify the most important explanatory predictors of well productivity within nine subareas and the composite area. Predictor variables representing initial gas production, the initial 180‐day water cut, and vertical depth vary spatially and are identified with geologically favorable areas. Well‐completion predictors include the well lateral length, number of fracture stages, volume of proppant per stage, and the volume of injected fluids per stage. The performance of methods is compared based on a common test sample. The analysis then examines the comparative predictive performance of the three algorithms for 1330 wells that had initiated production after the initial 7311 well sample had been producing. The computations of predictor importance identified the initial 180‐day water cut and the 30‐day initial gas production predictors as having a dominant influence in most subareas and for the composite area. The relative importance of well completion predictor variables, that is, the number of fracture stages per well, volume of injected proppant per stage, volume of injected fluids per stage, and lateral length, varied considerably across the subareas. For the common test or holdout sample, the models calibrated with the XGBoost algorithm had superior predictive power. The predictive power of all the algorithms trained on the data from the original sample suffered some loss when tested with a sample of wells that had started production after the end of that period. Implications of the empirical findings and strategies to mitigate loss of predictive power are discussed in the concluding section.

Statistical Analysis and Data Mining

MODFLOW-2000, the U.S. Geological Survey Modular Ground-Water Model--Documentation of the SEAWAT-2000 Version with the Variable-Density Flow Process (VDF) and the Integrated MT3DMS Transport Process (IMT)

SEAWAT-2000 is the latest release of the SEAWAT computer program for simulation of three-dimensional, variable-density, transient ground-water flow in porous media. SEAWAT-2000 was designed by combining a modified version of MODFLOW-2000 and MT3DMS into a single computer program. The code was developed using the MODFLOW-2000 concept of a process, which is defined as ?part of the code that solves a fundamental equation by a specified numerical method.? SEAWAT-2000 contains all of the processes distributed with MODFLOW-2000 and also includes the Variable-Density Flow Process (as an alternative to the constant-density Ground-Water Flow Process) and the Integrated MT3DMS Transport Process. Processes may be active or inactive, depending on simulation objectives; however, not all processes are compatible. For example, the Sensitivity and Parameter Estimation Processes are not compatible with the Variable-Density Flow and Integrated MT3DMS Transport Processes. The SEAWAT-2000 computer code was tested with the common variable-density benchmark problems and also with problems representing evaporation from a salt lake and rotation of immiscible fluids.

Open-File Report

Modeling transport of nutrients & sediment loads into Lake Tahoe under climate change

The outputs from two General Circulation Models (GCMs) with two emissions scenarios were downscaled and bias-corrected to develop regional climate change projections for the Tahoe Basin. For one model—the Geophysical Fluid Dynamics Laboratory or GFDL model—the daily model results were used to drive a distributed hydrologic model. The watershed model used an energy balance approach for computing evapotranspiration and snowpack dynamics so that the processes remain a function of the climate change projections. For this study, all other aspects of the model (i.e. land use distribution, routing configuration, and parameterization) were held constant to isolate impacts of climate change projections. The results indicate that (1) precipitation falling as rain rather than snow will increase, starting at the current mean snowline, and moving towards higher elevations over time; (2) annual accumulated snowpack will be reduced; (3) snowpack accumulation will start later; and (4) snowmelt will start earlier in the year. Certain changes were masked (or counter-balanced) when summarized as basin-wide averages; however, spatial evaluation added notable resolution. While rainfall runoff increased at higher elevations, a drop in total precipitation volume decreased runoff and fine sediment load from the lower elevation meadow areas and also decreased baseflow and nitrogen loads basin-wide. This finding also highlights the important role that the meadow areas could play as high-flow buffers under climatic change. Because the watershed model accounts for elevation change and variable meteorological patterns, it provided a robust platform for evaluating the impacts of projected climate change on hydrology and water quality.

Nevada;California

GFDL's CM2 global coupled climate models. Part I: Formulation and simulation characteristics

The formulation and simulation characteristics of two new global coupled climate models developed at NOAA's Geophysical Fluid Dynamics Laboratory (GFDL) are described. The models were designed to simulate atmospheric and oceanic climate and variability from the diurnal time scale through multicentury climate change, given our computational constraints. In particular, an important goal was to use the same model for both experimental seasonal to interannual forecasting and the study of multicentury global climate change, and this goal has been achieved. Tw o versions of the coupled model are described, called CM2.0 and CM2.1. The versions differ primarily in the dynamical core used in the atmospheric component, along with the cloud tuning and some details of the land and ocean components. For both coupled models, the resolution of the land and atmospheric components is 2?? latitude ?? 2.5?? longitude; the atmospheric model has 24 vertical levels. The ocean resolution is 1?? in latitude and longitude, with meridional resolution equatorward of 30?? becoming progressively finer, such that the meridional resolution is 1/3?? at the equator. There are 50 vertical levels in the ocean, with 22 evenly spaced levels within the top 220 m. The ocean component has poles over North America and Eurasia to avoid polar filtering. Neither coupled model employs flux adjustments. The co ntrol simulations have stable, realistic climates when integrated over multiple centuries. Both models have simulations of ENSO that are substantially improved relative to previous GFDL coupled models. The CM2.0 model has been further evaluated as an ENSO forecast model and has good skill (CM2.1 has not been evaluated as an ENSO forecast model). Generally reduced temperature and salinity biases exist in CM2.1 relative to CM2.0. These reductions are associated with 1) improved simulations of surface wind stress in CM2.1 and associated changes in oceanic gyre circulations; 2) changes in cloud tuning and the land model, both of which act to increase the net surface shortwave radiation in CM2.1, thereby reducing an overall cold bias present in CM2.0; and 3) a reduction of ocean lateral viscosity in the extratropics in CM2.1, which reduces sea ice biases in the North Atlantic. Both models have be en used to conduct a suite of climate change simulations for the 2007 Intergovernmental Panel on Climate Change (IPCC) assessment report and are able to simulate the main features of the observed warming of the twentieth century. The climate sensitivities of the CM2.0 and CM2.1 models are 2.9 and 3.4 K, respectively. These sensitivities are defined by coupling the atmospheric components of CM2.0 and CM2.1 to a slab ocean model and allowing the model to come into equilibrium with a doubling of atmospheric CO2. The output from a suite of integrations conducted with these models is freely available online (see http://nomads.gfdl.noaa.gov/). ?? 2006 American Meteorological Society.

Journal of Climate

A two-phase debris-flow model that includes coupled evolution of volume fractions, granular dilatancy, and pore-fluid pressure

Pore-fluid pressure plays a crucial role in debris flows because it counteracts normal stresses at grain contacts and thereby reduces intergranular friction. Pore-pressure feedback accompanying debris deformation is particularly important during the onset of debrisflow motion, when it can dramatically influence the balance of forces governing downslope acceleration. We consider further effects of this feedback by formulating a new, depth-averaged mathematical model that simulates coupled evolution of granular dilatancy, solid and fluid volume fractions, pore-fluid pressure, and flow depth and velocity during all stages of debris-flow motion. To illustrate implications of the model, we use a finite-volume method to compute one-dimensional motion of a debris flow descending a rigid, uniformly inclined slope, and we compare model predictions with data obtained in large-scale experiments at the USGS debris-flow flume. Predictions for the first 1 s of motion show that increasing pore pressures (due to debris contraction) cause liquefaction that enhances flow acceleration. As acceleration continues, however, debris dilation causes dissipation of pore pressures, and this dissipation helps stabilize debris-flow motion. Our numerical predictions of this process match experimental data reasonably well, but predictions might be improved by accounting for the effects of grain-size segregation.

Conference Paper

The calculation of aquifer chemistry in hot-water geothermal systems

The temperature and chemical conditions (pH, gas pressure, and ion activities) in a geothermal aquifer supplying a producing bore can be calculated from the enthalpy of the total fluid (liquid + vapor) produced and chemical analyses of water and steam separated and collected at known pressures. Alternatively, if a single water phase exists in the aquifer, the complete analysis (including gases) of a sample collected from the aquifer by a downhole sampler is sufficient to determine the aquifer chemistry without a measured value of the enthalpy. The assumptions made are that the fluid is produced from a single aquifer and is homogeneous in enthalpy and chemical composition. These calculations of aquifer chemistry involving large amounts of ancillary information and many iterations require computer methods. A computer program in PL-1 to perform these calculations is available from the National Technical Information Service as document PB-219 376.

Journal of Research of the U.S. Geological Survey

Some morphometric properties of experimentally cratered surfaces

The temperature and chemical conditions (pH, gas pressure, and ion activities) in a geothermal aquifer supplying a producing bore can be calculated from the enthalpy of the total fluid (liquid + vapor) produced and chemical analyses of water and steam separated and collected at known pressures. Alternatively, if a single water phase exists in the aquifer, the complete analysis (including gases) of a sample collected from the aquifer by a downhole sampler is sufficient to determine the aquifer chemistry without a measured value of the enthalpy. The assumptions made are that the fluid is produced from a single aquifer and is homogeneous in enthalpy and chemical composition. These calculations of aquifer chemistry involving large amounts of ancillary information and many iterations require computer methods. A computer program in PL-1 to perform these calculations is available from the National Technical Information Service as document PB-219 376.

Journal of Research of the U.S. Geological Survey

Debris flows: Behavior and hazard assessment

Debris flows are water-laden masses of soil and fragmented rock that rush down mountainsides, funnel into stream channels, entrain objects in their paths, and form lobate deposits when they spill onto valley floors. Because they have volumetric sediment concentrations that exceed 40 percent, maximum speeds that surpass 10 m/s, and sizes that can range up to ~109 m3, debris flows can denude slopes, bury floodplains, and devastate people and property. Computational models can accurately represent the physics of debris-flow initiation, motion and deposition by simulating evolution of flow mass and momentum while accounting for interactions of debris' solid and fluid constituents. The use of physically based models for hazard forecasting can be limited by imprecise knowledge of initial and boundary conditions and material properties, however. Therefore, empirical methods continue to play an important role in debris-flow hazard assessment.

Geology Today

SEAWAT Version 4: A Computer Program for Simulation of Multi-Species Solute and Heat Transport

The SEAWAT program is a coupled version of MODFLOW and MT3DMS designed to simulate three-dimensional, variable-density, saturated ground-water flow. Flexible equations were added to the program to allow fluid density to be calculated as a function of one or more MT3DMS species. Fluid density may also be calculated as a function of fluid pressure. The effect of fluid viscosity variations on ground-water flow was included as an option. Fluid viscosity can be calculated as a function of one or more MT3DMS species, and the program includes additional functions for representing the dependence on temperature. Although MT3DMS and SEAWAT are not explicitly designed to simulate heat transport, temperature can be simulated as one of the species by entering appropriate transport coefficients. For example, the process of heat conduction is mathematically analogous to Fickian diffusion. Heat conduction can be represented in SEAWAT by assigning a thermal diffusivity for the temperature species (instead of a molecular diffusion coefficient for a solute species). Heat exchange with the solid matrix can be treated in a similar manner by using the mathematically equivalent process of solute sorption. By combining flexible equations for fluid density and viscosity with multi-species transport, SEAWAT Version 4 represents variable-density ground-water flow coupled with multi-species solute and heat transport. SEAWAT Version 4 is based on MODFLOW-2000 and MT3DMS and retains all of the functionality of SEAWAT-2000. SEAWAT Version 4 also supports new simulation options for coupling flow and transport, and for representing constant-head boundaries. In previous versions of SEAWAT, the flow equation was solved for every transport timestep, regardless of whether or not there was a large change in fluid density. A new option was implemented in SEAWAT Version 4 that allows users to control how often the flow field is updated. New options were also implemented for representing constant-head boundaries with the Time-Variant Constant-Head (CHD) Package. These options allow for increased flexibility when using CHD flow boundaries with the zero-dispersive flux solute boundaries implemented by MT3DMS at constant-head cells. This report contains revised input instructions for the MT3DMS Dispersion (DSP) Package, Variable-Density Flow (VDF) Package, Viscosity (VSC) Package, and CHD Package. The report concludes with seven cases of an example problem designed to highlight many of the new features.

Techniques and Methods

The peg claims spodumene pegmatites, Maine

The Peg Claims pegmatites are located southwest of Rockland in the towns of Warren and Cushing, Knox County, Maine . These pegmatites are representative of a group of zoned, granitic, lithium-bearing pegmatites in which spodumene is present nearly from wall to wall. The pegmatites are discordant, steeply dipping, tabular bodies in the Penobscot quartz-mica schist near the Waldoboro granite. A narrow quartz-tourmaline-muscovite-apatite aureole is commonly developed around each of the pegmatites and around inclusions of country rock in the pegmatites . The pegmatites are zoned, and each may be subdivided into: (1) a narrow quartz-muscovite border zone; (2) a narrow albite-quartz-muscovite wall zone; (3) and an albite-quartz- spodumene -perthite core that constitutes most of the pegmatite . Cross-cutting, fine-grained, quartz-albite- spodumene -muscovite lenses are found within pegmatite cores. The bulk mineralogy and variations in the mineralogy from zone to zone of the largest body (Dike 1) were determined by megascopic mineral point-counts. There is a decrease of albite, quartz, and muscovite and an increase of spodumene and perthite from the border and wall zones into the core. The alkali contents of Dike 1 and of each of its zones were determined by flame photometer and X-ray fluorescence analyses. The amount of Na20 decreases and the amounts of K 2 O, Li 2 0, Rb 2 0, and CS 2 O increase from the border and wall zones into the core. Estimated bulk compositions of Dike 1 and of each of its zones were computed. It is concluded that the distribution, structural features, bulk chemistry, and the mineralogical, chemical, and textural zoning of the pegmatites are consistent with development by fractional crystallization of a pegma-titic fluid in a restricted system.

Maine

A numerical solution for the diffusion equation in hydrogeologic systems

The documentation of a computer code for the numerical solution of the linear diffusion equation in one or two dimensions in Cartesian or cylindrical coordinates is presented. Applications of the program include molecular diffusion, heat conduction, and fluid flow in confined systems. The flow media may be anisotropic and heterogeneous. The model is formulated by replacing the continuous linear diffusion equation by discrete finite-difference approximations at each node in a block-centered grid. The resulting matrix equation is solved by the method of preconditioned conjugate gradients. The conjugate gradient method does not require the estimation of iteration parameters and is guaranteed convergent in the absence of rounding error. The matrixes are preconditioned to decrease the steps to convergence. The model allows the specification of any number of boundary conditions for any number of stress periods, and the output of a summary table for selected nodes showing flux and the concentration of the flux quantity for each time step. The model is written in a modular format for ease of modification. The model was verified by comparison of numerical and analytical solutions for cases of molecular diffusion, two-dimensional heat transfer, and axisymmetric radial saturated fluid flow. Application of the model to a hypothetical two-dimensional field situation of gas diffusion in the unsaturated zone is demonstrated. The input and output files are included as a check on program installation. The definition of variables, input requirements, flow chart, and program listing are included in the attachments. (USGS)

Water-Resources Investigations Report

Improving our understanding of hydraulic-electrical relations: A case study of the surficial aquifer in Emirate Abu Dhabi

Transmissivity is a bulk hydraulic property that can be correlated with bulk electrical properties of an aquifer. In aquifers that are electrically-resistive relative to adjacent layers in a horizontally stratified sequence, transmissivity has been shown to correlate with bulk transverse resistance. Conversely, in aquifers that are electrically-conductive relative to adjacent layers, transmissivity has been shown to correlate with bulk longitudinal conductance. In both cases, previous investigations have relied on small datasets (on average less than eight observations) that have yielded coefficients of determination (R 2 ) that are typically in the range of 0.6 to 0.7 to substantiate these relations. Compared to previous investigations, this paper explores hydraulic-electrical relations using a much larger dataset. Geophysical data collected from 26 boreholes in Emirate Abu Dhabi, United Arab Emirates, are used to correlate transmissivity modeled from neutron porosity logs to the bulk electrical properties of the surficial aquifer that are computed from deep-induction logs. Transmissivity is found to be highly correlated with longitudinal conductance. An R 2 value of 0.853 is obtained when electrical effects caused by variations in pore-fluid salinity are taken into consideration.

Conference Paper

Late-kinematic timing of orogenic gold deposits and significance for computer-based exploration techniques with emphasis on the Yilgarn Block, Western Australia

Orogenic gold deposits are a widespread coherent group of epigenetic ore deposits that are sited in accretionary or collisional orogens. They formed over a large crustal-depth range from deep-seated low-salinity H 2 O–CO 2 ±CH 4 ±N 2 ore fluids and with Au transported as thio-complexes. Regional structures provide the main control on deposit distribution. In many terranes, first-order faults or shear zones appear to have controlled regional fluid flow, with greatest ore-fluid fluxes in, and adjacent to, lower-order faults, shear zones and/or large folds. Highly competent and/or chemically reactive rocks are the most common hosts to the larger deposits. Focusing of supralithostatic ore fluids into dilatant zones appears to occur late during the evolutionary history of the host terranes, normally within D 3 or D 4 in a D 1 –D 4 deformation sequence. Reactivation of suitably oriented pre-existing structures during a change in far-field stress orientation is a factor common to many deposits, and repeated reactivation may account for multiple mineralization episodes in some larger deposits. Absolute robust ages of mineralization support their late-kinematic timing, and, in general, suggest that deposits formed diachronously towards the end of the 100 to 200 m.y. long evolutionary history of hosting orogens. For example, in the Yilgarn Block, a region specifically emphasised in this study, orogenic gold deposits formed in the time interval between 40 and 90 m.y., with most about 60 to 70 m.y., after the youngest widespread basic-ultrabasic volcanism and towards the end of felsic magmatism. The late timing of orogenic gold deposits is pivotal to geologically-based exploration methodologies. This is because the present structural geometries of: (i) the deposits, (ii) the hosting goldfields, and (iii) the enclosing terranes are all essentially similar to those during gold mineralization, at least in their relative position to each other. Thus, interpretation of geological maps and cross-sections and three-dimensional models can be used to accurately simulate the physical conditions that existed at the time of ore deposition. It is particularly significant that the deposits are commonly related to repetitive and predictable geometries, such as structural heterogeneities within or adjacent to first-order structures, around rigid granitoid bodies, or in specific “locked-up” fold-thrust structures. Importantly, the two giant greenstone-hosted goldfields, Kalgoorlie and Timmins, show a remarkably similar geometry at the regional scale. Computer-based stress mapping and GIS-based prospectivity mapping are two computer-based quantitative methodologies that can utilize and take advantage of the late timing aspect of this deposit type to provide important geological aids in exploration, both in broad regions and more localized goldfields. Both require an accurate and consistent solid geology map, stress mapping requires knowledge of the far-field stresses during mineralization, and the empirical prospectivity mapping requires data from a significant number of known deposits in the terrane. The Kalgoorlie Terrane, in the Yilgarn Block, meets these criteria, and illustrates the potential of these methodologies in the exploration for orogenic gold deposits. Low minimum stress anomalies, interpreted to represent dilational zones during gold-related deformation, coincide well with the positions of known goldfields rather than individual gold deposits in the terrane, and there are additional as-yet unexplained anomalies. The prospectivity analysis confirms that predictable and repetitive factors controlling the siting of deposits are: (i) proximity to, and orientation and curvature of, granitoid-greenstone contacts, (ii) proximity to segments of crustal faults which strike in a preferred direction, (iii) proximity to specific lithological contacts which have similar preferred strike, (iv) proximity to anticlinal structures, and (v) the presence of preferred reactive host rocks (e.g., dolerite). The prospectivity map defines a series of anomalous areas, which broadly conform to those of the stress map (>78% correspondence). The most prospective category on this map covers less than 0.3% of the greenstone belts and yet hosts 16% of the known deposits, which have produced>80% of known gold. Thus, it discriminates in favour of the larger economically more-attractive deposits in the terrane. The successful application of stress mapping and prospectivity mapping to geology-based exploration for orogenic gold deposits indicates that more quantitative analysis of geological map data is a profitable line of research. The computer-based nature of these methodologies is ideal for the production of an ultimate, integrated, deposit target map, which can be compared to other, more conventional, targeting parameters such as geophysical and geochemical anomalies. Such an integrated strategy appears the way forward in the increasingly difficult task of cost-effective global exploration for orogenic gold deposits in poorly exposed terranes.

Western Australia

Changes in porosity and organic matter phase distribution monitored by NMR relaxometry following hydrous pyrolysis under uniaxial confinement

Artificial maturation methods are used to induce changes in source rock thermal maturity without the uncertainties that arise when comparing natural samples from a particular basin that often represent different levels of maturation and different lithofacies. A novel uniaxial confinement clamp was used on Woodford Shale cores in hydrous pyrolysis experiments to limit sample expansion by simulating the effect of overburden present during thermal maturation in natural systems. These samples were then subjected to X-ray computed tomography (X-CT) imaging and low-field nuclear magnetic resonance (LF-NMR) relaxometry measurements. LF-NMR relaxometry is a noninvasive technique commonly used to measure porosity and pore-size distributions in fluid-filled porous media, but may also measure hydrogen present in hydrogen-bearing organic solids. Standard T 1 and T 2 relaxation distributions were determined and two dimensional T 1 -T 2 correlation measurements were performed on the Woodford Shale cores. The T 1 -T 2 correlations facilitate resolution of organic phases in the system. The changes observed in NMR-relaxation times correspond to bitumen and lighter hydrocarbon production that occur as source rock organic matter matures. The LF-NMR porosities of the core samples at maximum oil generation are significantly higher than porosities measured by other methods. This discrepancy likely arises from the measurement of highly viscous organic constituents in addition to fluid-filled porosity. An unconfined sample showed shorter relaxation times and lower porosity. This difference is attributed to the lack of fractures observed in the unconfined sample by X-CT.

Conference Paper

A new analysis of caldera unrest through the integration of geophysical data and FEM modeling: The Long Valley caldera case study

The Long Valley Caldera, located at the eastern edge of the Sierra Nevada range in California, has been in a state of unrest since the late 1970s. Seismic, gravity and geodetic data strongly suggest that the source of unrest is an intrusion beneath the caldera resurgent dome. However, it is not clear yet if the main contribution to the deformation comes from pulses of ascending high-pressure hydrothermal fluids or low viscosity magmatic melts. To characterize the nature of the intrusion, we developed a 3D finite element model which includes topography and crust heterogeneities. We first performed joint numerical inversions of uplift and Electronic Distance Measurement baseline length change data, collected during the period 1985–1999, to infer the deformation-source size, position, and overpressure. Successively, we used this information to refine the source overpressure estimation, compute the gravity potential and infer the intrusion density from the inversion of deformation and gravity data collected in 1982–1998. The deformation source is located beneath the resurgent dome, at a depth of 7.5 ± 0.5 km and a volume change of 0.21 ± 0.04 km 3 . We assumed a rhyolite compressibility of 0.026 ± 0.0011 GPa −1 (volume fraction of water between 0% and 30%) and estimated a reservoir compressibility of 0.147 ± 0.037 GPa −1 . We obtained a density of 1856 ± 72 kg/m 3 . This density is consistent with a rhyolite melt, with 20% to 30% of dissolved hydrothermal fluids.

California

Origin of the pulse-like signature of shallow long-period volcano seismicity

Short-duration, pulse-like long-period (LP) events are a characteristic type of seismicity accompanying eruptive activity at Mount Etna in Italy in 2004 and 2008 and at Turrialba Volcano in Costa Rica and Ubinas Volcano in Peru in 2009. We use the discrete wave number method to compute the free surface response in the near field of a rectangular tensile crack embedded in a homogeneous elastic half space and to gain insights into the origin of the LP pulses. Two source models are considered, including (1) a vertical fluid-driven crack and (2) a unilateral tensile rupture growing at a fixed sub-Rayleigh velocity with constant opening on a vertical crack. We apply cross correlation to the synthetics and data to demonstrate that a fluid-driven crack provides a natural explanation for these data with realistic source sizes and fluid properties. Our modeling points to shallow sources (<1 km depth), whose signatures are representative of the Rayleigh pulse sampled at epicentral distances >∼1 km. While a slow-rupture failure provides another potential model for these events, the synthetics and resulting fits to the data are not optimal in this model compared to a fluid-driven source. We infer that pulse-like LP signatures are parts of the continuum of responses produced by shallow fluid-driven sources in volcanoes.

Journal of Geophysical Research B: Solid Earth

Ground-water contamination by organic bases derived from coal-tar wastes

A fluid sample from a shallow aquifer contaminated by coal-tar wastes was analyzed for organic bases. The sample consisted of a mixture of aqueous and oily-tar phases. The phases were separated by centrifugation and filtration. Organic bases were isolated from each phase by pH adjustment and solvent extraction. Organic bases in the oily-tar phase were further purified by neutral-alumina, micro-column adsorption chromatography. Separation and identification of the organic bases in each phase were achieved by using capillary gas chromatography-mass spectrometry-computer (GC-MS-COM) and probe distillation-high resolution mass spectrometry (PD-HRMS) techniques. Organic bases present in the aqueous phase included primary aromatic amines (such as aniline, alkylated anilines, and naphthylamines) as well as azaarenes (such as alkylated pyridines, quinolines, acridine, and benzoquinolines). The oily-tar phase contained acridine, benzacridines, dibenzacridines, and numerous other azaarenes, the elemental compositions of which were determined by PD-HRMS. Azaarenes in the oily-tar phase, varying in size from 6 to 12 rings, are reported for the first time. The origin and environmental significance of these compounds are discussed.

Environmental Toxicology and Chemistry

Geochemical models of metasomatism in ultramafic systems: Serpentinization, rodingitization, and sea floor carbonate chimney precipitation

In a series of water-rock reaction simulations, we assess the processes of serpentinization of harzburgite and related calcium metasomatism resulting in rodingite-type alteration, and seafloor carbonate chimney precipitation. At temperatures from 25 to 300??C (P = 10 to 100 bar), using either fresh water or seawater, serpentinization simulations produce an assemblage commonly observed in natural systems, dominated by serpentine, magnetite, and brucite. The reacted waters in the simulations show similar trends in composition with decreasing water-rock ratios, becoming hyper-alkaline and strongly reducing, with increased dissolved calcium. At 25??C and w/r less than ???32, conditions are sufficiently reducing to yield H2 gas, nickel-iron alloy and native copper. Hyperalkalinity results from OH- production by olivine and pyroxene dissolution in the absence of counterbalancing OH- consumption by alteration mineral precipitation except at very high pH; at moderate pH there are no stable calcium minerals and only a small amount of chlorite forms, limited by aluminum, thus allowing Mg2+ and Ca2+ to accumulate in the aqueous phase in exchange for H+. The reducing conditions result from oxidation of ferrous iron in olivine and pyroxene to ferric iron in magnetite. Trace metals are computed to be nearly insoluble below 300??C, except for mercury, for which high pH stabilizes aqueous and gaseous Hg??. In serpentinization by seawater at 300??C, Ag, Au, Pd, and Pt may approach ore-forming concentrations in sulfide complexes. Simulated mixing of the fluid derived from serpentinization with cold seawater produces a mineral assemblage dominated by calcite, similar to recently discovered submarine, ultramafic rock-hosted, carbonate mineral deposits precipitating at hydrothermal vents. Simulated reaction of gabbroic or basaltic rocks with the hyperalkaline calcium- and aluminum-rich fluid produced during serpentinization at 300??C yields rodingite-type mineral assemblages, including grossular, clinozoisite, vesuvianite, prehnite, chlorite, and diopside. ?? 2004 Elsevier Ltd.

Geochimica et Cosmochimica Acta