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Interactive PHREEQ-N-AMDTreat water-quality modeling tools to evaluate performance and design of treatment systems for acid mine drainage

The PHREEQ-N-AMDTreat aqueous geochemical modeling tools described herein simulate changes in pH and solute concentrations resulting from passive and active treatment of acidic or alkaline mine drainage (AMD). The “user-friendly” interactive tools, which are publicly available software, utilize PHREEQC equilibrium aqueous and surface speciation models and kinetics models for O 2 ingassing and CO 2 outgassing, iron and manganese oxidation and precipitation, limestone dissolution, and organic carbon oxidation combined with reduction of nitrate, sulfate, and ferric iron. Reactions with synthetic caustic chemicals (CaO, Ca(OH) 2 , NaOH, Na 2 CO 3 ) or oxidizing agents (H 2 O 2 ) also may be simulated separately or combined with sequential kinetic steps. A user interface facilitates input of water chemistry data for one or two (mixed) influent AMD solutions and adjustment of kinetic variables. Graphical and tabular output indicates the changes in pH, metals and other solute concentrations, total dissolved solids, and specific conductance of treated effluent plus the cumulative quantity of precipitated solids as a function of retention time or the amount of caustic agent added. By adjusting kinetic variables or chemical dosing, the effects of independent or sequential treatment steps that have different retention time (volume/flow rate), aeration rate, quantities of reactive solids, and temperature can be simulated for the specified influent quality. The size (land area) of a treatment system can then be estimated using reaction time estimates (volume for a corresponding treatment step is the product of reaction time and flow rate; area is volume divided by depth). Given the estimated system size, the AMDTreat cost-analysis model may be used to compute approximate costs for installation (capital) and annual operations and maintenance. Thus, various passive and/or active treatment strategies can be identified that could potentially achieve the desired effluent quality, but require different land area, equipment, and costs for construction and operation.

Applied Geochemistry↗

Leaching of trace elements from Pittsburgh coal mill rejects compared with coal combustion products from a coal-fired power plant in Ohio, USA

We investigated the leachability of elements from mill rejects from the high-sulfur, bituminous Upper Pennsylvanian Pittsburgh coal, using the synthetic groundwater leaching procedure (SGLP), long-term leaching (LTL), and the U.S. Environmental Protection Agency's (EPA's) toxicity characteristic leaching procedure (TCLP), and compared their leaching behavior with that of three coal combustion products (CCPs)—bottom ash, economizer fly ash , and fly ash—from the same coal. None of the environmentally hazardous Resource Conservation and Recovery Act of 1976 (RCRA) metals analyzed in the leachates from the mill rejects or the CCPs exceeded U.S. EPA toxicity characteristics (As, Ba, Cd, Cr, Hg, Pb, and Se). Most trace elements leached the least from mill rejects and bottom ash and leached the most from fly ash. The elements Ca, Co, Mg, Mn, and Sr, however, were more concentrated in mill reject leachates than CCP leachates. Most trace elements increased in concentration with increasing SGLP and LTL leaching duration, but As and V decreased in concentration with time in mill reject leachates, suggesting sorption or precipitation of these elements was occurring.

Ohio↗

SAR studies in the Yuma Desert, Arizona: Sand penetration, geology, and the detection of military ordnance debris

Synthetic Aperture Radar (SAR) images acquired over part of the Yuma Desert in southwestern Arizona demonstrate the ability of C-band (5.7-cm wavelength), L-band (24.5 cm), and P-band (68 cm) AIRSAR signals to backscatter from increasingly greater depths reaching several meters in blow sand and sandy alluvium. AIRSAR images obtained within the Barry M. Goldwater Bombing and Gunnery Range near Yuma, Arizona, show a total reversal of C- and P-band backscatter contrast (image tone) for three distinct geologic units. This phenomenon results from an increasingly greater depth of radar imaging with increasing radar wavelength. In the case of sandy- and small pebble-alluvium surfaces mantled by up to several meters of blow sand, backscatter increases directly with SAR wavelength as a result of volume scattering from a calcic soil horizon at shallow depth and by volume scattering from the root mounds of healthy desert vegetation that locally stabilize blow sand. AIRSAR images obtained within the military range are also shown to be useful for detecting metallic military ordnance debris that is located either at the surface or covered by tens of centimeters to several meters of blow sand. The degree of detectability of this ordnance increases with SAR wavelength and is clearly maximized on P-band images that are processed in the cross-polarized mode (HV). This effect is attributed to maximum signal penetration at P-band and the enhanced PHV image contrast between the radar-bright ordnance debris and the radar-dark sandy desert. This article focuses on the interpretation of high resolution AIRSAR images but also Compares these airborne SAR images with those acquired from spacecraft sensors such as ERS-SAR and Space Radar Laboratory (SIR-C/X-SAR).Synthetic Aperture Radar (SAR) images acquired over part of the Yuma Desert in southwestern Arizona demonstrate the ability of C-band (5.7-cm wavelength), L-band (24.5 cm), and P-band (68 cm) AIRSAR signals to backscatter from increasingly greater depths reaching several meters in blow sand and sandy alluvium. AIRSAR images obtained within the Barry M. Goldwater Bombing and Gunnery Range near Yuma, Arizona, show a total reversal of C- and P-band backscatter contrast (image tone) for three distinct geologic units. This phenomenon results from an increasingly greater depth of radar imaging with increasing radar wavelength. In the case of sandy- and small pebble-alluvium surfaces mantled by up to several meters of blow sand, backscatter increases directly with SAR wavelength as a result of volume scattering from a calcic soil horizon at shallow depth and by volume scattering from the root mounds of healthy desert vegetation that locally stabilize blow sand. AIRSAR images obtained within the military range are also shown to be useful for detecting metallic military ordnance debris that is located either at the surface or covered by tens of centimeters to several meters of blow sand. The degree of detectability of this ordnance increases with SAR wavelength and is clearly maximized on P-band images that are processed in the cross-polarized mode (HV). This effect is attributed to maximum signal penetration at P-band and the enhanced PHV image contrast between the radar-bright ordnance debris and the radar-dark sandy desert. This article focuses on the interpretation of high resolution AIRSAR images but also compares these airborne SAR images with those acquired from spacecraft sensors such as ERS-SAR and Space Radar Laboratory (SIR-C/X-SAR).

Remote Sensing of Environment↗

Development and evaluation of geochemical methods for the sourcing of archaeological maize

Strontium (Sr)-isotope values on bone from deer mice pairs from 12 field sites in the Chaco Canyon area, New Mexico, were compared with isotope values of synthetic soil waters from the same fields. The data indicate that mice obtain Sr from near-surface sources and that soil samples collected at depths ranging from 25 to 95 cm contain Sr that is more accessible to the deep roots of maize; thus, synthetic soil solutions provide better data for the sourcing of archaeological maize. However, the Sr-isotope composition of mice may be more valuable in sourcing archaeological remains of animals such as rabbit, turkey, and deer. In a separate study, five Native American maize (Zea mays L. ssp. mays) accessions grown out at New Mexico State University Agricultural Science Center, Farmington, New Mexico were used to determine if soil-water metal pairs partition systematically into cobs and kernels. The sampled maize included landraces from three Native American groups (Acoma, Hopi, Zuni) that still occupy the Four Corners area. Two cobs each were picked from 10 plants of each landrace. Partitioning of the Ba/Mn, Ba/Sr, Ca/Sr, and K/Rb metal pairs from the soil water to the cob appears to behave in a systematic fashion. In addition, 51 rare earth element (REE) pairs also appear to systematically partition from the soil water into cobs; however, the ratios of the REE dissolved in the soil waters are relatively invariant; therefore, the distribution coefficients that describe the partitioning of REE from the soil water to the cob may not apply to archeological cobs grown under chemically heterogeneous conditions. Partitioning of Ba/Rb, Ba/Sr, Mg/P, and Mn/P metal pairs from the soil water to kernels also behaves in a systematic fashion. Given that modern Native American landraces were grown under optimal environmental conditions that may not have been duplicated by prehistoric Native Americans, the distribution coefficients obtained in this study should be used with caution. ?? 2007 Elsevier Ltd. All rights reserved.

Journal of Archaeological Science↗

Predicting earthquakes by analyzing accelerating precursory seismic activity

During 11 sequences of earthquakes that in retrospect can be classed as foreshocks, the accelerating rate at which seismic moment is released follows, at least in part, a simple equation. This equation (1) is {Mathematical expression},where {Mathematical expression} is the cumulative sum until time, t, of the square roots of seismic moments of individual foreshocks computed from reported magnitudes;C and n are constants; and tfis a limiting time at which the rate of seismic moment accumulation becomes infinite. The possible time of a major foreshock or main shock, tf,is found by the best fit of equation (1), or its integral, to step-like plots of {Mathematical expression} versus time using successive estimates of tfin linearized regressions until the maximum coefficient of determination, r2,is obtained. Analyzed examples include sequences preceding earthquakes at Cremasta, Greece, 2/5/66; Haicheng, China 2/4/75; Oaxaca, Mexico, 11/29/78; Petatlan, Mexico, 3/14/79; and Central Chile, 3/3/85. In 29 estimates of main-shock time, made as the sequences developed, the errors in 20 were less than one-half and in 9 less than one tenth the time remaining between the time of the last data used and the main shock. Some precursory sequences, or parts of them, yield no solution. Two sequences appear to include in their first parts the aftershocks of a previous event; plots using the integral of equation (1) show that the sequences are easily separable into aftershock and foreshock segments. Synthetic seismic sequences of shocks at equal time intervals were constructed to follow equation (1), using four values of n. In each series the resulting distributions of magnitudes closely follow the linear Gutenberg-Richter relation log N=a-bM, and the product n times b for each series is the same constant. In various forms and for decades, equation (1) has been used successfully to predict failure times of stressed metals and ceramics, landslides in soil and rock slopes, and volcanic eruptions. Results of more recent experiments and theoretical studies on crack propagation, fault mechanics, and acoustic emission can be closely reproduced by equation (1). Rate-process theory and continuum damage mechanics offer leads toward understanding the physical processes. ?? 1989 Birkha??user Verlag.

Pure and Applied Geophysics PAGEOPH↗

Speciation Methods Used to Assess Potential Health Effects of Toxic Metals in Environmental Materials

Assessing potential exposures to toxic metals or metalloids such as arsenic and chromium in environmental materials is important in protecting public health. The chemical form of an element in, or released from, a material is also important, since some forms, such as Cr(VI), are more toxic than others, for example, Cr(III). We have used a variety of procedures to assess potential exposures to hexavalent chromium in ash and burned soils from October 2007 southern California wildfires. Synthetic lung-fluid and de-ionized water extractions simulate release in the lungs and potential environmental releases due to rainfall. Extracts were analyzed for specific chromium and arsenic species using HPLC-ICP-MS methodology. Results indicate that the highly oxidizing environment in wildfires promotes some chromium conversion to Cr(VI), and that the caustic alkalinity of ash enhances Cr(VI) release and stability in lung fluids and rainfall.

Open-File Report↗

Seismoelectric imaging of shallow targets

We have undertaken a series of controlled field experiments to develop seismoelectric experimental methods for near-surface applications and to improve our understanding of seismoelectric phenomena. In a set of off-line geometry surveys (source separated from the receiver line), we place seismic sources and electrode array receivers on opposite sides of a man-made target (two sand-filled trenches) to record separately two previously documented seismoelectric modes: (1) the electromagnetic interface response signal created at the target and (2) the coseismic electric fields located within a compressional seismic wave. With the seismic source point in the center of a linear electrode array, we identify the previously undocumented seismoelectric direct field, and the Lorentz field of the metal hammer plate moving in the earth's magnetic field. We place the seismic source in the center of a circular array of electrodes (radial and circumferential orientations) to analyze the source-related direct and Lorentz fields and to establish that these fields can be understood in terms of simple analytical models. Using an off-line geometry, we create a multifold, 2D image of our trenches as dipping layers, and we also produce a complementary synthetic image through numerical modeling. These images demonstrate that off-line geometry (e.g., crosswell) surveys offer a particularly promising application of the seismoelectric method because they effectively separate the interface response signal from the (generally much stronger) coseismic and source-related fields. ?? 2007 Society of Exploration Geophysicists.

Geophysics↗

Hydrothermal diamond-anvil cell: Application to studies of geologic fluids

The hydrothermal diamond-anvil cell (HDAC) was designed to simulate the geologic conditions of crustal processes in the presence of water or other fluids. The HDAC has been used to apply external pressure to both synthetic and natural fluid inclusions in quartz to minimize problems caused by stretching or decrepitation of inclusions during microthermometric analysis. When the HDAC is loaded with a fluid sample, it can be considered as a large synthetic fluid inclusion and therefore, can be used to study the PVTX properties as well as phase relations of the sample fluid. Because the HDAC has a wide measurement pressure-temperature range and also allows in-situ optical observations, it has been used to study critical phenomena of various chemical systems, such as the geologically important hydrous silicate melts. It is possible, when the HDAC is combined with synchrotron X-ray sources, to obtain basic information on speciation and structure of metal including rare-earth elements (REE) complexes in hydrothermal solutions as revealed by X-ray absorption fine structure (XAFS) spectra. Recent modifications of the HDAC minimize the loss of intensity of X-rays due to scattering and absorption by the diamonds. These modifications are especially important for studying elements with absorption edges below 10 keV and therefore particularly valuable for our understanding of transport and deposition of first-row transition elements and REE in hydrothermal environments.

Acta Petrologica Sinica↗

Behavioral, clinical, and pathological characterization of acid metalliferous water toxicity in mallards

From September to November 2000, United States Fish and Wildlife Service biologists investigated incidents involving 221 bird deaths at 3 mine sites located in New Mexico and Arizona. These bird deaths primarily involved passerine and waterfowl species and were assumed to be linked to consumption of acid metalliferous water (AMW). Because all of the carcasses were found in or near pregnant leach solution ponds, tailings ponds, and associated lakes or storm water retention basins, an acute-toxicity study was undertaken using a synthetic AMW (SAMW) formulation based on the contaminant profile of a representative pond believed to be responsible for avian mortalities. An acute oral-toxicity trial was performed with a mixed-sex group of mallards ( Anas platyrhynchos ). After a 24-h pretreatment food and water fast, gorge drinking was evident in both SAMW treatment and control groups, with water consumption rates greatest during the initial drinking periods. Seven of nine treated mallards were killed in extremis within 12 h after the initiation of dose. Total lethal doses of SAMW ranged from 69.8 to 270.1 mL/kg (mean ± SE 127.9 ± 27.1). Lethal doses of SAMW were consumed in as few as 20 to 40 min after first exposure. Clinical signs of SAMW toxicity included increased serum uric acid, aspartate aminotransferase, creatine kinase, potassium, and P levels. PCV values of SAMW-treated birds were also increased compared with control mallards. Histopathological lesions were observed in the esophagus, proventriculus, ventriculus, and duodenum of SAMW-treated mallards, with the most distinctive being erosion and ulceration of the kaolin of the ventriculus, ventricular hemorrhage and/or congestion, and duodenal hemorrhage. Clinical, pathological, and tissue-residue results from this study are consistent with literature documenting acute metal toxicosis, especially copper (Cu), in avian species and provide useful diagnostic profiles for AMW toxicity or mortality events. Blood and kidney Cu concentrations were 23- and 6-fold greater, respectively, in SAMW mortalities compared with controls, whereas Cu concentrations in liver were not nearly as increased, suggesting that blood and kidney concentrations may be more useful than liver concentrations for diagnosing Cu toxicosis in wild birds. Based on these findings and other reports of AMW toxicity events in wild birds, we conclude that AMW bodies pose a significant hazard to wildlife that come in contact with them.

New Mexico, Arizona↗

EPA method 1312 (synthetic precipitation leaching procedure); leachate chemistry data for solid mine waste composite samples from Silverton and Leadville, Colorado

The EPA Method 1312 Synthetic Precipitation Leaching Procedure (SPLP) leachate chemistry data for mine waste samples is presented. Four mine waste composite samples were collected from Silverton (YUK and MAY) and Leadville (SUN and VEN), Colorado and were extracted following the EPA Method 1312 procedure. Leachate pH values ranged from 2.68 to 3.37 and the samples were ranked by increasing pH: VEN < SUN < YUK < MAY. Specific conductivity values ranged from 203 µS to 1080 µS and the samples were ranked by increasing specific conductivity: MAY < YUK < SUN < VEN. For selected metal concentrations, no consistent pattern presented itself. MAY is the sample that typically has the lowest metal concentrations with the exception of nickel, zinc, and lead. The samples had SPLP leachate concentrations below the EPA Method 1311 Toxicity Characteristic Leaching Procedure (TCLP) regulatory levels.

Colorado↗

Environmental geochemistry of abandoned mercury mines in West-Central Nevada, USA

The Humboldt River is a closed basin and is the longest river in Nevada. Numerous abandoned Hg mines are located within the basin, and because Hg is a toxic heavy metal, the potential transport of Hg from these mines into surrounding ecosystems, including the Humboldt River, is of environmental concern Samples of ore, sediment, water, calcines (roasted ore), and leachates of the calcines were analyzed for Hg and other heavy metals to evaluate geochemical dispersion from the mines. Cinnabar-bearing ore samples collected from the mines contain highly elevated Hg concentrations, up to 6.9 %, whereas calcines collected from the mines contain up to 2000 mg Hg/kg. Stream-sediment samples collected within 1 km of the mines contain as much as 170 mg Hg/kg, but those collected distal from the mines (> 5 km) contain < 1 mg Hg/kg, indicating significant geochemical dispersion of Hg downstream from the mines. Sediment samples collected from the Humboldt River basin contain ??? 0.28 mg Hg/kg. Leachate samples of the calcines obtained by using a synthetic water leaching technique contain as much as 1500 ??g Hg/l, suggesting that some calcines contain soluble Hg compounds. However, much lower Hg concentrations were found in water samples collected from the Humboldt River system, and these were below the 0.012 ??g/l Hg standard used to protect against chronic effects to aquatic wildlife. Mercury transference from these mines to the Humboldt River basin is generally minor because the mines are typically > 8 km from the Humboldt River, and Hg is transported and diluted through a large volume of pediment before it reaches the Humboldt River. ?? 2002 Elsevier Science Ltd. All rights reserved.

Conference Paper↗

Zinc isotope and transition-element dynamics accompanying hydrozincite biomineralization in the Rio Naracauli, Sardinia, Italy

The Rio Naracauli in SW Sardinia drains part of the Ingurtosu Zn&ndash;Pb mining district, and contains extreme concentrations of dissolved Zn at near-neutral pH. In the upper reaches of the stream, pH, alkalinity and Zn concentrations are such that hydrozincite [Zn 5 (CO 3 ) 2 (OH) 6 ] precipitates in a biologically mediated process facilitated by a microalga ( Chlorella sp.) and a cyanobacterium ( Scytonema sp.). Values of &delta; 66 Zn in water and solid samples ranged from &minus; 0.35&permil; to + 0.5&permil; relative to the JMC 3-0749-Lyon standard, and closely follow a mass-dependent fractionation line. Two composite samples of sphalerite, the primary ore mineral in the Ingurtosu deposits, had an average &delta; 66 Zn of + 0.15&permil;, similar to sphalerite measured elsewhere in hydrothermal mineral deposits. Zinc isotope measurements of the stream water and the hydrozincite forming in the stream show a consistent preference for the heavy isotope, 66 Zn, in the hydrozincite relative to 64 Zn. Synthetic hydrozincites produced without added bacteria have &delta; 66 Zn identical to the dissolved Zn, thus suggesting a biologically mediated mineralization process in Rio Naracauli. The average fractionation, &Delta; hdz-water , is 0.35&permil;, the magnitude of which is consistent with other studies, and suggests an extracellular mechanism of the biomineralization process. Zinc concentration and dissolved &delta; 66 Zn steadily decrease in the reach of the stream where the biomineralization occurs. The biomineralization process also leads to the sequestration of Pb, Cu and Ni in the hydrozincite lattice, and the coeval precipitation of an amorphous CdCO 3 solid, prompting the suggestion that if optimized, the biomineralization process might represent a feasible passive remediation strategy for streams with high Zn and other metals, and with near-neutral pH.

Sardinia↗

Pallid sturgeon basin-wide contaminants assessment

Pallid sturgeon (Scaphirhynchus albus), listed as endangered in 1990 under the federal Endangered Species Act (United States Fish and Wildlife Service (USFWS), 1990), have declined due to habitat loss, commercial fishing, and hybridization. Pollution in the Missouri and Mississippi Rivers has to-date only received minor attention as a factor in the on-going decline of wild pallid sturgeon populations (Jacobson et al. 2016a; Bergman 2008). Pallid sturgeon experts and contaminant specialists conceived of the Pallid Sturgeon Basin-Wide Contaminants Assessment (Assessment) to identify potentially harmful contaminants (contaminants of concern), their distribution within pallid sturgeon habitat, and their effects on pallid sturgeon at the landscape level. Extant water quality and analytical chemistry data from samples of river water, sediment, and sturgeon tissues from past studies, assessments, or monitoring activities throughout the species’ range were used to establish a list of contaminants. The list includes: metal and non-metal elements, pesticides, organic industrial chemicals, hormones, nutrients, and other potential water quality contaminants. Environmental samples collected from January 1, 2001 through December 31, 2014, when available, were used for all evaluations. This report is effectively a screening level hazard assessment whereby contituents of concern that may pose a potential harm to pallid sturgeon have been identified. These constituents of concern warrant further examination to determine the level of risk they pose to pallid sturgeon. The Assessment process was one of comparing the existing environmental data for individual constituents to reference values for adverse effects on fish specifically or aquatic life generally. The product of the Assessment is a simplified summary that is geographically organized by pallid sturgeon management unit that generally categorizes each individual contaminant or water quality constituent according to operationally defined levels of concern. This hazard assessment identifies potential constituents of concern to pallid sturgeon and may support prioritization for future data collection and research to enable a quantitative risk assessment. Regional data density at spatial and temporal scales notwithstanding, the Assessment points to some generalities in contaminant concerns within and across management units. Metals but not pesticides are the predominant contaminant of concern in the Great Plains Management Unit (GPMU). In the Central Lowlands Management Unit (CLMU), selenium exceeds benchmark levels. Triazine herbicides are potentially of concern in all but the GPMU. Concentrations of legacy contaminants such as PCBs and DDT and its metabolites exceeded benchmarks in samples from the CLMU, Interior Highlands Mangement Unit (IHMU), and Coastal Plains Management Unit (CPMU), but local and national trends indicate environmental levels of these contaminants continue to decline. Observed concentrations of nutrients and indicators of nutrient pollution were above benchmark levels throughout the pallid sturgeon’s range; however, the significance for pallid sturgeon health specifically is unknown. Almost no information exists on contemporary contaminants of concern such as the natural and synthetic estrogens (estradiol, ethinyl estradiol, and estrone) or polybrominated diphenyls (PBDEs). There are considerable informational data gaps for contaminants throughout the species’ range. Water quality measurements were the most frequent data encountered whereas, sediment and tissue data were orders of magnitude less frequent. The paucity of sediment and tissue concentrations, particularly the latter, prevents any meaningful conclusions regarding adverse effects of these contaminants on the growth and reproduction of pallid sturgeon. However, the Assessment could form the basis for regional workshops with subject matter specialists to develop plans to evaluate the contaminants most likely to affect pallid sturgeon health.

Missouri River basin, Mississippi River basin↗

Persistence and potential effects of complex organic contaminant mixtures in wastewater-impacted streams

Natural and synthetic organic contaminants in municipal wastewater treatment plant (WWTP) effluents can cause ecosystem impacts, raising concerns about their persistence in receiving streams. In this study, Lagrangian sampling, in which the same approximate parcel of water is tracked as it moves downstream, was conducted at Boulder Creek, Colorado and Fourmile Creek, Iowa to determine in-stream transport and attenuation of organic contaminants discharged from two secondary WWTPs. Similar stream reaches were evaluated, and samples were collected at multiple sites during summer and spring hydrologic conditions. Travel times to the most downstream (7.4 km) site in Boulder Creek were 6.2 h during the summer and 9.3 h during the spring, and to the Fourmile Creek 8.4 km downstream site times were 18 and 8.8 h, respectively. Discharge was measured at each site, and integrated composite samples were collected and analyzed for >200 organic contaminants including metal complexing agents, nonionic surfactant degradates, personal care products, pharmaceuticals, steroidal hormones, and pesticides. The highest concentration (>100 μg L –1 ) compounds detected in both WWTP effluents were ethylenediaminetetraacetic acid and 4-nonylphenolethoxycarboxylate oligomers, both of which persisted for at least 7 km downstream from the WWTPs. Concentrations of pharmaceuticals were lower (<1 μg L –1 ), and several compounds, including carbamazepine and sulfamethoxazole, were detected throughout the study reaches. After accounting for in-stream dilution, a complex mixture of contaminants showed little attenuation and was persistent in the receiving streams at concentrations with potential ecosystem implications.

Colorado, Iowa↗

Zinc adsorption effects on arsenite oxidation kinetics at the birnessite-water interface

Arsenite is more toxic and mobile than As(V) in soil and sediment environments, and thus it is advantageous to explore factors that enhance oxidation of As(III) to As(V). Previous studies showed that manganese oxides, such as birnessite (??-MnO2), directly oxidized As(III). However, these studies did not explore the role that cation adsorption has on As(III) oxidation. Accordingly, the effects of adsorbed and nonadsorbed Zn on arsenite (As(III)) oxidation kinetics at the birnessite-water interface were investigated using batch adsorption experiments (0.1 g L-1; pH 4.5 and 6.0; I = 0.01 M NaCl). Divalent Zn adsorption on synthetic ??-MnO 2 in the absence of As(III) increased with increasing pH and caused positive shifts in electrophoretic mobility values at pH 4-6, indirectly suggesting inner-sphere Zn adsorption mechanisms. Arsenite was readily oxidized on birnessite in the absence of Zn. The initial As(III) oxidation rate constant decreased with increasing pH from 4.5 to 6.0 and initial As(III) concentrations from 100 to 300 ??M. Similar pH and initial As(III) concentration effects were observed in systems when Zn was present (i.e., presorbed Zn prior to As(III) addition and simultaneously added Zn-As(III) systems), but As(III) oxidation reactions were suppressed compared to the respective control systems. The suppression was more pronounced when Zn was presorbed on the ??-MnO 2 surfaces as opposed to added simultaneously with As(III). This study provides further understanding of As(III) oxidation reactions on manganese oxide surfaces under environmentally applicable conditions where metals compete for reactive sites.

Environmental Science & Technology↗

Geochemical characterization of slags, other mine waste, and their leachate from the Elizabeth and Ely Mines (Vermont), the Ducktown Mining District (Tennessee), and the Clayton Smelter Site (Idaho)

Waste-rock material produced at historic metal mines contains elevated concentrations of potentially toxic trace elements. Two types of mine waste were examined in this study: sintered waste rock and slag. The samples were collected from the Elizabeth and Ely mines in the Vermont copper belt (Besshi-type massive sulfide deposits), from the Copper Basin mining district near Ducktown, Tennessee (Besshi-type massive sulfide deposits), and from the Clayton silver mine in the Bayhorse mining district, Idaho (polymetallic vein and replacement deposits). The data in this report are presented as a compilation with minimal interpretation or discussion. A detailed discussion and interpretation of the slag data are presented in a companion paper. Data collected from sintered waste rock and slag include: (1) bulk rock chemistry, (2) mineralogy, (3) and the distribution of trace elements among phases for the slag samples. In addition, the reactivity of the waste material under surficial conditions was assessed by examining secondary minerals formed on slag and by laboratory leaching tests using deionized water and a synthetic solution approximating precipitation in the eastern United States.

Idaho, Tennessee, Vermont↗

Role of microbial iron reduction in the dissolution of iron hydroxysulfate minerals

Iron-hydroxysulfate minerals can be important hosts for metals such as lead, mercury, copper, zinc, silver, chromium, arsenic, and selenium and for radionuclides such as 226Ra. These mineral-bound contaminants are considered immobilized under oxic conditions. However, when anoxic conditions develop, the activities of sulfate- or iron-reducing bacteria could result in mineral dissolution, releasing these bound contaminants. Reduction of structural sulfate in the iron-hydroxysulfate mineral jarosite by sulfate-reducing bacteria has previously been demonstrated. The primary objective of this work was to evaluate the potential for anaerobic dissolution of the iron-hydroxysulfate minerals jarosite and schwertmannite at neutral PH by iron-reducing bacteria. Mineral dissolution was tested using a long-term cultivar, Geobacter metallireducens strain GS-15, and a fresh isolate Geobacter sp. strain ENN1, previously undescribed. ENN1 was isolated from the discharge site of Shadle Mine, in the southern anthracite coalfield of Pennsylvania, where schwertmannite was the predominant iron-hydroxysulfate mineral. When jarosite from Elizabeth Mine (Vermont) was provided as the sole terminal electron acceptor, resting cells of both G. metallireducens and ENN1 were able to reduce structural Fe(III), releasing Fe+2, SO4-2, and K+ ions. A lithified jarosite sample from Utah was more resistant to microbial attack, but slow release of Fe+2 was observed. Neither bacterium released Fe+2 from poorly crystalline synthetic schwertmannite. Our results indicate that exposure of jarosite to iron-reducing conditions at neutral pH is likely to promote the mobility of hazardous constituents and should therefore be considered in evaluating waste disposal and/or reclamation options involving jarosite-bearing materials.

Journal of Geophysical Research G: Biogeosciences↗

I. Thermal evolution of Ganymede and implications for surface features. II. Magnetohydrodynamic constraints on deep zonal flow in the giant planets. III. A fast finite-element algorithm for two-dimensional photoclinometry

The work is divided into three independent papers: PAPER I: Thermal evolution models are presented for Ganymede, assuming a mostly differentiated initial state of a water ocean overlying a rock layer. The only heat sources are assumed to be primordial heat (provided by accretion) and the long-lived radiogenic heat sources in the rock component. As Ganymede cools, the ocean thins, and two ice layers develop, one above composed of ice I, and the other below composed of high-pressure polymorphs of ice. Subsolidus convection proceeds separately in each ice layer, its transport of heat calculated using a simple parameterized convection scheme and the most recent data on ice rheology. The model requires that the average entropy of the deep ice layer exceed that of the ice I layer. If the residual ocean separating these layers becomes thin enough, then a Rayleigh-Taylor-like ("diapiric") instability may ensue, driven by the greater entropy of the deeper ice and merging the two ice mantles into a single convective layer. This instability is not predicted by linear analysis but occurs for plausible finite amplitude perturbations associated with large Rayleigh number convection. The resulting warm ice diapirs may lead to a dramatic "heat pulse" at the surface and to fracturing of the lithosphere, and may be directly or indirectly responsible for resurfacing and grooved terrain formation on Ganymede. The timing of this event depends rather sensitively on poorly known rheological parameters but could be consistent with chronologies deduced from estimated cratering rates. Irrespective of the occurrence or importance of the heat pulse, we find that lithospheric fracturing requires rapid stress loading (on a timescale ≾ 10 4 ) years). Such a timescale can be realized by warm ice diapirism, but not directly by gradual global expansion. In the absence of any quantitative and self-consistent model for the resurfacing of Ganymede by liquid water, we favor resurfacing by warm ice flows,which we demonstrate to be physically possible, a plausible consequence of our models, compatible with existing observations, and a hypothesis testable by Galileo. We discuss core formation as an alternative driver for resurfacing, and conclude that it is less attractive. We also consider anew the puzzle of why Callisto differs so greatly from Ganymede, offering several possible explanations. The models presented do not provide a compelling explanation for all aspects of Ganymedean geological evolution, since we have identified several potential problems, most notably the apparently extended period of grooved terrain formation (several hundred million years), which is difficult to reconcile with the heat pulse phenomenon. PAPER II: The observed zonal flows of the giant planets will, if they penetrate below the visible atmosphere, interact significantly with the planetary magnetic field outside the metalized core. The appropriate measure of this interaction is the Chandrasekhar number Q = ( H 2 )/(4πρνα 2 λ) (where H = radial component of the magnetic field, ν = eddy viscosity, λ = magnetic diffusivity, α -1 = lengthscale on which λ varies); at depths where Q ≳ 1 the velocity will be forced to oscillate on a small lengthscale or decay to zero. We estimate the conductivity due to semiconduction in H 2 (Jupiter, Saturn) and ionization in H 2 O (Uranus, Neptune) as a function of depth; the value λ ≃ 10 10 cm 2 s -1 needed for Q = 1 is readily obtained well outside the metallic core (where λ ≃ 10 2 cm 2 s -1 ). These assertions are quantified by a simple model of the equatorial zonal jet in which the flow is assumed uniform on cylinders concentric with the spin axis, and the viscous and magnetic torques on each cylinder are balanced. We solve this "Taylor constraint" simultaneously with the dynamo equation to obtain the velocity and magnetic field in the equatorial plane. With this model we reproduce the widely differing jet widths of Jupiter and Saturn (though not the flow at very high or low latitudes) using ν = 2500 cm 2 s -1 , consistent with the requirement that viscous dissipation not exceed the specific luminosity. A model Uranian jet consistent with the limited Voyager data can also be constructed, with appropriately smaller ν, but only if one assumes a two-layer interior. We tentatively predict a wide Neptunian jet. For Saturn (but not Jupiter or Uranus) the model has a large magnetic Reynolds number where Q = 1 and hence exhibits substantial axisymmetrization of the field in the equatorial plane . This effect may or may not persist at higher latitudes. The one-dimensional model presented is only a first step. Variation of the velocity and magnetic field parallel to the spin axis must be modeled in order to answer several important questions, including: 1) What is the behavior of flows at high latitudes, whose Taylor cylinders are interrupted by the region with Q ≳ 1? 2) To what extent is differential rotation in the envelope responsible for the spin-axisymmetry of Saturn's magnetic field? PAPER III: It is shown that the problem of two-dimensional photoclinometry (PC) -- the reconstruction of a surface z ( x , y ) from a brightness image B( x , y ) -- may be formulated in a natural way in terms of finite elements. The resulting system of equations is underdetermined as a consequence of the lack of boundary conditions for z , but a unique solution may be chosen by minimizing a function S expressing the "roughness" of the surface. An efficient PC algorithm based on this formulation is presented, requiring ~ 10.66 (four-byte) memory locations and ~10 4 floating multiplications/additions per pixel, and incorporating: 1) Minimization of the roughness by the penalty method, which yields the smallest set of equations. 2) Iterative solution of the nonlinear equations by Newton's method. 3) Solution of the linearized equations by an inner iterative cycle of successive over-relaxation, which takes advantage of the extreme sparseness of the system. 4) Multigridding, in which the solutions to the smaller problems obtained by reducing the resolution are used recursively to greatly speed convergence at the higher resolutions, and 5) A rapid noniterative initial estimate of z obtained by exploiting the special symmetry of the equations obtained in the first linearization. The algorithm is extensively demonstrated on 200 by 200 pixel synthetic "images" generated from digital topographic data for northern Utah over a range of phase angles. Rms error in the solution is ~ 22 m, out of ~ 660 m total relief. The error is dominated by "stripes" with the same azimuth as the light source, resulting from use of the roughness criterion in lieu of boundary conditions; the rms error along profiles parallel to the stripes is only ~ 2-8 m, depending on the phase angle. Satisfactory solutions are obtained even in the presence of quantization error, noise, and moderate blur in the image. Applications of the PC algorithm to both remote sensing and photomicrography are sketched; a photoclinometric map of a low-relief Precambrian era fossil is presented as an example of the latter. Prospects for dealing with photometrically inhomogeneous surfaces, and an extension of the method to the analysis of side-looking radar data ("radarclinometry") are also discussed.

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